CN1919942A

CN1919942A - Curable composition, ink composition, inkjet recording method

Info

Publication number: CN1919942A
Application number: CN 200610121635
Authority: CN
Inventors: 渡边孝太郎
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2005-08-23
Filing date: 2006-08-23
Publication date: 2007-02-28

Abstract

The present invention provides a curable composition comprising a compound having a single partial structure containing a 4- or more-membered cyclic ether represented by the following formula (I) and a partial structure represented by the following formula (II): wherein in formula (II), R 1 represents an alkylene group, a cycloalkylene group or an arylene group, and n represents an integer of 1 to 8.

Description

Curable compositions, ink composite and ink jet recording method

Technical field

The present invention relates to be advantageously used in the method for curable compositions, the ink composite that comprises this curable compositions that is advantageously used in ink-vapor recording, the ink jet recording method of ink composite, paint, tackiness agent etc., the printing material that uses this ink jet recording method manufacturing, the planographic printing plate that uses this ink composite acquisition and production planographic printing plate.The invention still further relates to novel oxetane compound.

Background technology

The cyclic ether compounds of known for example 3-or 4-person's ring shows high reactivity, and as the polymerisable compound that is included in the curable compositions, can use thermopolymerization to these compositions, for example make polymerization (for example referring to TOHKEMY (JP-A) 11-43540 and 11-60702) with light cationoid polymerisation or acid anhydrides.

Many oxetane compounds that can be used for the light cationoid polymerisation or use the thermopolymerization of acid anhydrides (for example referring to JP-A 2002-317139 number, JP-A 2005-2191 number and JP-A 2000-63371 number) have been reported so far.For example, JP-A discloses the oxetane compound of being represented by following structural formula ((methyl) acrylate of oxygen heterocyclic ring butane ring) for 2000-63371 number.

In addition, advised comprising activity (active) the energy-ray solidified jetted ink of epoxy compounds, the oxyethane ring of described epoxy compounds is connected to one another by the connection chain with branched structure.But the connection chain in the epoxy compounds (hydrophobic connection chain) causes the problem (for example referring to JP-A 2005-41892 number) of adhesivity reduction of printing ink and the recording medium of there.

Have manyly on the recording medium of for example paper, to form the image recording process of image, comprise xerox method, distillation or melting heat transfer method and ink ejecting method based on viewdata signal.In these methods, because ink ejecting method is by only ink-jet and directly form image on recording medium in required image-region, thereby use printing ink more efficiently, in the device of cheapness so it prints but favourable with lower running cost because of allowing.In addition, ink ejecting method also is low noise, is favourable as image recording process therefore.

Ink ejecting method not only allows to print on common paper, and can print on the recording medium that does not absorb water of for example plastic sheet and tinsel, quickens printing in the method and improves picture quality but press for recently.Ink-jet after drying and solidify the required time of ink droplet and have very big influence for the quality of printing efficiency and printed images.

In ink jet recording method, the recording method of using by radiation exposure solidified ink-jet recording ink is arranged.In the method, can be by improving printing efficiency and picture quality with radiation exposure curing ink droplet immediately or behind the ink-jet specified time.

If can improve this usefulness for example radiation exposure of UV-light and the sensitivity of solidified ink-jet recording ink, perhaps improve the efficient of actinic radiation-curable printing ink, can obtain many benefits so, for example reduction of the raising of ink-vapor recording efficient, power consumption, because load reduces the life-span of ray generator prolongs and prevented low molecular weight substance owing to solidify deficiency and evaporate.In addition, it is effectively that sensitivity improves for the intensity that increases the image that forms with ink jet recording method, and particularly when using this ink composite and prepare planographic printing plate, it causes the increase of image section hardness, thereby the increase printing durability.

Use is recently just causing people's attention by the ink ejecting method of the ink composite of the actinic radiation-curable of for example UV-light, because this ink composite is tasteless relatively and quick-drying, and allows record on the recording medium that absorbs a small amount of printing ink; And the ink composite at radical polymerization hardened ultraviolet light polymerization that is used for ink ejecting method (for example Japanese patent application is examined open (JP-A) 63-235382,3-216379 and 5-214280 number and Japanese Patent Application Publication (JP-B) 6-21256 and 6-62905 number) is disclosed.

In addition, for provide make image sensitivity and with the adhesivity of recording medium higher and even can ink bleed when the printing on being difficult to the carrier that writes down by ink jet recording method usually in the above yet, and stability is higher and do not have the little skin irritation or an ink-jet recording ink of sensitization, disclose and comprised polymerizable compound, particularly the composition of the acrylate of free redical polymerization and tinting material (for example JP-A 2003-192943 and 2003-192944 number).

The printing ink of these free redical polymerizations be excellent aspect curing speed and provide not can ink bleed image, but have the shortcoming that the adhesivity with recording medium reduces because of the volumetric shrinkage of setting up period.

Therefore, in order to improve the adhesivity with recording medium, advised the ink composite (for example JP-A is 9-183928 number) of the anti-cationically polymerizable that shrinks during ultraviolet light polymerization.But the printing ink of these cationically polymerizables has insufficient stability because of the reaction of the acid that wherein produces in time between the shelf lives, and this commercialization for these printing ink is maximum obstacle.In order to improve stability in storage, the compositions and methods of having advised adding basic cpd or add thermogenesis alkali (for example JP-A 2003-312121,2003-341217 and 2004-91558 number).But, use basic cpd to cause occurring new problem: because it has suppressed the function of the acid of exposure generation, so add the curing efficiency that basic cpd has reduced printing ink.

In addition, for example traditional curable compositions of above-mentioned printing ink causes the problem that curing reaction takes place inadvisablely when storing under hot environment.

At present as mentioned above, still there are not to be applied to UV cured printing ink composition, formation for the extremely sensitive film of radiation exposure and at excellent aspect the intensity and also heat-stable curable compositions.

Summary of the invention

The present invention makes considering under the above-mentioned situation.

The invention provides the curable compositions that solidifies extremely sensitively and form high-strength coating for radiation exposure.

The present invention also provides for radiation exposure solidifies extremely sensitively and can form high quality graphic, and with the ink composite of the adhesivity excellence of recording medium and the ink jet recording method that uses this ink composite.

The method that the present invention also provides printing material, planographic printing plate and use to produce planographic printing plate for extremely sensitive ground of radiation exposure solidified ink composite.

The present invention further provides new trimethylene oxide.

A first aspect of the present invention provides curable compositions, it comprises a kind of compound, and described compound has single 4 Yuans cyclic ethers or the part-structure of more Yuans cyclic ethers and the part-structure of being represented by following general formula (II) that comprises by following general formula (I) expression:

In general formula (II), R ¹Expression alkylidene group, ring alkylidene group (cycloalkylene group) or arylidene, and n represents 1 to 8 integer.

A second aspect of the present invention provides the ink composite that comprises according to curable compositions of the present invention.Ink composite of the present invention is applicable to ink-vapor recording.

A third aspect of the present invention provides a kind of ink jet recording method, and it comprises by ink jet recording device and spraying on recording medium according to ink composite of the present invention; Solidify the ink composite that sprays with the dynamic rays irradiation then.

A fourth aspect of the present invention provides the printing material by ink jet recording method record according to the present invention.

A fifth aspect of the present invention provides the method for producing planographic printing plate, and it comprises that injection is solidified the ink composite of injection to form hydrophobic image with the dynamic rays irradiation then according to ink composite of the present invention on carrier.

A sixth aspect of the present invention provides the planographic printing plate of being produced by the method for production planographic printing plate according to the present invention.

A seventh aspect of the present invention provides the compound of being represented by following logical formula V:

In logical formula V, R ^1AAnd R ^4AEach represents alkyl, cycloalkyl or aryl independently; R ^3AExpression alkylidene group, ring alkylidene group or arylidene; And n ^AThe integer of expression 1 to 8.

Can be according to curable compositions of the present invention as the ink composite of for example UV curing inks, paint, tackiness agent etc. and the optical mode prepared material, colour filter, CD etc. that are used for resist.

Particularly curable compositions can be advantageously used for inkjet ink composition, and the adhesivity that this ink composite according to the present invention solidifies, obtains high-quality image and itself and recording medium sensitively to the ray height of for example UV-light is excellent.Said composition also shows stability in storage.

In addition, when using ink jet recording method of the present invention, even when being ejected on the non-absorbent recording medium, ink composite also can solidify extremely sensitively, directly forms the high strength image area in the above based on numerical data.Therefore, can be used for preparation according to ink composite of the present invention and particularly have A2 paper or more large-area planographic printing plate, and the planographic printing plate that so obtains is being superior aspect the printing wearing quality.

Description of drawings

Fig. 1 is the compound 1 that obtains among the embodiment 8 of expression ¹The figure of H-NMR results of spectral measurements.

Fig. 2 is the compound (a-1) that obtains among the embodiment 9 of expression ¹The figure of H-NMR results of spectral measurements.

Embodiment

[curable compositions]

Curable compositions according to the present invention comprises a kind of compound, and this compound has and comprises the single 4 Yuans cyclic ethers or the part-structure of more Yuans cyclic ethers and by the part-structure (following at random be called " specific polymerizable compound ") of following general formula (II) expression by following general formula (I) expression.

In general formula (II), R ¹Expression alkylidene group, ring alkylidene group or arylidene, and n represents 1 to 8 integer.

Composition according to the present invention is by the radiation exposure cured compositions.

" ray " among the present invention is not particularly limited, thereby as long as it provides energy produce to cause material by irradiation to composition, and the example comprises ray widely, for example alpha-ray, gamma-rays, X ray, ultraviolet ray, visible light and electron beam.Wherein, from solidifying the utilizability of sensitivity and equipment, ultraviolet ray and electron beam are preferred, and ultraviolet ray is particularly preferred.Therefore, according to curable compositions of the present invention preferably by as the uviolizing of ray and cured compositions.

The ink composite of representing to comprise curable compositions according to the particularly preferred embodiment of curable compositions of the present invention.Hereinafter, will take ink composite (according to ink composite of the present invention), illustrate according to curable compositions of the present invention, but the present invention be not limited to this as an example.

(specific polymerizable compound)

The following describes according to specific polymerizable compound of the present invention.

Specific polymerizable compound is that single part-structure comprises by 4 Yuans cyclic ethers of following general formula (I) expression or more Yuans cyclic ethers (following at random be called " part-structure (I) ") and the part-structure compound by following general formula (II) expression (following at random be called " part-structure (II) ") in its molecular structure.

According to specific polymerizable compound of the present invention preferably by from aftermentioned by acid polymerization reaction that produces the acidic compound of radiation exposure and solidified compound.

4 Yuans cyclic ethers or more Yuans cyclic ethers of comprising in the part-structure (I) preferably have the cyclic ethers of 3-9 carbon atom, and are more preferably the cyclic ethers with 3-7 carbon atom.Specifically, from reactivity, 4 Yuans cyclic ethers or more Yuans cyclic ethers of comprising in the part-structure (I) preferably include following cyclic ethers especially.

Part-structure (I) if possible can have one or more substituting group, and substituent example comprises halogen atom, alkoxyl group, aryloxy, nitro and amino.

According to the present invention, in described specific polymerizable compound, comprise a part-structure (I).

In part-structure (II), R ¹Expression alkylidene group, ring alkylidene group or arylidene.

By R ¹The alkylidene group of expression comprises and has 2-12 the alkylidene group of (preferred 2-8 and more preferably 2-6) individual carbon atom.Specifically, alkylidene group comprises ethylidene, propylidene, isopropylidene, butylidene, pentylidene, inferior hexyl etc.

By R ¹The ring alkylidene group of expression comprises and has 4-12 the ring alkylidene group of (preferred 4-8 and more preferably 5-7) individual carbon atom.Specifically, the ring alkylidene group comprises from suberyl, cyclohexyl, cyclopentyl, bicyclic radicals and to eliminate a formed group of hydrogen atom etc.

By R ¹The arylidene of expression comprises and has 6-12 the arylidene of (preferred 6-12 and more preferably 6-8) individual carbon atom.Specifically, arylidene comprises from phenyl, xenyl, naphthyl or benzyl, preferably eliminates a formed group of hydrogen atom etc. from phenyl, benzyl.

When to introduce substituting group be possible, R ¹Can further be substituted.Substituent example comprises halogen atom, alkoxyl group, aryloxy, nitro and amino.But, R ¹Preferably do not have substituent alkylidene group, ring alkylidene group or arylidene.

Consider low viscosity and high susceptibility, n represents the integer from 1-8, preferably from the integer of 1-6, and more preferably from the integer of 2-4.

Part-structure (II) links to each other by the carbon atom of the cyclic ethers that comprises in the linking group of for example alkylidene group and the part-structure (I).Can comprise one or two or more a plurality of part-structure (II) in the specific polymerizable compound.

The particularly preferred embodiment of specific polymerizable compound is to comprise part-structure (I) and comprise the trimethylene oxide structure with 3 carbon atoms in specific polymerizable compound, and part-structure (II) has the alkyl of 1-4 carbon atom as R ¹, and n is the integer from 2-4.

Hereinafter, with the example of having listed according to specific polymerizable compound of the present invention [exemplary compounds (1) is to (18)], but the invention is not restricted to these examples.

To specify the method for producing specific polymerizable compound below.But the method for producing specific polymerizable compound is not limited to this.

For instance, can produce specific polymerizable compound by following production method.

(1) raw material

The raw material of specific polymerizable compound will be described below.

Any raw material can be with the raw material that acts on specific polymerizable compound, as long as they can produce oxetane compound according to Motoi method (Motoi etc., Bull.Chem.Soc.Jpn.61,1998) in dehydrochlorination reaction.Specifically, by the trimethylene oxide alkylol cpd of following general formula (III) expression and comprise halogen atom for example or the ether compound of representing by following general formula (IV) of the leavings group of sulfonate ester group between etherification reaction in can produce specific polymerizable compound.

In general formula (III), R ¹¹Expression alkyl, cycloalkyl or aryl; And R ¹²Expression alkylidene group, ring alkylidene group or arylidene.In general formula (IV), R ¹³Expression alkylidene group, ring alkylidene group or arylidene, and R ¹⁴Expression alkyl, cycloalkyl or aryl.N represents 1 to 8 integer.X represents the leavings group of halogen atom for example or sulfonate ester group.

Trimethylene oxide alkylol cpd by general formula (III) expression comprises 3-methyl-3-oxetane methanol, 3-methyl-3-trimethylene oxide ethanol, 3-methyl-3-trimethylene oxide propyl alcohol, 3-ethyl-3-oxetane methanol, 3-ethyl-3-trimethylene oxide ethanol, 3-ethyl-3-trimethylene oxide propyl alcohol, 3-propyl group-3-oxetane methanol, 3-propyl group-3-trimethylene oxide ethanol, 3-propyl group-3-trimethylene oxide propyl alcohol etc., and these compounds can use separately or being used in combination with two or more materials.

Ether compound by the leavings group with halogen atom for example or sulfonate ester group of general formula (IV) expression can be 2-chloroethyl ether for instance, 2-bromotrifluoromethane ether, 3-chloropropyl ether, 3-bromopropyl ether, 4-chlorobutyl ether, 4-brombutyl ether, 2-bromotrifluoromethane methyl ether, ethylene glycol 2-bromotrifluoromethane ether, two (2-chloroethyl) ether, two (2-bromotrifluoromethane) ether, two (3-chloropropyl) ether, two (3-bromopropyl) ether, two (4-chlorobutyl) ether, two (4-brombutyl) ether, two (2-bromotrifluoromethane) ether, 1, two (2-chloroethoxy) ethane of 2-, 1,2-ethylene dichloride etc., these compounds can use separately or being used in combination with two or more materials.

Be not particularly limited by the trimethylene oxide alkylol cpd of general formula (III) expression and reaction ratio by the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (IV) expression, but by the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (IV) expression with respect to 1 mole of consumption by the trimethylene oxide alkylol cpd of general formula (III) expression in the scope of 0.1-10 mole.By the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (IV) expression with respect to 1 mole of consumption by the ring-type epoxy alkylol cpd of general formula (III) expression more preferably in the scope of 0.3-3.0 mole.

(2) temperature of reaction

Temperature of reaction in specific polymerizable compound is produced will be described below.For example consider that the productive rate of specific polymerizable compound determines temperature of reaction, but it is preferably in 0-100 ℃ scope for instance.Be lower than the reactive violent violent reduction that reduces and may cause productive rate that 0 ℃ temperature of reaction causes reaction raw materials, cause restriction spendable organic solvent kind and be higher than 100 ℃ temperature of reaction.Therefore, the temperature of reaction during specific polymerizable compound is produced is more preferably in 10-90 ℃ scope, and more more preferably in 20-80 ℃ scope.

(3) reaction times

Reaction times in specific polymerizable compound is produced will be described below.Consider the productive rate of specific polymerizable compound and temperature of reaction determining the reaction times, but for instance when temperature of reaction is 0-100 ℃ its preferably in 10 minutes to 100 hours scope.Be shorter than the increase that reaction times of 10 minutes causes residual unreacting material amount, and the reaction times of being longer than 100 hours causes the reduction of productivity.Therefore, the reaction times during specific polymerizable compound is produced is more preferably in 30 minutes to 50 hours scope, and more more preferably in 1-10 hour scope.

(4) reaction environment (pH)

Reaction environment (pH) in specific polymerizable compound is produced will be described below.Consider the productive rate of specific polymerizable compound and other factors to determine reaction environment (pH value), still for instance its preferably in the scope of 5-14.Be lower than 5 pH value and may cause the increase of amount of by-products and the reduction of productive rate, and cause restriction raw materials used kind greater than 14 pH value.Therefore, the pH value during specific polymerizable compound is produced is more preferably in the scope of 6-14, and more more preferably in the scope of 7-14.In order in above-mentioned scope, to regulate the pH value, preferably add the alkali of sodium hydroxide for example or potassium hydroxide.

(5) phase-transfer catalyst

The phase-transfer catalyst that uses in specific polymerizable compound is produced will be described below.Preferred add be used for improving the trimethylene oxide alkylol cpd and have halogen atom for example or the ether compound of the leavings group of sulfonate ester group between reactive phase-transfer catalyst, for instance with respect to 100 its consumptions of weight part raw material gross weight in the scope of 0.1-30 weight part.The phase-transfer catalyst consumption that adds is lower than the violent reduction that 0.1 weight part can cause reactive violent reduction and productive rate in the raw material, and addition can cause the difficulty of purifying greater than 30 weight parts.Therefore, with respect to 100 weight part raw materials, the amount of the phase-transfer catalyst that adds during the specific polymerizable compound preparation is more preferably in the scope of 1.0-20.0 weight part, more more preferably in the scope of 2.0-10.0 weight part.

Phase-transfer catalyst is not particularly limited, but preferably quaternary ammonium salt, quaternary alkylphosphonium salt or their mixture for instance.Its concrete example comprise tetra-n-butyl ammonium bromide, 4 bromide, benzyltrimethylammonium bromide, cetyl trimethylammonium bromide, triethyl hexadecyl brometo de amonio, trioctylphosphine methyl brometo de amonio, first base three phenyl phosphonium bromides, triethyl n-Hexadecane base phosphonium bromide, 4-phenyl phosphonium bromide, four butyl phosphonium bromides etc. with and two or more mixture.

(6) organic solvent

The organic solvent that uses in specific polymerizable compound is produced will be described below.From productivity, organic solvent preferably raw material good solvent and under atmospheric pressure boiling point be 250 ℃ or lower.The example of organic solvent comprise hydrocarbon (for example hexane, heptane and octane), halohydrocarbon (for example methylene dichloride and chloroform), ether (for example diethyl ether, dibutyl ether, glycol dimethyl ether, tetrahydrofuran (THF) and diox), ketone (for example acetone, methylethylketone, mibk and pimelinketone), ester (for example ethyl acetate, butylacetate, pentyl acetate and gamma-butyrolactone), aromatic hydrocarbon (for example benzene, toluene and dimethylbenzene) with and two or more mixture.

Can from ¹H-NMR and IR spectrum confirm the structure by the specific polymerizable compound of aforementioned production method acquisition.

Based on the total solids level that constitutes according to curable compositions of the present invention, the content of specific polymerizable compound is preferably 1-90 weight %, more preferably 1-70 weight %, and more preferably 1-50 weight % again.

In above-mentioned specific polymerizable compound, the compound of being represented by following logical formula V is novel oxetane compound.

In logical formula V, by R ^1AOr R ^4AThe alkyl of expression comprises and has 1-10 the alkyl of (preferred 1-6 and more preferably 1-4) individual carbon atom.Specifically, this alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl etc.

In logical formula V, by R ^1AThe alkyl of expression is methyl, ethyl, propyl group or sec.-propyl preferably, and is more preferably methyl, ethyl or propyl group.

By R ^4AThe alkyl of expression is methyl, ethyl, propyl group or sec.-propyl preferably, and is more preferably methyl, ethyl or propyl group.

In logical formula V, by R ^1AOr R ^4AThe cycloalkyl of expression comprises and has 4-12 the cycloalkyl of (preferred 5-7 and more preferably 5-6) individual carbon atom.Specifically, this cycloalkyl comprises suberyl, cyclohexyl, cyclopentyl, bicyclic radicals etc.

By R ^1AThe cycloalkyl of expression is suberyl, cyclohexyl or cyclopentyl preferably, and is more preferably suberyl or cyclohexyl.

By R ^4AThe cycloalkyl of expression is suberyl, cyclohexyl or cyclopentyl preferably, and is more preferably suberyl or cyclohexyl.

By R ^1AOr R ^4AThe aryl of expression comprises and has 6-12 the aryl of (preferred 6-12 and more preferably 6-8) individual carbon atom.Specifically, this aryl comprises phenyl, xenyl, naphthyl, benzyl etc.

By R ^1AThe aryl of expression is phenyl, xenyl, naphthyl or benzyl preferably, and is more preferably phenyl or benzyl.

By R ^4AThe aryl of expression is phenyl, xenyl, naphthyl or benzyl preferably, and is more preferably phenyl or benzyl.

By R ^3AThe alkylidene group of expression comprises and has 2-12 the alkylidene group of (preferred 2-8 and more preferably 2-6) individual carbon atom.Specifically, this alkylidene group comprises ethylidene, propylidene, isopropylidene, butylidene, pentylidene, hexylidene etc.

By R ^3AThe ring alkylidene group of expression comprises and has 4-12 the ring alkylidene group of (preferred 4-8 and more preferably 5-7) individual carbon atom.Specifically, the ring alkylidene group comprises from suberyl, cyclohexyl, cyclopentyl, bicyclic radicals and to eliminate a formed group of hydrogen atom etc.

By R ^3AThe arylidene of expression comprises and has 6-12 the arylidene of (preferred 6-12 and more preferably 6-8) individual carbon atom.Specifically, arylidene comprises from phenyl, xenyl, naphthyl or benzyl, preferably eliminates a formed group of hydrogen atom etc. from phenyl, benzyl.

When to introduce substituting group be possible, R ^1A, R ^3AAnd R ^4ACan further be substituted.Substituent example comprises halogen atom, alkoxyl group, aryloxy, nitro, amino etc.

The preferred embodiment of the compound of being represented by logical formula V is R wherein ^1ABe alkyl, R with 1-4 carbon atom ^3ABe to have the alkylidene group of 1-4 carbon atom and be R ^4AIt is compound with alkyl of 1-4 carbon atom.

n ^AExpression 1 to 8 integer, and preferably from the integer of 1-6 is more preferably from the integer of 2-4.At the compound of representing by logical formula V during as the polymerizable compound in the curable compositions, the n in logical formula V ^AWhen being 1 to 8 integer, can obtain to have the curable compositions of low viscosity and high susceptibility.

The specific examples of the compound of being represented by logical formula V is corresponding to above-mentioned (1) to (6), (13) and (14) of listing as the exemplary compounds of specific polymerizable compound, but never is confined to these concrete examples by leading to the compound that formula V represents.

(1) raw material

The raw material that below explanation is used for the oxetane compound represented by logical formula V.

Any raw material can be with the raw material that acts on the oxetane compound of being represented by logical formula V, as long as they can produce oxetane compound according to Motoi method (Motoi etc., Bull.Chem.Soc.Jpn.61,1998) in dehydrochlorination reaction.Specifically, by the trimethylene oxide alkylol cpd of following general formula (VI) expression and comprise halogen atom for example or the leavings group of sulfonate ester group by the etherification reaction between the ether compound of following general formula (VII) expression in can produce by leading to the oxetane compound that formula V is represented.

In general formula (VI), R ^1AExpression alkyl, cycloalkyl or aryl.In general formula (VII), R ^3AExpression alkylidene group, ring alkylidene group or arylidene, and R ^4AExpression alkyl, cycloalkyl or aryl; n ^AThe integer of expression 1-8.X represents the leavings group of halogen atom for example or sulfonate ester group.

Specific examples by the trimethylene oxide alkylol cpd of general formula (VI) expression comprises 3-methyl-3-oxetane methanol, 3-ethyl-3-oxetane methanol, 3-propyl group-3-oxetane methanol etc., and these compounds can use separately or being used in combination with two or more materials.

Specific examples by the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (VII) expression comprises 2-chloroethyl ether, 2-bromotrifluoromethane ether, 3-chloropropyl ether, 3-bromopropyl ether, 4-chlorobutyl ether, 4-brombutyl ether, 2-bromotrifluoromethane methyl ether, ethylene glycol 2-bromotrifluoromethane ether, Diethylene Glycol ethyltoluene sulfonyl ether etc., and these compounds can use separately or being used in combination with two or more materials.

Be not particularly limited by the trimethylene oxide alkylol cpd of general formula (VI) expression and reaction ratio by the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (VII) expression, but by the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (VII) expression with respect to 1 mole of consumption by the trimethylene oxide alkylol cpd of general formula (VI) expression in the scope of 0.1-10 mole.By the ether compound of the leavings group with halogen atom for example or sulfonate ester group of general formula (VII) expression with respect to 1 mole of consumption by the ring-type epoxy alkylol cpd of general formula (VI) expression more preferably in the scope of 0.3-3.0 mole.

(2) temperature of reaction

Temperature of reaction in the oxetane compound of being represented by logical formula V is produced will be described below.For example consider that the productive rate of this oxetane compound determines temperature of reaction, but it is preferably in 0-100 ℃ scope for instance.Be lower than the reactive violent violent reduction that reduces and may cause productive rate that 0 ℃ temperature of reaction causes reaction raw materials, cause restriction spendable organic solvent kind and be higher than 100 ℃ temperature of reaction.Therefore, the temperature of reaction during oxetane compound is produced is more preferably in 10-90 ℃ scope, and more more preferably in 20-80 ℃ scope.

(3) reaction times

Reaction times in the oxetane compound of being represented by logical formula V is produced will be described below.Consider the productive rate of oxetane compound and temperature of reaction determining the reaction times, but for instance when temperature of reaction is 0-100 ℃ its preferably in 10 minutes to 100 hours scope.Be shorter than the increase that reaction times of 10 minutes causes residual unreacting material amount, and the reaction times of being longer than 100 hours causes the reduction of productivity.Therefore, the reaction times during oxetane compound is produced is more preferably in 30 minutes to 50 hours scope, and more more preferably in 1-10 hour scope.

(4) reaction environment (pH)

Reaction environment (pH) in the oxetane compound of being represented by logical formula V is produced will be described below.The productive rate of consideration oxetane compound and other factors are with definite reaction environment (pH value), but it is preferably in the scope of 5-14 for instance.Be lower than 5 pH value and may cause the increase of amount of by-products and the reduction of productive rate, and cause restriction raw materials used kind greater than 14 pH value.Therefore, the pH value during oxetane compound is produced is more preferably in the scope of 6-14, and more more preferably in the scope of 7-14.In order to regulate the pH value in above-mentioned scope, preferably add the alkali of sodium hydroxide for example or potassium hydroxide.

(5) phase-transfer catalyst

The phase-transfer catalyst that uses in the oxetane compound of being represented by logical formula V is produced will be described below.Preferred add be used for improving the trimethylene oxide alkylol cpd and have halogen atom for example or the ether compound of the leavings group of sulfonate ester group between reactive phase-transfer catalyst, for instance with respect to 100 its consumptions of weight part raw material gross weight in the scope of 0.1-30 weight part.The phase-transfer catalyst consumption that adds is lower than the violent reduction that 0.1 weight part can cause reactive violent reduction and productive rate in the raw material, and addition can cause the difficulty of purifying greater than 30 weight parts.Therefore, with respect to 100 weight part raw materials, the amount of the phase-transfer catalyst that adds during the oxetane compound preparation is more preferably in the scope of 1.0-20.0 weight part, more more preferably in the scope of 2.0-10.0 weight part.

(6) organic solvent

The organic solvent that uses in the oxetane compound of being represented by logical formula V is produced will be described below.From productivity, organic solvent preferably the good solvent of raw material and its under atmospheric pressure boiling point be 250 ℃ or lower.The example of organic solvent comprise hydrocarbon (for example hexane, heptane and octane), halohydrocarbon (for example methylene dichloride and chloroform), ether (for example diethyl ether, dibutyl ether, glycol dimethyl ether, tetrahydrofuran (THF) and diox), ketone (for example acetone, methylethylketone, mibk and pimelinketone), ester (for example ethyl acetate, butylacetate, pentyl acetate and gamma-butyrolactone), aromatic hydrocarbon (for example benzene, toluene and dimethylbenzene) with and two or more mixture.

Can from ¹H-NMR and IR spectrum confirm the structure by the novel oxetane compound of aforementioned production method acquisition.

Except described specific polymerizable compound, can also in the scope that can not damage advantageous effect of the present invention, comprise other polymerisable compound (cationically polymerizable compound) as described below according to curable compositions of the present invention.

In the present invention, in following specific polymerizable compound, do not comprise being selected from least a compound in epoxy compounds and the oxetane compound, thus and other polymerizable compound that preferably uses the Vinyl Ether compound to shrink as composition with specific polymerizable compound combination effectively reduction setting up period.

(other polymerizable compound)

Other cationically polymerizable compound that uses among the present invention is not particularly limited, as long as it is following by from by acid polymerization reaction that produces the acidic compound of radiation exposure and solidified compound, and can use be called in the monomeric various cationically polymerizable monomers of light cationoid polymerisation one of any.That the monomeric example of cationically polymerizable comprises is that epoxy compounds, Vinyl Ether compound and other are described in JP-A 6-9714,2001-31892,2001-40068,2001-55507,2001-310938,2001-310937 and 2001-220526 number and other patent etc., be not included in the oxetane compound in the specific polymerizable compound of the present invention.

Epoxy compounds comprises aromatic epoxide, cycloaliphatic epoxides, aromatic epoxide etc.

For instance, the aromatic oxygenation thing is two or the polyglycidyl ether for preparing in the reaction of the polyphenol with at least one aromatic nucleus or its oxirane (alkyleneoxide) adducts and Epicholorohydrin, and the example comprises two or the polyglycidyl ether etc. of two or polyglycidyl ether, Hydrogenated Bisphenol A or its oxirane adducts of dihydroxyphenyl propane or its oxirane adducts.Oxirane is oxyethane, propylene oxide etc.

Cycloaliphatic epoxides preferably comprises for instance by the oxygenant epoxidation with hydrogen peroxide for example or peracid and has the epoxy cyclohexane that the compound (for example tetrahydrobenzene or cyclopentenes) of at least one naphthenic ring obtains or the compound of cyclopentane epoxide.

The example of aliphatic epoxide comprises two or polyglycidyl ether of aliphatic polyol or its oxirane adducts, and its typical example comprises alkylene glycol diglycidylether (ethylene glycol diglycidylether for example, propylene glycol diglycidylether and 1, the 6-hexanediol diglycidyl ether), polyvalent alcohol polyglycidyl ether (for example two or triglycidyl ether of glycerine or its oxirane adducts), polyalkylene glycol diglycidylether (for example diglycidylether of the diglycidylether of polyoxyethylene glycol or its oxirane adducts and polypropylene glycol or its oxirane adducts) or the like.Described oxirane is oxyethane, propylene oxide etc.

Below detailed description is used for simple function group of the present invention or multi-group epoxy compound.

The example of functional group's epoxy compounds comprises phenyl glycidyl ether, to tert-butyl-phenyl glycidyl ether, butylglycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl allyl ether, 1,2-butylene oxide ring, 1,3-divinyl list oxirane (1,3-butadienemonooxide), 1,2-epoxy dodecane, Epicholorohydrin, 1,2-epoxy decane, Styrene oxide 98min., epoxy cyclohexane, 3-methacryloxy methyl epoxy cyclohexane, 3-acryloyl-oxy ylmethyl epoxy cyclohexane, 3-ethene epoxy cyclohexane etc.

Multi-group epoxy compound's example comprises bisphenol A diglycidyl ether, the Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, brominated bisphenol A diglycidylether, brominated bisphenol F diglycidylether, brominated bisphenol S diglycidylether, epoxy-Novolak resin, the Hydrogenated Bisphenol A diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, A Hydrogenated Bisphenol A S diglycidylether, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy)-hexanaphthene--diox, two (3,4-epoxycyclohexyl methyl) adipic acid ester, vinyl epoxy cyclohexane, 4 vinyl epoxy cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-epoxy-6 '-methylcyclohexanecarboxylic acid ester, methylene radical-two (3, the 4-epoxy cyclohexane), the Dicyclopentadiene (DCPD) diepoxide, ethylene glycol bis (3,4-epoxycyclohexyl methyl) ether, ethylenebis (3, the 4-epoxycyclohexane carboxylate), phthalic acid epoxy six hydrogen dioctyl esters, phthalic acid epoxy six hydrogen two-2-ethylhexyl, 1, the 4-butanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, 1,1,3-14 carbon diene diepoxides, the limonene diepoxide, 1,2,7,8-diepoxy octane, 1,2,5,6-diepoxy cyclooctane etc.

In these epoxy compoundss, from curing speed, aromatic series and aliphatic epoxide are preferred, and aliphatic epoxide is particularly preferred.

The Vinyl Ether examples for compounds comprises two-or three-Vinyl Ether compound, for example ethylene glycol bisthioglycolate Vinyl Ether, Diethylene Glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butyleneglycol divinyl ether, hexylene glycol divinyl ether, cyclohexanedimethanol divinyl ether and trimethylolpropane tris Vinyl Ether; And single Vinyl Ether compound, for example ethyl vinyl ether, normal-butyl Vinyl Ether, isobutyl vinyl ether, octadecyl Vinyl Ether, cyclohexyl Vinyl Ether, hydroxybutyl Vinyl Ether, 2-ethylhexyl Vinyl Ether, cyclohexanedimethanol list Vinyl Ether, n-propyl Vinyl Ether, isopropyl-ethylene ether, isopropenyl ethers-O-propylene carbonate, dodecyl Vinyl Ether, Diethylene Glycol list Vinyl Ether and octadecyl Vinyl Ether etc.

Hereinafter, will describe simple function group and polyfunctional group Vinyl Ether in detail.

The example of simple function group Vinyl Ether comprises ethylene methacrylic ether, ethyl vinyl ether, propyl vinyl ether, the normal-butyl Vinyl Ether, tertiary butyl Vinyl Ether, 2-ethylhexyl Vinyl Ether, the n-nonyl Vinyl Ether, the lauryl Vinyl Ether, the cyclohexyl Vinyl Ether, the cyclohexyl methyl Vinyl Ether, 4-methylcyclohexyl ethylene methacrylic ether, benzyl ethylene ether, the dicyclopentenyl Vinyl Ether, 2-two cyclopentenes oxygen base ethyl vinyl ethers, the methoxy ethyl Vinyl Ether, the ethoxyethyl group Vinyl Ether, the butoxyethyl group Vinyl Ether, the methoxyethoxyethyl Vinyl Ether, the ethoxy ethoxy ethyl vinyl ether, the methoxy poly (ethylene glycol) Vinyl Ether, the tetrahydrofurfuryl Vinyl Ether, 2-hydroxyethyl Vinyl Ether, 2-hydroxypropyl Vinyl Ether, 4-hydroxyl butyl vinyl ether, 4-methylol cyclohexyl methyl Vinyl Ether, Diethylene Glycol list Vinyl Ether, the polyoxyethylene glycol Vinyl Ether, chloroethyl vinyl ether, the chlorobutyl Vinyl Ether, the chloroethoxy ethyl vinyl ether, the phenylethyl Vinyl Ether, phenoxy group polyoxyethylene glycol Vinyl Ether etc.

The example of polyfunctional group Vinyl Ether comprises divinyl ether, for example ethylene glycol bisthioglycolate Vinyl Ether, Diethylene Glycol divinyl ether, polyoxyethylene glycol divinyl ether, propylene glycol divinyl ether, butyleneglycol divinyl ether, hexylene glycol divinyl ether, bisphenol-A epoxy alkane divinyl ether and Bisphenol F oxirane divinyl ether; Polyfunctional group Vinyl Ether, for example trimethylolethane trimethacrylate Vinyl Ether, the trimethylolpropane tris Vinyl Ether, two TriMethylolPropane(TMP)s, four Vinyl Ethers, glycerine triethylene ether, tetramethylolmethane four Vinyl Ethers, Dipentaerythritol five Vinyl Ethers, Dipentaerythritol six Vinyl Ethers, the ethylene oxide adduct of trimethylolpropane tris Vinyl Ether, the propylene oxide adduct of trimethylolpropane tris Vinyl Ether, the ethylene oxide adduct of two TriMethylolPropane(TMP)s, four Vinyl Ethers, two TriMethylolPropane(TMP) tetrem alkene ether ring Ethylene Oxide adductss, the ethylene oxide adduct of tetramethylolmethane four Vinyl Ethers, the propylene oxide adduct of tetramethylolmethane four Vinyl Ethers, the propylene oxide adduct of the ethylene oxide adduct of Dipentaerythritol six Vinyl Ethers and Dipentaerythritol six Vinyl Ethers.

From curing efficiency, with the adhesivity of recording medium with form the surface hardness of image, two-or the triethylene ether compound be preferred as the Vinyl Ether compound, and the divinyl ether compound is particularly preferred.

Known any other oxetane compound, specifically for example the compound that does not have part-structure (II) described in JP-A 2001-220526,2001-310937 and 2003-341217 number when it is correct can be when selecting as other trimethylene oxide that is used in combination in the present invention.The compound of the oxygen heterocyclic ring butane ring that is used in combination with curable compositions according to the present invention preferably has a compound to four trimethylene oxide rings in structure.Use this compound can be more easily with the viscosity controller of ink composite in handling favourable scope, and for instance when it is used for ink composite, obtain after curing printing ink with the adhesivity excellence of recording medium.

The examples for compounds that has one or two trimethylene oxide ring among the present invention in the additional molecule that uses comprises by the compound of following general formula (1) to (3) expression etc.

R ^A1Expression hydrogen atom, alkyl, fluoro-alkyl, allyl group, aryl, furyl or thienyl with 1-6 carbon atom with 1-6 carbon atom.If two R are arranged in the molecule ^A1Group, they can be mutually the same or different.The example of alkyl comprises methyl, ethyl, propyl group and butyl etc., and the preferred embodiment of fluoro-alkyl replaces the alkyl of any or a plurality of hydrogen atoms with fluorine atom above comprising.

R ^A2The expression hydrogen atom, have 1-6 carbon atom alkyl, have 2-6 carbon atom thiazolinyl, have aromatic nucleus group, have 2-6 carbon atom alkyl-carbonyl, have the alkoxy carbonyl of 2-6 carbon atom or have the N-alkyl-carbamoyl of 2-6 carbon atom.The example of alkyl comprises methyl, ethyl, propyl group and butyl etc.; And the example of thiazolinyl comprises 1-propenyl, 2-propenyl, 2-methyl isophthalic acid-propenyl, 2-methyl-2-propenyl, 1-butylene base, crotyl and 3-butenyl etc.; And the examples of groups with aromatic nucleus comprises phenyl, benzyl, fluoro benzyl, methoxy-benzyl and phenoxy group ethyl etc.The example of alkyl-carbonyl comprises ethyl carbonyl, propyl group carbonyl and butyl carbonyl etc.; The example of alkoxy carbonyl comprises ethoxy carbonyl, propoxycarbonyl and butoxy carbonyl etc.; And the example of N-alkyl-carbamoyl comprises ethylamino formyl radical, propyl group formamyl, butyl formamyl and amyl group formamyl etc.In addition, R ^A2Can have substituting group, and substituent example comprises alkyl and the fluorine atom with 1-6 carbon atom.

R ^A3Expression straight or branched alkylidene group, straight or branched poly-(alkylene oxide) base, straight or branched unsaturated alkyl, carbonyl or contain carbonyl alkylidene group, carboxylic alkylidene group, contain formamyl alkylidene group or following shown in group.The example of alkylidene group comprises ethylidene, propylidene and butylidene etc.; And the example that poly-(alkylene oxide) base comprises comprises poly-(ethoxy) base and poly-(third oxygen) base etc.The example of unsaturated alkyl comprises propenylidene, methyl propenylidene and crotonylidene etc.

Work as R ^A3When being one of multivalence group, R ^A4Expression hydrogen atom, alkyl, alkoxyl group, halogen atom, nitro, cyano group, sulfydryl, low alkyl group carboxyl, carboxyl or formamyl with 1-4 carbon atom with 1-4 carbon atom.

R ^A5Expression oxygen or sulphur atom, methylene radical, NH, SO, SO ₂, C (CF ₃) ₂Or C (CH ₃) ₂R ^A6Expression has the alkyl or the expression aryl of 1-4 carbon atom; And n represents 0-2,000 integer.R ^A7Expression has alkyl, the aryl of 1-4 carbon atom or the monoradical with following structure.In the structure below, R ^A8Expression has the alkyl or aryl of 1-4 carbon atom, and m is the integer of 0-100.

Examples for compounds by general formula (1) expression comprises 3-ethyl-3-methylol trimethylene oxide (OXT-101: by Toagosei Co., Ltd. production), 3-ethyl-3-(2-ethyl hexyl oxy methyl) (OXT-212: by Toagosei Co., Ltd. produce) and 3-ethyl-3-phenoxymethyl trimethylene oxide (OXT-211: by Toagosei Co., Ltd. produces).Examples for compounds by general formula (2) expression comprises 1, and 4-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] benzene (OXT-121:Toagosei Co., Ltd.).In addition, by the examples for compounds of general formula (3) expression comprise two (3-ethyl-3-trimethylene oxide ylmethyl) ethers (OXT-221:Toagosei Co., Ltd.).

Examples for compounds with 3 or 4 trimethylene oxide rings comprises the compound of being represented by following general formula (4).

In general formula (4), R ^A1Identical with in the top general formula (1).Multivalence linking group R ^A9Example comprise branched alkylidene (for example group of representing by following group A-C) with 1-12 carbon atom, poly-(alkylene oxide) group (for example group of representing by following group D) of side chain and side chain polysiloxane group (for example group of representing by following group E) or the like.J is 3 or 4.

In group A, R ^A10Expression methyl, ethyl or propyl group.In group D, p is the integer of 1-10.

Other example of the preferred oxetane compound that uses in the present invention comprises the compound that has the trimethylene oxide ring on the side chain of being represented by following general formula (5).

In general formula (5), R ^A8With identical in the top general formula.R ^A11Expression has the alkyl of 1-4 carbon atom, for example methyl, ethyl, propyl group or butyl, and perhaps trialkylsilkl, and r is 1-4.

[0021] of top JP-A 2003-341217 number understands that in detail these have the compound of trimethylene oxide ring to [0084] section, and the described compound in there can be advantageously used in the present invention.

The oxetane compound of describing among JP-A 2004-91556 number also can be used for the present invention.Its [0022] to [0058] section in describe these compounds in detail.

Be used for oxetane compound of the present invention, from the viscosity and the binding property of ink composite, it is preferred using the compound with a trimethylene oxide ring.

When being used in combination specific polymerizable compound and another kind of cationically polymerizable compound in the present invention, this specific polymerizable compound is preferably 10: 1 to 10: 100 with the content ratio of another kind of cationically polymerizable compound, more preferably 10: 3 to 10: 80, and more preferably 10: 5 to 10: 60 again.

(the acidic compound of radiation exposure)

Preferably comprise by the acidic compound of radiation exposure (following be called arbitrarily " light acid producing agent ") according to curable compositions of the present invention.

In the present invention, the acid that is produced by radiation exposure causes the polyreaction and the curing of polymerizable compound.

Light cationoid polymerisation light trigger, optical free radical polymerization light initiator, the light discoloring agent is to tinting material, light alterant (photoalterant), perhaps ((wavelength is the UV-light of 400-200nm for example to be used for the light of little resist (microresists) by light, far ultraviolet rays yue, preferred especially g-ray, the h-ray, i-ray or KrF excimer laser beam), the ArF excimer laser beam, electron beam, the X-ray, molecule or ionic fluid etc.) the acidic compound of irradiation can be when suitably selecting with acting on according to the light acid producing agent in the ink composite of the present invention.

The example of light acid producing agent comprises salt compound, for example diazonium salt, microcosmic salt, sulfosalt and salt compounded of iodine and sulfonate compound, for example imino-sulfonate, oxime sulfonate, diazonium two sulfones (diazodisulfones), two sulfones (disulfones) and under radiation exposure, decompose and acidic adjacent nitrobenzyl sulfonate or the like.

Other example that shines acidic compound (light acid producing agent) by ray or other exciting light that uses among the present invention is included in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal etc., Polymer, 21,423 (1980) and other document in the diazonium salt described; At United States Patent (USP) the 4th, 069,055,4,069, No. 056 and Re27,992, JP-A 3-140, the ammonium salt of describing in No. 140 and other document; At D.C.Necker etc., Macromolecules, 17,2468 (1984), C.S.Wen etc., Teh.Proc.Conf.Rad.Curing ASIA, the 478th page, Tokyo, (in October, 1988), United States Patent (USP) the 4th, 069,055 and 4,069, the microcosmic salt of describing in No. 056 and other document; At J.V.Crivello etc., Macromolecules, 10 (6), 1307 (1977), Chem.﹠amp; Eng.News, the 28th volume, the 31st page, 1988), No. the 104th, 143,339,049 and 410,201, EP, JP-A 2-150,848 and 2-296, the salt compounded of iodine of describing in No. 514 and other document;

At J.V.Crivello etc., Polymer J.17,73 (1985), J.V.Crivello etc., J.Org.Chem., 43,3055 (1978), W.R.Watt etc., J.Polymer Sci., PolymerChem.Ed., 22,1789 (1984), J.V.Crivello etc., Polymer Bull., 14,279 (1985), J.V.Crivello etc., Macromolecules, 14 (5), 1141 (1981), J.V.Crivello etc., J.Polymer Sci., Polymer Chem.Ed., 17,2877 (1979), EP the 370th, 693,161,811,410,201,339,049,233,567,297,443 and 297, No. 442, United States Patent (USP) the 3rd, 902,114,4,933,377,4,760,013,4,734,444 and 2,833, No. 827, German Patent the 2nd, 904,626,3,604,580 and 3,604, No. 581, the sulfosalt of describing in JP-A 7-28237 and 8-27102 number and other document;

At J.V.Crivello etc., Macromolecules, 10 (6), 1307 (1977), J.V.Crivello etc., J.Polymersci., Polymer Chem.Ed., 17,1047 (1979) and other document in the selenium salt described; For example at C.S.Wen etc., Teh, Proc.Conf.Rad.Curing ASIA, the 478th page, Tokyo, the salt of for example arsenic salt of describing in (1988) and other document October; At United States Patent (USP) the 3rd, 905, the organic halogen compound of describing in No. 815, JP-B 46-4605, JP-A 48-36281,55-32070,60-239736,61-169835,61-169837,62-58241,62-212401,63-70243 and 63-298339 number and other document; At K.Meier etc., J.Rad.Curing, 13 (4), 26 (1986), T.P.Gill etc., Inorg.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.Res., 19 (12), 377 (1896), organo-metallic/Organohalogen compounds of describing in JP-A 2-161445 number and other document;

In S.Hayase etc., J.Polymer Sci., 25,753 (1987), E.Reichmanis etc., J.Polymer Sci., Polymer Chem.Ed., 23,1 (1985), Q.Q.Zhu etc., J.Photochem., 36,85,39,317 (1987), B.Amit etc., Tetrahedron Lett., (24) 2205 (1973), D.H.R.Barton etc., J.Chem Soc., 3571 (1965), P.M.Collins etc., J.Chem.Soc., Perkin I, 1695 (1975), M.Rudinstein etc., Tetrahedron Lett., (17), 1445 (1975), J.W, Walker etc., J.Am.Chem.Soc., 110,7170 (1988), S.C.Busman etc., J.Imaging Technol., 11 (4), 191 (1985), H.M.Houlihan etc., Macromolecules, 21,2001 (1988), P.M.Collins etc., J.Chem.Soc., Chem.Commun., 532 (1972), S.Hayase etc., Macromolecules, 18,1799 (1985), E.Reichmanis etc., J.Electrochem.Soc., Solid State Sci.Technol., 130 (6), F.M.Houlihan etc., Macromolcules, 21,2001 (1988), EP the 0290th, 750,046,083,156,535,271,851 and 0,388, No. 343, United States Patent (USP) the 3rd, 901,710 and 4,181, No. 531, the light acid producing agent of describing in JP-A 60-198538 and 53-133022 number and other document that contains adjacent nitrobenzyl blocking group;

Photolysis and acidic sulphones, for example at M.TUNOOKA etc., PolymerPreprints Japan, 35 (8), G.Berner etc., J.Rad.Curing, 13 (4), W.J.Mijs etc., Coating Technol., 55 (697), 45 (1983), Akzo, H.Adachi etc., PolymerPreprints Japan, 37 (3), EP the 0199th, 672,84515,044,115,618,564 and 0101, No. 122, United States Patent (USP) the 4th, 371,605 and 4,431,774, the imino-sulfonate of describing among the JP-A 64-18143,2-245756 and 3-140109 number and other document; The stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate compound of in JP-A 61-166544 and 2-71270 number and other document, describing; And diazo-ketones sulfone (diazoketosulfone) and diazonium two sulfones (diazosulfone) compound in JP-A 3-103854,3-103856 and 4-210960 number and other document, described.

In addition, can also use and above-mentionedly have by the compound of the acidic group of light or on main chain or side chain, have the polymkeric substance of such compound, comprise that those are at M.E.Woodhouse etc., J.Am.Chem.Soc., 104,5586 (1982), S.P.Pappas etc., J.Imaging Sci., 30 (5), 218 (1986), S.Kondo etc., Macromol.Chem., RapidCommun., 9,625 (1988), Y.Yamada etc., Makromol.Chem., 152,153,163 (1972), J.V.Crivello etc., J.Polymer Sci., Polymer Chem.Ed., 17,3845 (1979), United States Patent (USP) the 3rd, 849,137, German Patent the 3rd, 914, No. 407, JP-A 63-26653,55-164824,62-69263,63-146038,63-163452, the compound of describing in 62-153853 and 63-146029 number and other document.The example comprises salt (for example diazonium salt, ammonium salt, microcosmic salt, salt compounded of iodine, sulfosalt, selenium salt and arsenic salt), organic halogen compound, organo-metallic/Organohalogen compounds, comprises the light acid producing agent of adjacent nitrobenzyl blocking group, decomposes acidic sulphones (for example imino-sulfonate, stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate compound, diazo-ketones sulfone and diazonium two sulphones) by photochemistry.

Can also use at V.N.R.Pillai, Synthesis, (1), 1 (1980), A.Abad etc., Tetrahedron Lett., (47) 4555 (1971), D.H.R.Barton etc., J.Chem.Soc., (C), 329 (1970), United States Patent (USP) the 3rd, 779,778, describe among No. the 126th, 712, the EP by the acidic compound of light.

The preferred embodiment that is used for smooth acid producing agent of the present invention comprises by following general formula (b1), (b2) and (b3) compound of expression.

In general formula (b1), R ²⁰¹, R ²⁰²And R ²⁰³Each represents organic group independently.

X represents non-nucleophilic negatively charged ion, and preferably azochlorosulfonate acid anion, carboxyl root negatively charged ion, two (alkyl sulphonyl) amide anion, three (alkyl sulphonyl) methide negatively charged ion, BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-Group shown in perhaps preferably has the organic anion of one or more carbon atom.

Preferred organic anion is included in the organic anion shown in the following general formula.

Rc ¹The expression organic group.

For instance, Rc ¹Organic group is the group with 1-30 carbon atom, and preferably alkyl, cycloalkyl, aryl or wherein two or more these groups by linking group, for example singly-bound ,-O-,-CO ₂-,-S-,-SO ₃-or-SO ₂N (Rd ¹)-connected to one another group.

Rd ¹Expression hydrogen atom or alkyl.Rc ³, Rc ⁴And Rc ⁵Each represents organic group independently.

Rc ³, Rc ⁴Or Rc ⁵Organic group preferably with Rc ¹Identical organic group, and the special perfluoro alkyl group that preferably has 1-4 carbon atom.

Rc ³And Rc ⁴Can be combined with one another to ring.

By connecting Rc ³And Rc ⁴The group that forms for example is alkylidene group or arylidene, but preferably has the perfluorinated alkylidene group of 2-4 carbon atom.

Rc ¹Or Rc ³To Rc ⁵Organic group most preferably be the alkyl that the hydrogen on 1 is replaced by fluorine atom or fluoroalkyl, the perhaps phenyl that replaces with fluorine atom or fluoroalkyl.The existence of fluorine atom or fluoroalkyl is effective for increasing the acid of the acid that produced by rayed and improving its sensitivity.

R ²⁰¹, R ²⁰²Or R ²⁰³Organic group normally have 1-30 carbon atom, the group of preferred 1-20 carbon atom, and R ²⁰¹To R ²⁰³In two can be bonded to each other, form ring structure, it can comprise oxygen or sulphur atom or ester, acid amides or carbonyl.For instance, by in conjunction with R ²⁰¹To R ²⁰³In two groups and the group that forms is alkylidene group (for example butylidene or a pentylidene).

R ²⁰¹, R ²⁰²And R ²⁰³The specific examples of organic group comprise and following compound (b1-1), (b1-2) and (b1-3) corresponding group.

The light acid producing agent can be the compound that has multiple bond in the structure by general formula (b1) expression.For example, it can be the compound with following structure: wherein by the R in the compound of general formula (b1) expression ²⁰¹To R ²⁰³One of at least directly or by linking group with by another by the R in the compound of general formula (b1) expression ²⁰¹To R ²⁰³One of at least combination.

Preferred again compound (b1) comprises following compound (b1-1), (b1-2) and (b1-3).

Compound (b1-1) is the aryl sulphur compound, wherein R in general formula (b1) ²⁰¹To R ²⁰³One of at least be aryl, promptly have the aryl sulfonium ion as its cationic compound.

R in the aryl sulphur compound ²⁰¹To R ²⁰³Can be aryl entirely, perhaps R alternatively ²⁰¹To R ²⁰³In one or two can be that aryl and another are alkyl or cycloalkyl.

The example of aryl sulphur compound comprises triaryl sulphur compound, alkyl diaryl sulphur compound, dialkyl aryl sulphur compound, diaryl cycloalkyl sulphur compound, aryl bicyclic alkyl sulphur compound etc.

Aryl in the aryl sulphur compound is for example aryl of phenyl or naphthyl or for example indyl or pyrryl heteroaryl preferably, and is more preferably phenyl or indoles residue.When the aryl sulphur compound had two or more aryl, these two or more aryl can be identical or differ from one another.

The alkyl that the aryl sulphur compound can have on demand preferably has the straight or branched alkyl of 1-15 carbon atom, and the example comprises methyl, ethyl, propyl group, normal-butyl, sec-butyl and the tertiary butyl etc.

The cycloalkyl that the aryl sulphur compound can have on demand preferably has the cycloalkyl of 3-15 carbon atom, and the example comprises cyclopropyl, cyclobutyl and cyclohexyl etc.

R ²⁰¹To R ²⁰³In aryl, alkyl or cycloalkyl can have alkyl (alkyl that for example has 1-15 carbon atom), cycloalkyl (cycloalkyl that for example has 3-15 carbon atom), aryl (aryl that for example has 6-14 carbon atom), alkoxyl group (alkoxyl group that for example has 1-15 carbon atom), halogen atom, hydroxyl or thiophenyl as substituting group.Substituent preferred embodiment comprises straight or branched alkyl with 1-12 carbon atom, have the cycloalkyl of 3-12 carbon atom and have straight chain, side chain or the cyclic alkoxy of 1-12 carbon atom; And most preferably be the alkoxyl group that has the alkyl of 1-4 carbon atom and have 1-4 carbon atom.R ²⁰¹To R ²⁰³In all or any one can have substituting group.In addition, work as R ²⁰¹To R ²⁰³In any one when being aryl, preferred substituents replaces in the contraposition of aryl.

Compound (b1-2) hereinafter will be described.

Compound (b1-2) is the compound by general formula (b1) expression, wherein R ²⁰¹To R ²⁰³Each represents to comprise the organic group of non-aromatic ring independently.Aromatic nucleus comprises and contains heteroatomic aromatic nucleus.

R ²⁰¹To R ²⁰³In comprise non-aromatic ring organic group have 1-30 carbon atom and preferred 1-20 carbon atom usually.

R ²⁰¹To R ²⁰³Each represents alkyl, cycloalkyl, allyl group or vinyl to be more preferably straight chain, side chain or cyclic 2-oxoalkyl group or alkoxy carbonyl methyl independently and preferably, and the special preferably 2-oxoalkyl group of straight or branched.

R ²⁰¹To R ²⁰³Alkyl can be the straight or branched group, and the 2-oxoalkyl group that preferably has the straight or branched alkyl (for example methyl, ethyl, propyl group, butyl or amyl group) of 1-10 carbon atom and straight chain, side chain for instance, and the alkoxy carbonyl methyl is preferred.

For instance, R ²⁰¹To R ²⁰³Cycloalkyl preferably have the cycloalkyl (for example cyclopentyl, cyclohexyl or norborneol alkyl) of 3-10 carbon atom; And ring-type 2-oxoalkyl group is preferred.

R ²⁰¹To R ²⁰³The preferred embodiment of straight chain, side chain or cyclic 2-oxoalkyl group comprise above-mentionedly having＞alkyl and the cycloalkyl of C=O at 2.

For instance, R ²⁰¹To R ²⁰³The alkoxy carbonyl methyl in alkoxyl group preferably have the alkoxyl group (for example methoxyl group, oxyethyl group, propoxy-, butoxy or pentyloxy) of 1-5 carbon atom.

R ²⁰¹To R ²⁰³Can replace with halogen atom, alkoxyl group (alkoxyl group that for example has 1-5 carbon atom), hydroxyl, cyano group or nitro in addition.

Compound (b1-3) is the compound by following general formula (b1-3) expression, the compound that promptly has benzoyl group sulfosalt structure.

In general formula (b1-3), R ^1cTo R ^5cEach represents hydrogen or alkyl, cycloalkyl or alkoxyl group independently.

R ^6cAnd R ^7cEach represents hydrogen atom or alkyl or cycloalkyl independently.

R ^xAnd R ^yEach represents alkyl, cycloalkyl, allyl group or vinyl independently.R ^1cTo R ^5c, R ^6cAnd R ^7cOr R ^xAnd R ^yIn any two or more can be bonded to each other, form ring structure.

Zc ^-Represent non-nucleophilic negatively charged ion, and identical with non-nucleophilic negatively charged ion X-in the general formula (b1).

R ^1cTo R ^7cAlkyl can be the straight or branched group, and the example comprises having 1-20 carbon atom, the straight or branched alkyl (for example methyl, ethyl, straight or branched propyl group, straight or branched butyl and straight or branched amyl group) of preferred 1-12 carbon atom.

For instance, R ^1cTo R ^7cCycloalkyl can be cycloalkyl (for example cyclopentyl or cyclohexyl) with 3-8 carbon atom.

R ^1cTo R ^5cAlkoxyl group can be straight chain, side chain or cyclic group, and the example comprises the alkoxyl group with 1-10 carbon atom, preferably has the straight or branched alkoxyl group (for example methoxyl group, oxyethyl group, straight or branched propoxy-, straight or branched butoxy and straight or branched pentyloxy) of 1-5 carbon atom and the cycloalkyloxy (for example cyclopentyloxy and cyclohexyloxy) with 3-8 carbon atom.

By in conjunction with R ^1cTo R ^5c, R ^6cAnd R ^7cOr R ^xAnd R ^yIn the examples of groups of any two or more formation comprise butylidene and pentylidene etc.Ring structure can comprise oxygen or sulphur atom or ester or amido linkage.

Preferably, R ^1cTo R ^5cMiddle part is straight or branched alkyl, cycloalkyl or straight chain, side chain or cyclic alkoxy group, and more preferably, radicals R ^1cTo R ^5cIn carbon add up to 2-15.Under such condition, acid producing agent is more soluble in solvent, thereby has suppressed particulate generation between the shelf lives.

R ^xAnd R ^yAlkyl and cycloalkyl comprise R ^1cTo R ^7cAlkyl and cycloalkyl.

R ^xAnd R ^yIn each preferably 2-oxoalkyl group or alkoxy carbonyl methyl.

For instance, the 2-oxoalkyl group is to have at 2＞R of C=O group ^1cTo R ^5cAlkyl and cycloalkyl.

The example of the alkoxyl group in the alkoxy carbonyl methyl be used for R ^1cTo R ^5cAlkyl in those are identical.

R ^xAnd R ^yEach preferably has more than or equal to the alkyl of 4 carbon atoms or alkoxyl group, is more preferably to have more than or equal to 6 and be more preferably alkyl or the alkoxyl group that has more than or equal to 8 carbon atoms again.

At general formula (b2) with (b3), R ²⁰⁴To R ²⁰⁷Each represents that independently aryl, alkyl or cycloalkyl, X-represent non-nucleophilic negatively charged ion, and identical with non-nucleophilic negatively charged ion X-in the general formula (b1).

R ²⁰⁴To R ²⁰⁷Aryl phenyl or naphthyl and be more preferably phenyl preferably.

R ²⁰⁴To R ²⁰⁷Alkyl can be the straight or branched group, and for example preferably have the straight or branched alkyl (for example methyl, ethyl, propyl group, butyl or amyl group) of 1-10 carbon atom.For instance, R ²⁰⁴To R ²⁰⁷Cycloalkyl preferably have the cycloalkyl (for example cyclopentyl, cyclohexyl or norcamphyl) of 3-10 carbon atom.

R ²⁰⁴To R ²⁰⁷The substituent example that can have comprises alkyl (alkyl that for example has 1-15 carbon atom), cycloalkyl (cycloalkyl that for example has 3-15 carbon atom), aryl (aryl that for example has 6-15 carbon atom), alkoxyl group (alkoxyl group that for example has 1-15 carbon atom), halogen atom, hydroxyl or thiophenyl etc.

Comprise by following general formula (b4), (b5) and (b6) compound of expression by other suitable example of exciting light or the acidic compound of radiation exposure.

At general formula (b4) in (b6), Ar ³And Ar ⁴Each represents aryl independently.

R ²⁰⁶, R ²⁰⁷And R ²⁰⁸Each represents alkyl, cycloalkyl or aryl independently.

A represents alkylidene group, alkenylene or arylidene.

In the superincumbent smooth acid producing agent, preferably by the compound of general formula (b1) to (b3) expression etc.In these light acid producing agents, the compound that preferably has the sulfosalt structure, the compound that more preferably has the arylsulfonium salts structure, and the compound that especially preferably has three (chloro-phenyl-) sulfosalt structure.Light acid producing agent with three (chloro-phenyl-) sulfosalt structure comprises that the instantiation compound of enumerating below (b-37) is to (b-40).

As the preferred embodiment that is used for smooth acid producing agent of the present invention (b), listed example (b-1) below to (b-96), but the present invention is not limited to these examples.

In addition, can also preferred use Miao Shu De oxazole derivative, s-pyrrolotriazine derivatives etc. to [000] section at JP-A 2002-122994 number [0029].

In addition, can also preferably use at JP-A 2002-122994 number [0037] salt and sulfonate compound to [0063] section illustrated.

Light acid producing agent (b) can be separately or being used in combination with two or more.

Based on the total solids level in the ink composite, the light acid producing agent (b) in the ink composite is preferably 0.1-20 weight %, more preferably 0.5-10 weight % and more preferably 1-7 weight % again.

(tinting material)

Also comprise tinting material according to ink composite of the present invention.

Be used for tinting material of the present invention and be not particularly limited, be preferred still, and can use for example known tinting material of soluble dye according to suitable selection at pigment superior aspect weathering resistance and the color reproducibility and oil-soluble colourant.Preferably, the tinting material that is advantageously used in the ink composite according to the present invention can not be used as polymerization starter in polyreaction (being curing reaction).

This is that sensitivity reduces for the curing reaction that prevents to cause owing to dynamic rays.

＜pigment 〉

Pigment is not particularly limited, and can use any pigment that is purchased commonly used, comprises organic and mineral dye, is dispersed in pigment dispersion in the insoluble resin and the surface pigment with the resin grafting.In addition, can also use painted resin particle.

For instance, this pigment is included in Seijiro Itoh Ed., " Ganryo no Jiten (Dictionary of Pigments) " (2000), W.Herbst K.Hunger, IndustrialOrganic Pigments " and JP-A 2002-12607,2002-188025,2003-26978 and 2003-342503 number in the pigment described.

Operable in the present invention organic and specific examples mineral dye of xanchromatic that shows comprises monoazo-dyes (for example C.I. Pigment Yellow 73 1 (fast yellow G etc.) and C.I. Pigment Yellow 73 74), diazo pigment (for example C.I. pigment Yellow 12 (the yellow AAA of diazonium etc.) and C.I. pigment yellow 17), non-p-diaminodiphenyl azo pigment (for example the C.I. Pigment Yellow 73 180), azo lake pigment (for example C.I. Pigment Yellow 73 100 (tartrazine lake etc.)), concentrate azo pigment (for example C.I. Pigment Yellow 73 95 (concentrating azophosphine GR etc.)), matching stain pigment lake (for example C.I. Pigment Yellow 73 115 (quinoline yellow lake etc.)), basic dyestuff pigment lake (for example C.I. Pigment Yellow 73 18 (thioflavine color lake etc.)), anthraquinone pigment (for example fravantrone Huang (Y-24)), iso-dihydro-indole (isoindolinone) pigment (for example yellow 3RLT (Y-110) of iso-dihydro-indole), quinophtharone pigment (for example quinophtharone Huang (Y-138)), isoindoline pigment (for example isoindoline Huang (Y-139), nitroso pigments is C.I. Pigment Yellow 73 153 (nitroso-group nickel yellow etc.) for example), metal complex salt azomethine pigment (for example C.I. pigment 117 (copper azomethine Huang etc.)) or the like.

The pigment example that shows redness or magenta comprises monoazo-dyes (for example C.I. pigment red 3 (toluidine red etc.)), diazo pigment (for example C.I. pigment red 38 (pyrazolone red B etc.)), azo lake pigment (for example C.I. Pigment red 53:1 (Lake red C etc.) and C.I. Pigment red 57:1 (brilliant carmine 6B etc.)), concentrate azo pigment (for example C.I. Pigment red 144 (concentrating azophloxine BR etc.)), matching stain pigment lake (for example C.I. Pigment red 174 (phloxine B color lake etc.)), basic dyestuff pigment lake (for example C.I. pigment red 81 (rhodamine 6G color lake etc.)), anthraquinone pigment (for example C.I. Pigment red 177 (dianthraquinone is red etc.)), thioindigo pigment (for example C.I pigment Red 88 (thioindigo is purplish red etc.)), perynone pigment (for example C.I. Pigment red 194 (perynone is red etc.)), perylene pigment (C.I. pigment red 149 (perylene is scarlet etc.) for example, quinacridone pigment (for example C.I. pigment violet 19 (unsubstituted quinacridone) and C.I. pigment red 122 (quinacridone magenta etc.)), iso-dihydro-indole pigment (for example C.I. Pigment red 180 (the red 2BLT of iso-dihydro-indole etc.)), alizarine lake dyestuff (C.I. pigment Red 83 (madder lake etc.) or the like for example.

The pigment example that shows blueness or cyan comprises diazotizing dyes (for example C.I. Pigment blue 25 (dianisidine blue etc.)), phthalocyanine pigment (for example C.I. pigment Blue 15 (phthalocyanine blue etc.)), matching stain pigment lake (for example C.I. Pigment blue 24 (peacock blue lake etc.)), basic dyestuff pigment lake (for example C.I. pigment blue 1 (Victria pure blue B O color lake etc.)), anthraquinone pigment (for example C.I. pigment blue 60 (indigo etc.)), alkali blue pigment (for example C.I. pigment 18 (alkali blue V-5:1)) or the like.

Show green pigment example and comprise phthalocyanine pigment (for example C.I. pigment Green 7 (phthalocyanine green) and C.I. pigment green 36 (phthalocyanine green)), azo metal complex pigment (for example C.I. Pigment green 8 (nitroso-group is green)) or the like.

Show bisque pigment example and comprise isoindoline pigment (for example orange 66 (isoindoline is orange) of C.I. pigment) and anthraquinone pigment (orange 51 (the dichloro pyranthrone is orange) of C.I. pigment for example.

The pigment example that shows black comprises that carbon black, titanium are black, nigrosine etc.

The specific examples of white pigment comprises white lead carbonate (2PbCO ₃Pb (OH) ₂, so-called silvery white), zinc oxide (ZnO, so-called zinc white), titanium dioxide (TiO ₂, so-called titanium white), strontium titanate (SrTiO ₃, so-called titanium strontium white) etc.

Titanium dioxide has than lower density of other white pigment and the specific refractory power of Geng Gao, at chemistry or physically be more stable, therefore has bigger sheltering and painted potentiality as pigment, and is being excellent aspect acidproof or alkali and other environmental factors.Therefore, using titanium dioxide is preferred as white pigment.Can use other white pigment (comprising above-mentioned those pigment white pigment in addition) when needing.

For dispersed color, can use any dispersion machinery, for example ball mill, sand mill, masher, roller crusher, jet mill, homogenizer, paint shaker, kneading machine, agitator, Henschel mixing tank, colloidal mill, ultrasonic wave homogenizer, pearl mill and wet jet mill.

Can also during dispersing of pigments, add dispersion agent.The example of dispersion agent comprises polyacrylic ester, multivalence aliphatic carboxylic acid, naphthene sulfonic acid/formalin condenses, polyoxyethylene alkyl phosphate, pigment derivative of salt, high-molecular weight polycarboxylate, high-molecular weight unsaturated acid ester, high-molecular weight multipolymer, the modification of carboxylicesters, long-chain polyaminoamide and the high molecular acid esters of hydroxyl etc.The polymeric dispersant that use is purchased, for example the Solsperse series product of being produced by Zeneca also are preferred.

Can use and be suitable for the dispersing of pigments auxiliary agent as dispersing auxiliary.With respect to 100 weight part pigment, preferably add the dispersion agent and the dispersing auxiliary of 1-50 weight part.

Can add the dispersion medium of solvent, perhaps alternatively, can use top cationically polymerizable compound (lower-molecular-weight component) and do not use solvent as the various components in the ink composite (for example pigment); But preferably do not contain solvent according to ink composite of the present invention, because said composition is at the printing ink that is applied to the actinic radiation-curable of post-hardening on the recording medium.Because residual solvent causes the reduction of solvent resistance and causes the problem of VOC (volatile organic compounds) in the hardened ink image.From above-mentioned, preferably use the cationically polymerizable compound as dispersion medium, and to select the minimum cationically polymerizable monomer of its medium viscosity be preferred for dispersibility and the processing characteristics of improving ink composite.

The mean diameter of pigment is preferably in the scope of 0.02-0.4 micron, more preferably in the scope of 0.02-0.1 micron, and more more preferably in the scope of 0.02-0.07 micron.

Select pigment, dispersion agent and dispersion medium and determine to disperse and filtration condition according to the mode that the mean diameter of granules of pigments drops in the above-mentioned preferable range.Stability in storage, transparency and the curing efficiency of control particle diameter to prevent stopping up shower nozzle and to keep printing ink.

＜dyestuff 〉

Be used for preferably oil-soluble colourant of dyestuff of the present invention.Specifically, the dyestuff preferably solubleness in water (being dissolved in the painted dosage of 100 grams in the water) is less than or equal to 1 gram under 25 ℃, preferably be less than or equal to 0.5 gram, and is more preferably less than or equals 0.1 gram.Therefore, preferably use so-called water-insoluble and oil-soluble dyestuff.

As for being used for dyestuff of the present invention, preferably on aforesaid basic dye structure, introduce oil-soluble group to guarantee the dyestuff of dissolving aequum in ink composite.

The example of oil-soluble group comprises the long-chain branched-chain alkyl; the long-chain branched alkoxy; long-chain branched alkane sulfenyl; long-chain branched-chain alkyl alkylsulfonyl; long-chain side chain acyloxy; long-chain branched alkoxy carbonyl; long-chain props up chain acyl; long-chain side chain amido; the branched-chain alkyl sulfonamido; long-chain branched alkylamino alkylsulfonyl and the aryl that comprises these long-chain substitution in side chain bases; aryloxy; aryloxy carbonyl; aryl carbonyl oxygen base; aromatic yl aminocarbonyl; n-aryl sulfonyl and Arenesulfonyl amino etc.

Alternatively, can also on the water-soluble dye that comprises carboxylic acid or sulfonic acid group, introduce oil-soluble group by using long-chain branched-chain alcoho, amine, phenol or anils, for example alkoxy carbonyl, aryloxycarbonyl, alkylamino alkylsulfonyl or fragrant amino-sulfonyl.

Oil-soluble colourant preferably have 200 ℃ or lower, more preferably 150 ℃ or lower, and more preferably 100 ℃ or lower fusing point again.Use the low melting point oil-soluble colourant can limit tinting material in ink composite crystal settling and improve the stability in storage of ink composite.Dyestuff preferably has high oxidizing potential, because it has improved fade resistance, particularly by fading that the oxidizing substance of for example ozone causes.Therefore, be used for oil-soluble colourant of the present invention and preferably have oxidizing potential more than or equal to 1.0V (relatively SCE).Oxidizing potential is preferably higher, and the dyestuff that therefore has more than or equal to the oxidizing potential of 1.1V (SCE relatively) is preferred, and is particularly preferred more than or equal to the oxidizing potential of 1.5V (SCE relatively).

Yellow dyes with structure of being represented by the general formula of describing among the JP-A 2004-250483 (Y-I) is preferred.

The example of particularly preferred dyestuff comprises the dyestuff of expression in the general formula (Y-II) to (Y-IV) among [0034] section of JP-A 2004-250483 number, and its typical example comprises the compound that JP-A 2004-250483 number [0060] describes to [0071] section.Oil-soluble colourant by wherein said general formula (Y-I) expression not only can use in Yellow ink, and can use in any other color ink of for example black and redness.

The compound that has by the structure of the general formula (3) among JP-A 2002-114930 number and (4) expression is preferred as magenta dye, and its typical example comprises the compound that JP-A 2002-114930 number [0054] describes to [0073] section.

Particularly preferred dyestuff is the azoic dyestuff of general formula (M-1) to (M-2) expression described to [0122] section by JP-A 2002-121414 number [0084], and its typical example is included in the compound that JP-A 2002-121414 number [00123] describes to [0132] section.Not only magenta ink can be used for by general formula (3), (4) with (M-1) to the oil-soluble colourant of (M-2) expression, and for example any other color ink of black and red ink can be used for.

The dyestuff of general formula (IV-3) to (IV-4) expression of preferably describing to [0078] section by the dyestuff of general formula (I) to (IV) expression of describing among JP-A 2001-181547 number and JP-A 2002-121414 number [0063] as cyan dye, and its typical example is included in JP-A 2001-181547 number [0052] to [0066] section and the compound described to [0081] section of JP-A 2002-121414 number [0079].

Particularly preferred dyestuff is the general formula (C-I) described to [0196] section by JP-A 2002-121414 number [0133] and (C-II) phthalocyanine pigment of expression, and the phthalocyanine pigment of more preferably being represented by general formula (C-II) again.Its typical example is included in the compound that JP-A 2002-121414 number [0198] describes to [0201] section.By general formula (I) to (IV), (IV-D) to (IV-4), (C-I) and (C-II) oil-soluble colourant of expression not only can be used for cyan ink, and can be used for for example any other color ink of black and green ink.

Oxidizing potential

Those skilled in the art can easily determine the oxidizing potential (Eox) according to dyestuff of the present invention.For instance, at P.Delahay, " New Instrumental Method inElectrochemistry " (1954, Interscience Publishers), A.J.Bard etc., and " Electrochemical Methods " (1980, John Wiley ﹠amp; Sons) and AkiraFujishima etc., and " Electrochemical Measurement Methods " (1984, these methods have been described in GihodoShuppan).

Specifically, by in the solvent of for example dimethyl formamide of the supporting electrolyte that contains sodium perchlorate for example or perchloric acid tetrapropyl ammonium or acetonitrile, dissolving 1 * 10 ^-2To 1 * 10 ^-6The specimen of mol concentration; And the supposition in cyclic voltammetric or direct current polarogram equipment, use carbon (GC) as working electrode, rotating platinum electrode (RPE) as counter electrode, the oxidation wave that applies the voltage acquisition by anode side (upper side) is a straight line, by joining and the oxidation wave straight line and saturation currnet collinear joining (perhaps itself and the parallel collinear joining of vertical line of passing through the peak electromotive force) of determining oxidation wave straight line and residual current-potential line, and determine to obtain oxidation wave at the voltage of the relative SCE in collinear center (saturated calomel electrode) that connects these two joinings.Under the influence of voltage difference between liquid and sample solution resistivity, this value may depart from about tens millivolts degree, but by using standard model (for example quinhydrones) can guarantee the reproducibility of electromotive force.Can suitably select the supporting electrolyte and the solvent that use according to the oxidizing potential of specimen and solvability.Akira Fujishima etc., " Electrochemical MeasurementMethods " (1984, Gihodo Shuppan) have been described the supporting electrolyte and the solvent that use in the 101st to 118 page.

Hereinafter, will list the specific examples that is used for dyestuff of the present invention, but be not limited to these typical examples.

In general formula, each is to (X ¹¹, X ¹²) and (Y ¹¹, Y ¹²) specific examples can be any order.

In solid matter, preferably in composition, add consumption and be preferably 1-20 weight %, the more preferably tinting material of 2-10 weight %.

(other component)

Other additive that in the present invention, adds when hereinafter explanation being needed.

＜UV light absorber 〉

In order to improve weather-proof stability and to prevent the variable color of gained image, can in ink composite according to the present invention, add UV light absorber.

The example of this UV light absorber is included in the benzotriazole cpd of describing in JP-A 58-185677,61-190537,2-782,5-197075 and 9-34057 number and other document; The benzophenone compound of in JP-A 46-2784 and 5-194483 number, No. the 3214463rd, United States Patent (USP) and other document, describing; The styracin compound of in JP-B 48-30492 and 56-21141, JP-A 10-88106 number and other document, describing; The triaizine compounds of in JP-A 4-298503,8-53427,8-239368,10-182621 and 8-501291 number and other document, describing; The compound of in No. the 24239th, Research Disclosure, describing; Luminous compound, for example stilbene and benzoazole compounds by absorbing ultraviolet ray; So-called white dyes or the like.

Can be suitably according to using the decision addition, still consumption is approximately 0.5-15 weight % solid matter usually.

＜sensitizing agent 〉

For the acid that improves the light acid producing agent produces efficient and improves the sensitization wavelength, can in ink composite according to the present invention, add sensitizing agent when needing.Sensitizing agent is had no particular limits, as long as it can be with electronics or energy transfer mechanism sensitization light acid producing agent.Its preferred examples comprises aromatic fused ring compound (for example anthracene, 9,10-dialkoxy anthracene, pyrene and perylene), aromatic ketone compound (for example methyl phenyl ketone, benzophenone, thioxanthone and Michler's keton) and heterogeneous ring compound (for example thiodiphenylamine and N-Fang Ji oxazole diketone (N-aryloxazolydinones)).Suitably determine addition according to using, but usually with respect to the light acid producing agent, its addition is preferably 0.01-1 mole %, more preferably 0.1-0.5 mole %.

＜antioxidant 〉

In order to improve the stability of ink composite, can add antioxidant.The example of antioxidant comprises that those are examined at EP and disclose the careful antioxidant of describing in No. 3435443, JP-A 54-48535,62-262047,63-113536,63-163351,2-262654,2-71262,3-121449,5-61166 and 5-119449 number, United States Patent (USP) the 4814262nd and No. 4980275 and other document that discloses of the 223739th, 309401,309402,310551,310552 and No. 459416, German Patent.

Suitably determine addition according to using, but its addition approximately is 0.1-8 weight % in solid matter usually.

＜discoloration inhibitor 〉

Any may be used in the discoloration inhibitor of various organic and based on metal complexes according to ink composite of the present invention.The example of organic discoloration inhibitor comprises quinhydrones, alkoxyl group phenol, dialkoxy phenol, phenol, aniline, amine, indane, chroman (chromane), alkoxyl aniline, heterogeneous ring compound etc.The example of metal complex discoloration inhibitor comprises nickel complex, zinc complex etc., and its typical example is included in the compound of describing in Research Disclosure No. 17643 (VII-I to J section), the 15162nd phase of ibid., the 18716th phase of ibid. (the 650th page of left column), the 36544th phase of ibid. (the 527th page), the 307105th phase of ibid. (the 872nd page) and ibid. the 15162nd interim patent of quoting; And the compound that in the general formula of typical compound of describing in the 127th to 137 page for JP-A 62-215272 number and exemplary compounds, comprises.Suitably determine addition according to using, but it approximately is 0.1-8 weight % in solid matter usually.

＜conducting salt 〉

In order to control the physical properties during the ink-jet, can in ink composite according to the present invention, add conducting salt, for example potassium sulfocyanate, lithium nitrate, ammonium thiocyanate or dimethylamine hydrochloride.

＜solvent 〉

In order to improve the adhesivity with recording medium, the organic solvent that adds utmost point trace in ink composite according to the present invention is effective.

The example of solvent comprises ketone solvent (for example acetone, methylethylketone and diethyl ketone), alcoholic solvent (for example methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, 1-butanols and the trimethyl carbinol), chloro solvent (for example chloroform and methylene dichloride), aromatic solvent (for example benzene and toluene), ester solvent (for example ethyl acetate, butylacetate and isopropyl acetate), ether solvents (for example diethyl ether, tetrahydrofuran (THF) He diox), glycol ether solvent (for example ethylene glycol monomethyl ether and glycol dimethyl ether) or the like.

In the case, the amount of adding solvent is in the scope that can not cause anti-solvent and VOC problem, and is therefore preferred at the 0.1-5 of whole ink composite weight %, more preferably in the scope of 0.1-3 weight %.

＜polymkeric substance 〉

In order to adjust the physical properties of film, can in ink composite, add various polymkeric substance.The example of this polymkeric substance comprises acrylate copolymer, polyvinyl butyral resin, urethane resin, polyamide resin, vibrin, Resins, epoxy, phenol resins, polycarbonate resin, polyvinyl butyral resin, vinyl-formal resin, shellac, Vinylite, acrylic resin, rubber resin, wax, other natural resin etc.Can use these resins with the combination of two or more.Wherein, be preferred by ethylene copolymer with Acrylic Acid Monomer copolymerization acquisition.In addition, comprise " containing carboxylic monomer ", " alkylmethacrylate " or " alkyl acrylate " also can be preferred for polymeric adhesive as the multipolymer of structural unit as the copolymerization component.

＜tensio-active agent 〉

Can in ink composite according to the present invention, add tensio-active agent.

Tensio-active agent comprises the tensio-active agent that those are described in JP-A 62-173463 and 62-183457 number.The example comprises for example aniorfic surfactant of dialkyl sulfosuccinates, sulfonated alkyl naphathalene and soap; The nonionic surface active agent of polyethylene oxide alkyl ethers, polyoxyethylene allylic alkylation allyl ethers, acetylene ethylene glycol and polyoxyethylene-polyoxypropylene block copolymers for example; Cationic surfactant of alkylammonium salt and quaternary ammonium salt or the like for example.Can use organofluorine compound substitution list surface-active agent.Organofluorine compound is preferably hydrophobic.The example of organofluorine compound comprises fluorochemical surfactants, oily fluorochemical (for example fluorocarbon oil) and solid fluoride resin (for example tetrafluoroethylene resin); And its typical example comprises the compound of those descriptions in JP-B 57-9053 (the 8th to 17 row) and JP-A 62-135826 number.

In addition, can in ink composite according to the present invention, add level dyeing additive, matting agent, the wax that is used to adjust the film physical properties when needing, perhaps be used to improve the adhering tackifier with recording medium, for example polyolefine and can not suppress polymeric PET.

The representative instance of tackifier be included in the high molecular binder resin described among the 5th to 6 page of the JP-A 2001-49200 (for example have multipolymer, the methacrylic ester of the alcohol of 1-20 carbon atom on methacrylic ester and the alkyl and have 3-14 carbon atom the aliphatics cyclic alcohol multipolymer, methacrylic ester and have the multipolymer of the aromatic alcohols of 6-14 carbon atom) and comprise lower molecular weight binder resin of polymerizable unsaturated bond or the like.

The preferred embodiment of ink composite

As mentioned above, use according to the ink composite (according to ink composite of the present invention) of curable compositions of the present invention comprise specific polymerizable compound, by the acidic compound of radiation exposure and other additive as required, for example other polymerizable compound and tinting material.With respect to the gross weight of ink composite, the content of tinting material is preferably 1-10 weight %, more preferably 2-8 weight %, and comprise that the total content of the polymerizable compound of specific polymerizable compound is preferably 1-97 weight %, more preferably 30-95 weight %.With respect to the total polymerizable compound that comprises specific polymerizable compound, be preferably 0.01-20 weight %, more preferably 0.1-20 weight % by the content of the acidic compound of radiation exposure.

When using ink composite according to the present invention as ink-jet recording ink, from ejection efficiency, under injection temperature (for example 40-80 ℃, preferred 25-30 ℃), the viscosity of ink-jet recording ink is preferably 7-30cm Pas, more preferably 7-20m Pas.According to the viscosity of ink composite of the present invention 35-500mPas preferably for example, be more preferably 35-200mPas under the room temperature (25-30 ℃).Preferably suitably regulate composition, thereby make ink composite according to the present invention have viscosity in above-mentioned scope.By the viscosity under the increase room temperature, even can prevent also that when using the porous recording medium printing ink from infiltrating in the recording medium, and reduce unhardened monomeric amount and smell.Preferably, can also when the ejection ink droplet, suppress ink bleed, therefore improve picture quality.

According to the surface tension of ink composite of the present invention 20-30mN/m and be more preferably 23-28mN/m preferably.When at various recording mediums, when for example using on polyolefine, PET, White Board and the uncoated paper according to ink composite of the present invention, in order to prevent ink bleed and infiltration, its surface tension is preferably greater than or equals 20mN/m, and for improve with preferred its surface tension of the consistency of recording medium more than or equal to 30mN/m.

Ink composite according to the present invention is advantageously used for ink-jet recording ink.When as ink-jet recording ink, in ink-jet printer, ink composite is sprayed onto on the recording medium, the ink composite by radiation exposure sclerosis ejection comes record then.

The print that so obtains with printing ink is being superior aspect the intensity of the hardened image-region by for example ultraviolet dynamic rays irradiation, therefore said composition not only can be used to form image but also can be used for many application, for example forms the ink receiving layer (image-region) of planographic printing plate.

[ink jet recording method]

The ink jet recording method (according to ink jet recording method of the present invention) that advantageously uses according to ink composite of the present invention will be described below.

Ink jet recording method comprises by ink jet recording device ink composite according to the present invention is sprayed onto on the recording medium, solidifies the ink composite of ejection by the dynamic rays irradiation then.

The recording medium that can use according to ink composite of the present invention is not particularly limited, and the example comprises the paper of coating for example commonly used and uncoated paper and is used for the various nonabsorbable resin materials of so-called soft packaging and membranaceous resin molding thereof, and the representative instance of various plastic films comprises PET film, OPS film, OPP film, ONy film, PVC film, PE film, TAC film etc.The example that can be used as other plastics of recording medium material comprises polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubber etc.In addition, metal and glass also can be used as recording medium.

During curing heat-resisting contraction and ink composite according to the present invention superior aspect the adhesivity of base material (recording medium) have both make for example because the curing of printing ink and the heat during contraction or the curing reaction and curl easily or the film (for example the PET film of thermal contraction, OPS film, OPP film, ONy film and PVC film) of distortion on, also can form the advantage of HD image.

Other example that is used for recording materials of the present invention comprises the following carrier that is used for planographic printing plate.

Be applied to comprise alpha-ray, gamma-rays, X ray, ultraviolet ray, visible rays, infrared rays, electron beam etc. according to the example of the dynamic rays of ink jet recording method of the present invention.The peak wavelength of dynamic rays is preferably 200-600nm, 300-450nm more preferably, and 350-420nm more preferably again.In addition, the output of dynamic rays preferably is less than or equal to 2,000mJ/cm ², 10-2 more preferably, 000mJ/cm ², 10-1 more preferably again, 000mJ/cm ², and be preferably 50-800mJ/cm especially ²

In ink jet recording method according to the present invention, be 10-1 preferably especially with emission 350-420nm emission wavelength peak and the maximal illumination on the recording medium surface, 000mW/cm ²The uviolizing ink composite.

Below will be at planographic printing plate according to the present invention, according to the favourable application of ink jet recording method of the present invention and prepare explanation in the explanation of method of planographic printing plate and can be used for according to other condition of ink jet recording method of the present invention with about the details of ink jet recording method and other.

By using, can make the point of inkjet compositions directly keep constant and even on the different recording medium of various surface wettabilities, also can obtain the image of quality improvement according to ink jet recording method of the present invention.In order to obtain the coloured image among the present invention, preferably form image one by one from the lower coloured image of brightness.If from the lower printing ink stack printing ink of brightness, ray is not easy to arrive following printing ink, causes curing efficiency reduction, the increase of levels of residual monomers, the generation and the adhering reduction of smell usually.Although dynamic rays can be shone on the full-colour image simultaneously, shine in order to quicken to solidify the every kind of coloured image that preferably order is formed.

[planographic printing plate and the method for producing planographic printing plate]

Production is the method for the production planographic printing plate that comprises the steps according to the method for planographic printing plate of the present invention: ink composite according to the present invention is sprayed onto on the carrier, solidify the ink composite of ejection by the dynamic rays irradiation then, thereby form hydrophobic image.

According to planographic printing plate of the present invention also is the planographic printing plate for preparing according to the method for producing planographic printing plate of the present invention, the hydrophobic image that it has carrier and forms on this carrier.

Usually use and have the so-called PS plate of the oleophylic photosensitive resin layer that on hydrophilic support, forms as planographic printing plate.Usually also removing non-image district by dissolving subsequently produces the PS plate by the mask exposure (face exposure) through graphic arts film (lith film).Recently, wherein handle electronicly, store and the digital technique of output image information is just becoming more and more general, and need the image output method compatible that upgrade with digital technique by computer.What developing as a result, is directly by do not use " Computer To Plate (CTP) technology " of graphic arts film according to digitized graphic information scanning with the ray (for example laser beam) of high directivity.

In the present invention, as the method for the acquisition planographic printing plate that allows this scan exposure, adopt and directly use ink composite or jet ink recording ink compound to prepare the method for planographic printing plate.In the methods of the invention, get off to form required printing plate by in ink-jet or other process, going up ink-jet and the ink composite of ejection or ink-jet recording ink are exposed to dynamic rays with image (preferred hydrophobic image) at carrier (preferred hydrophilic support).According to ink composite of the present invention or ink-jet recording ink is ink composite or the ink-jet recording ink that is suitable for this method.

＜carrier 〉

Carrier (recording medium) according to planographic printing plate of the present invention is not particularly limited, as long as it is a size inflexible plate-shaped support.This carrier is hydrophilic support preferably.The example comprises paper, with plastic material (polyethylene for example, polypropylene or polystyrene) laminated paper, metal sheet (aluminium for example, zinc and copper coin), plastic film (cellulose diacetate for example, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, the film of polycarbonate and polyvinylacetal), have the paper of the laminated layer of above-mentioned metal or vapor deposited layers or plastic film or the like.For instance, preferred carrier is polyester film and aluminium sheet.Wherein, dimensional stabilizing and relatively cheap aluminium sheet are preferred.

Preferred aluminium sheet is pure aluminium sheet and comprises the alloy sheets of aluminium as main ingredient and a small amount of extraneous element, perhaps can be laminated or deposits the plastic film of aluminium.Extraneous element in the aluminium alloy comprises silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium.The content of extraneous element preferably is less than or equal to 10 weight % in the alloy.Although fine aluminium is most preferred in the present invention, because because the problem of refining process is difficult to prepare pure aluminium fully, so aluminium sheet can comprise a spot of extraneous element.Composition to aluminium sheet is not particularly limited, and can use any known raw material commonly used.

The thickness of carrier is 0.1-0.6 millimeter and more preferably 0.15-0.4 millimeter preferably.

Aluminium sheet is preferably accepted surface finishing before use and is handled, and for example surface coarsening is handled or anodic oxidation treatment.Improve the wetting ability of carrier and the adhesivity between image recording layer and the carrier by surface finishing.Before surface coarsening is handled,, for example make aluminium sheet accept skimming treatment with tensio-active agent, organic solvent, alkaline aqueous solution etc. in order to remove lip-deep rolling oil.

The whole bag of tricks can be used for the surface coarsening of aluminium sheet, and the example comprises mechanical surface roughening treatment, electrochemical surface roughening treatment (surface coarsening by the electrochemical dissolution surface) and chemical surface roughening treatment (surface coarsening by the chemical dissolution surface).

Can use any method well known in the art, for example ball polishing, scratch brushing, blowing polishing and polishing are as the mechanical surface method of roughening.Alternatively, can use the printing transferring method of during the hot rolling of aluminium, using the roll transfer surface irregularity of surface imperfection.

For instance, can be by in the electrolyte solution that comprises acid (for example hydrochloric acid or nitric acid), carrying out the electrochemical surface alligatoring to vector administration alternating-current or direct current.Again alternatively, can also use the method for the use nitration mixture of in JP-A 54-63902 number, describing.

In order to improve wear resistance, when needing by using the aqueous solution etching of potassium hydroxide for example or sodium hydroxide, when needing then further after the neutralization in anode oxidation process the aluminium sheet after the treat surface roughening treatment.

The ionogen that can use various formation porous oxide films is as the ionogen that uses in the process of anodic oxidation aluminium sheet.Usually use sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or their mixing acid.Suitably determine electrolytical concentration according to electrolytical kind.

The condition of anode oxidation process is according to employed change of electrolyte, and therefore do not specify, but electrolyte concentration is 1-80 weight % usually; Fluid temperature 5-70 ℃; Current density 5-60A/dm ²Voltage 1-100V; And electrolysis time 10 seconds to 5 minutes.The amount of formed anode oxide film is preferably 1.0-5.0g/m ²And 1.5-4.0g/m more preferably ²In the superincumbent scope, can advantageously obtain favourable planographic printing plate aspect the scuff resistance in printing durability and non-image district.

The carrier that can use the surface finishing with above-mentioned anode oxide film is as the carrier that is used for the present invention, but in order further to improve and the adhesivity on upper strata, wetting ability, resistance to crocking, heat insulating ability and other, it can accept other processing when needing, and is for example enlarging described in JP-A 2001-253181 and 2001-322365 number or the processing of closed porosity or it is immersed in the surface hydrophilic that comprises in the hydrophilic compounds aqueous solution handles.Reaming or sealing treatment are not limited to aforesaid method, and can use any known method.

＜micropore sealing 〉

Can by Vapor Seal, only with the fluorine zirconic acid handle, with the Sodium Fluoride of the aqueous solution sealing that comprises inorganic fluorine compounds handle, Vapor Seal in the presence of lithium chloride or seal with hot water and to carry out micropore and seal.

In aforesaid method, it is preferred using micropore sealing, vapor seal or the hot water sealing of the aqueous solution that comprises inorganic fluorine compounds.Below every kind of method will be described.

-micropore sealing in comprising the aqueous solution of inorganic fluorine compounds

The inorganic fluorine compounds that uses in the micropore sealing in comprising the aqueous solution of inorganic fluorine compounds is metal fluoride preferably.

The example comprises Sodium Fluoride, Potassium monofluoride, Calcium Fluoride (Fluorspan), magnesium fluoride, sodium fluozirconate, potassium fluozirconate, titanium sodium fluoride, potassium fluotitanate, ammonium fluozirconate, ammonium titanium fluoride, potassium fluotitanate, fluorine zirconic acid, hydrofluotitanic acid, hexafluorosilicic acid, nickelous fluoride, ferric fluoride, hexafluorophosphoric acid and hexafluorophosphoric acid ammonium.Wherein, sodium fluozirconate, titanium sodium fluoride, fluorine zirconic acid and hydrofluotitanic acid are preferred.

In order to seal the micropore in the anode oxide film fully, the concentration of inorganic fluorine compounds is preferably greater than or equals 0.01 weight % in the aqueous solution, more preferably greater than or equal 0.05 weight %, and from resistance to crocking, it preferably is less than or equal to 1 weight %, is more preferably less than or equals 0.5 weight %.

The aqueous solution that comprises inorganic fluorine compounds preferably also comprises phosphate compounds.The existence of phosphate compounds is favourable, because it can effectively increase the wetting ability on anode oxide film surface and printing efficiency and the resistance to crocking during the printing.

The preferred embodiment of phosphate compounds comprises the metal phosphate of basic metal for example or alkaline-earth metal.

Its typical example comprises zinc phosphate, aluminum phosphate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, monoammonium phosphate, potassium dihydrogen phosphate, monosodium phosphate, potassium primary phosphate, dipotassium hydrogen phosphate, calcium phosphate, microcosmic salt, secondary magnesium phosphate, trimagnesium phosphate, ferrous phosphate, tertiary iron phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, Sodium phosphate dibasic, lead phosphate, Secondary ammonium phosphate, monocalcium phosphate, Trilithium phosphate, phospho-wolframic acid, ammonium phosphowolframate, Tungstophosphoric acid, sodium salt, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite, Tri sodium Phosphate and trisodium phosphate.Wherein, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, potassium primary phosphate and dipotassium hydrogen phosphate are preferred.

Combination to inorganic fluorine compounds and phosphate compounds is not particularly limited, but the aqueous solution preferably comprise at least sodium fluozirconate as inorganic fluorine compounds and at least SODIUM PHOSPHATE, MONOBASIC as phosphate compounds.

In order to improve printing efficiency and the resistance to crocking during the printing, the concentration of phosphate compounds is preferably greater than or equals 0.01 weight %, more preferably greater than or equal 0.1 weight %, and from solvability, it preferably is less than or equal to 20 weight %, is more preferably less than or equals 5 weight %.

Ratio to compound in the aqueous solution is not particularly limited, but the weight ratio of inorganic fluorine compounds and phosphate compounds is preferably 1/200 to 10/1 and more preferably 1/30 to 2/1.

In addition, the temperature of the aqueous solution is preferably 20 ℃ or higher, and more preferably 40 ℃ or higher, and preferred 100 ℃ or lower, more preferably 80 ℃ or lower.The pH of the aqueous solution is preferably greater than or equals 1, more preferably greater than or equal 2, and preferably be less than or equal to 11, be more preferably less than or equal 5.

Micropore enclosure method in comprising the aqueous solution of inorganic fluorine compounds is not particularly limited, and the example comprises dipping method and spraying method.These methods can only be implemented once or repeatedly, and can be used in combination two or more these methods.

Wherein, dipping method is preferred.When using dipping method to handle, the treatment time is preferably greater than or equals 1 second, more preferably greater than or equal 3 seconds, and preferably be less than or equal to 100 seconds, be more preferably less than or equal 20 seconds.

Micropore sealing in steam

For instance, can contact the micropore sealing that is implemented in the steam continuously or discontinuously with anode oxide film by making the steam under high pressure or the normal pressure.

The temperature of steam is preferably 80 ℃ or higher, and more preferably 95 ℃ or higher, and preferred 105 ℃ or lower.

The pressure of steam is preferably in that (normal atmosphere-50mmAq) is to (normal atmosphere+300mmAq), perhaps (1.008 * 10 ⁵To 1.043 * 10 ⁵Pa) in the scope.

Be preferably greater than the duration of contact of steam or equal 1 second, more preferably greater than or equal 3 seconds, and preferably be less than or equal to 100 seconds, be more preferably less than or equal 20 seconds.

Micropore sealing in hot water

For example, be immersed in the micropore sealing that is implemented in the hot water in the hot water by the aluminium sheet that will have formed anode oxide film.

Hot water can comprise inorganic salt (for example phosphoric acid salt) or organic salt.

The temperature of hot water is preferably 80 ℃ or higher, and more preferably 95 ℃ or higher, and preferred 100 ℃ or lower.

Dipping time in hot water is preferably greater than or equals 1 second, more preferably greater than or equal 3 seconds, and preferably be less than or equal to 100 seconds, be more preferably less than or equal 20 seconds.

Be used for hydrophilicity-imparting treatment of the present invention and be included in United States Patent (USP) the 2nd, 714, the alkalimetal silicate method of describing in 066,3,181,461,3,280,734 and 3,902,734.In the method, in the aqueous solution of water glass, flood and the electrolysis carrier for instance.Also be included in describe among JP-B 36-22063 number handle the method for carrier and at United States Patent (USP) the 3rd, 276 with potassium fluozirconate, the method for describing in 868,4,153,461 and 4,689,272 of handling with polyvinylphosphonic acid.

Carrier preferably has the average centerline roughness of 0.10-1.2 micron.In above-mentioned scope, can advantageously obtain the adhesivity of required and image recording layer, favourable printing durability and favourable resistance to crocking.

In on the surface of above-mentioned hydrophilic support, spraying according to ink composite of the present invention or jet ink recording ink compound, preferably ink composite or jet ink recording ink compound are heated to preferred 40-80 ℃, more preferably 25-30 ℃ temperature, viscosity drop with ink composite is low to moderate preferred 7-30m Pas, more preferably 7-20m Pas thus.Especially, because provide better effect, using 25 ℃ of following ink viscosities is preferred as the ink composite of 35-500mPs.Use this method that high ink-jet stability is provided.

Usually, comprise that the actinic radiation-curable ink composite according to ink composite of the present invention has than aqueous ink common oil ink composition or the higher viscosity of ink-jet recording ink, and its viscosity during according to ink-jet temperature fluctuation and noticeable change.The fluctuation of ink viscosity has very big influence for droplet size and ink ejection velocity, so cause the reduction of picture quality.Therefore, need keep temperature-resistant during the ink-jet as far as possible.Therefore, preferably temperature setting of temperature among the present invention control width ± 5 ℃ is more preferably temperature setting ± 2 ℃, and is more preferably temperature setting ± 1 ℃ again.

(ink jet recording device)

Be not particularly limited being used for ink jet recording device of the present invention, and can use any ink jet recording device that can be purchased.That is, in the present invention, ink jet recording device document image on recording medium that can be purchased by use.

For instance, be used for ink jet recording device of the present invention and have ink feeding system, temperature sensor and gamma ray source.

For instance, ink feeding system further has the storage tank that stores inkjet compositions, ink supply pipe, inkjet compositions charging-tank, strainer and the piezoelectric ink jet head before ink gun just.Piezoelectric ink jet head allows with for example 320 * 320 to 4,000 * 4, and 000dpi is preferred 400 * 400 to 1,600 * 1,600dpi, and more preferably the resolving power of 720 * 720dpi is sprayed 1-100pl, the multiple dimensioned point (multi-sized dot) of preferred 8-30pl amount." dpi " among the present invention means counting of every 2.54cm.

As mentioned above, preferably the actinic radiation-curable printing ink with ejection is heated to special constant temp, therefore preferred insulation and the zone of heating from the ink supply jar to ink gun.The method of controlled temperature is not particularly limited, thereby and preferred for instance water back unit according to ink flow and envrionment temperature controlled temperature suitably, simultaneously by each temperature sensor monitors.With temperature sensor be placed on ink supply jar and ink gun nozzle near.In addition, in order to prevent the influence of environment, preferred thermal isolation or protection heating head unit to equipment.In order to shorten required starting time of heating or, its and other unit is insulated and reduce the thermal capacitance of whole heating unit in order to reduce the loss of heat energy.

Solidify by the irradiation of dynamic rays and to be sprayed onto the lip-deep ink composite of hydrophilic support.If in ink composite, have sensitizing dye with polymerization starter (light trigger), sensitizing dye in the system is activated to excited state by the assimilating activity ray, when contacting, quickened the decomposition of polymerization starter, and allowed to be cured more delicately reaction with polymerization starter.

The example of dynamic rays comprises alpha-ray, gamma-rays, electron beam, X ray, ultraviolet ray, visible light or infrared rays or the like.The peak wavelength of dynamic rays can change according to the absorbent properties of the sensitization tinting material in the ink composite, but it is 200-600nm for instance, is preferably 300-450nm, and 350-420nm more preferably.In addition, the polymerization initiating system among the present invention is enough responsive for the ray under the low output.Therefore the favourable output of ray for example is to be less than or equal to 2,000mJ/cm ², be preferably 10-2,000mJ/cm ², 20-1 more preferably, 000mJ/cm ², and 50-800mJ/cm more preferably again ²For instance, at 10-2,000mW/cm ²And preferred 20-1,000mW/cm ²Exposure plane illumination under shine dynamic rays.

Be extensive use of mercury lamp, gas or solid statelaser etc. as the dynamic rays source, and in the ultraviolet curing ink-jet printer, be extensive use of mercury lamp and metal halide lamp.But, from environment protection, present press for no mercury device, replacing mercury lamp with GaN semiconductor ultraviolet launching device is very useful on industry or environment.In addition, therefore LED (UV-LEDs) and LD (UV-LDs) size is little, the life-span is long, efficient is high and cost is low has caused people's attention as actinic radiation-curable ink-jet printer light source.

In the present invention, can use photodiode (LED) or laser diode (LD) as the dynamic rays light source.If ultraviolet source is desirable, particularly can use ultraviolet LED or ultraviolet LD.For example, launching main emmission spectrum can obtain from Nichia Corporation at the purple LED of the light of 365-420nm wavelength zone.If have the only preferred of short wavelength more, United States Patent (USP) the 6th, 084, the LED that discloses for No. 250 mainly at 300-370nm wavelength zone divergent-ray.Alternatively, other ultraviolet LED also can be purchased, therefore can the different ray of irradiation ultraviolet radiation band.Most preferred gamma ray source is UV-LED among the present invention, and particularly preferably is the UV-LED of peak wavelength in the 350-420nm scope.

In addition, the maximal illumination of LED on recording medium is preferably 10-2,000mW/cm ², 20-1 more preferably, 000mW/cm ², and be preferably 50-800mJ/cm2 especially.

In the present invention, preferably ink composite is exposed in the dynamic rays for example 0.01-120 second, preferred 0.1-90 second.

The illuminate condition and the basic illuminating method of dynamic rays are disclosed among JP-A 60-132767 number.Specifically, in so-called reciprocal process (shuttle process), promptly expose by mobile ejection head unit and the light source that is arranged in ink discharge device ejection head unit both sides.For some time after ink-jet (0.01-0.5 second for example, preferred 0.01-0.3 second, and more preferably 0.01-0.15 second) back irradiation dynamic rays.Short as far as possible by the control ink-jet time, be sprayed onto the seepage of the printing ink on the recording medium before can preventing to solidify.So, can in addition on the porous recording medium, infiltrate front irradiation printing ink in the impenetrable degree of depth of light at printing ink, suppress the unreacted residual monomer and therefore reduce smell.

Alternatively, can use from the light of another fixed light source sclerosis printing ink.The brochure of WO99/54415 disclose as illuminating method the method for using optical fiber with parallel ultraviolet ray, i.e. method of shining posting field from the specularly reflected jiong directional light that is positioned on the ejection head unit side.

Therefore,, solidify the ink composite of ejection, can on carrier surface, form hydrophobic image by using according to ink composite of the present invention and by the irradiation of dynamic rays according to the method for producing planographic printing plate of the present invention.

Embodiment

Hereinafter, specify the present invention, but be to be understood that the present invention is not subjected to the restriction of these embodiment with reference to embodiment and comparing embodiment.

Embodiment 1-1

The preparation of printing ink

＜Yellow ink 1 〉

-C.I. pigment yellow 13 5 weight parts

-light cationic polymerization initiators: triphenyl sulfosalt

(UV 1-6992 is produced by Dow Chemical Company) 6 weight parts

-sensitizing dye: 9,10-dibutoxy anthracene 3 weight parts

-polymerizable compound

Monomer: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate

(Celoxide 2021A: produce) 35 weight parts by Daicel UCB

Monomer: 3, two (3-the oxetanyl)-5-oxa-nonanes of 7-

(OXT-221: by Toagosei Co., Ltd. produces) 40 weight parts

Monomer: following compound (a-1) 11 weight parts

＜magenta ink 1 〉

-C.I. Pigment red 57:1 5 weight parts

-light cationic polymerization initiators: triphenyl sulfosalt

(UVI-6992 is produced by Dow Chemical Company) 6 weight parts

-sensitizing dye: 9,10-dibutoxy anthracene 3 weight parts

-polymerizable compound

Monomer: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate

(Celoxide 2021A: produce) 35 weight parts by Daicel UCB

Monomer: 3, two (3-the oxetanyl)-5-oxa-nonanes of 7-

(OXT-221: by Toagosei Co., Ltd. produces) 40 weight parts

Monomer: following compound (a-1) 11 weight parts

＜cyan ink 1 〉

-C.I. pigment Blue 15: 35 weight parts

-light cationic polymerization initiators: triphenyl sulfosalt

(UVI-6992 is produced by Dow Chemical Company) 6 weight parts

-sensitizing dye: 9,10-dibutoxy anthracene 3 weight parts

-polymerizable compound

Monomer: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate

(Celoxide 2021A: produce) 35 weight parts by Daicel UCB

Monomer: 3, two (3-the oxetanyl)-5-oxa-nonanes of 7-

(OXT-221: by Toagosei Co., Ltd. produces) 40 weight parts

Monomer: following compound (a-1) 11 weight parts

＜black ink 1 〉

-C.I. Pigment black 75 weight parts

-light cationic polymerization initiators: triphenyl sulfosalt

(UVI-6992 is produced by Dow Chemical Company) 6 weight parts

-sensitizing dye: 9,10-dibutoxy anthracene 3 weight parts

-polymerizable compound

Monomer: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate

(Celoxide 2021A: produce) 35 weight parts by Daicel UCB

Monomer: 3, two (3-the oxetanyl)-5-oxa-nonanes of 7-

(OXT-221: by Toagosei Co., Ltd. produces) 40 weight parts

Monomer: following compound (a-1) 11 weight parts

It is 2 microns strainer that the various thick colored ink 1 of so preparation is filtered by filtering accuracy, obtains versicolor printing ink 1.

The evaluation of ink jet image record and multicolor image

What then, use to be equipped with the piezoelectric ink jet mouth is purchased ink jet recording device document image on recording medium.Ink feeding system is by ink storage tank, supply pipe, just ink supply jar, strainer and the piezoelectric ink jet head before ink gun formed, and insulation and the zone of heating from the ink supply jar to ink gun.With temperature sensor be placed on ink supply jar and shower nozzle mouth near, and the control mentioned nozzle area is always 70 ℃ ± 2 ℃ temperature.Drive ink gun sprays the 8-30pl amount with the resolving power of 720 * 720dpi many sizes point.Adjust exposure system, main-scanning speed and frequency of injection, make at ink jet to recording medium after last 0.1 second, at first with 100mW/cm ²Plane of exposure illumination irradiation UV-A bundle.When making the time shutter variable, the irradiation exposure energy." dpi " among the present invention means counting of every 2.54cm.

According to black, cyan, magenta and xanchromatic order, under 25 ℃ envrionment temperature, pursue-repeat to spray every kind of color ink of preparation like this, and use the metal halide lamp Vzero085 that makes by IntegrationTechnology after each ink-jet, to use UV-irradiation.At every kind of color 100mJ/cm ²Following each image of exposure of constant total exposure energy, thereby completely solidified is sticking when it becomes hand inspection.Go up document image at recording medium (polypropylene screen of the transparent biaxial stretching of the alumina supporter of surface coarsening, the surface finishing that is suitable for printing, soft vinyl chloride sheet and flow coat paper and commercially available recovery paper), and printing ink provides favourable image and does not have point fuzziness on All Media.Even when using described printing ink to form image on no wooden oar paper, printing ink can fully harden before it is seeped into the back side and can not produce the smell that comes from unreacted monomer.In addition, the printing ink that writes down on film is enough flexible, and stripping test is measured according to the glass paper tape, and printing ink does not have crackle when bending film, does not perhaps have adhering problem.

Embodiment 2

＜magenta ink 2 〉

Except in the magenta ink 1 of embodiment 1 preparation, being used as in the monomer of polymerizable compound, outside compound (a-2) the replacement 11 weight part compounds (a-1) with 11 weight parts below, according to the mode preparation red ink 2 similar to magenta ink 1.

Compound (a-2)

Embodiment 3

＜magenta ink 3 〉

Except being used as outside 3 weight parts " 9; 10-dibutoxy anthracene " of sensitizing dye in the magenta ink 1 that replaces preparation in embodiment 1 with 3 weight parts " Darocur ITX (producing) ", according to the mode preparation red ink 3 similar to magenta ink 1 by Ciba Specialty Chemicals.

Embodiment 4

＜magenta ink 4 〉

Except the oxidizing potential below 5 weight parts be+5 weight parts " C.I. Pigment red 57:1 " that the oil-soluble colourant M-1 of 1.37V replaces using in the magenta ink 1 of preparation in embodiment 1, according to the mode preparation red ink 4 similar to magenta ink 1.

Embodiment 5

＜magenta ink 5 〉

Except below 5 weight parts " oil-soluble colourant M-2 (oxidizing potential :+0.94V) " 5 weight parts " C.I. Pigment red 57:1 " that replace using in the magenta ink 1 of preparation in embodiment 1, according to the mode preparation red ink 5 similar to magenta ink 1.

Embodiment 6

＜magenta ink 6 〉

Except being used as " UV1-6992 " of 6 weight parts of light cationic polymerization initiators in the magenta ink 1 that replaces preparation in embodiment 1 with the instantiation compound of listing above (b-39) of 6 weight parts, according to the mode preparation red ink 5 similar to magenta ink 1.

Comparing embodiment 1

＜magenta ink 7 〉

Except in the magenta ink 1 of embodiment 1 preparation, being used as in the monomer of polymerizable compound, with 51 weight parts 3, two (3-the oxetanyl)-5-oxa-nonane (OXT-221: of 7-by Toagosei Co., Ltd. produce) replacement 40 weight parts 3, two (3-the oxetanyl)-5-oxa-nonane (OXT-221: of 7-by Toagosei Co., Ltd. produce) and 11 weight part compounds (a-1) outside, according to the mode preparation red ink 7 similar to magenta ink 1.

Comparing embodiment 2

＜magenta ink 8 〉

Except in the magenta ink 1 of embodiment 1 preparation, being used as in the monomer of polymerizable compound, outside the comparative compound 1 replacement 11 weight part compounds (a-1) with 11 weight parts below, according to the mode preparation red ink 8 similar to magenta ink 1.

It is 2 microns strainer that every kind of crude product red ink 2-8 that will prepare in embodiment 2-6 and comparing

embodiment

1 and 2 filters by absolute filtering accuracy, obtains the printing ink 2-8 of every kind of magenta.

Under the ink-jet temperature, the ink viscosity of the every kind of ink composite for preparing in embodiment and comparing embodiment is all in the scope of 7-20mPas.

(ink jet image record)

By using so every kind of magenta ink 2-8 of preparation in embodiment 2-6 and comparing

embodiment

1 and 2, and the magenta ink 1 of preparation in embodiment 1, according to forming magenta color image with embodiment 1 similar methods.

(ink jet image evaluation)

Curing sensitivity, adhesivity and the thermotolerance of the every kind of image that on commercially available recovery paper, forms according to following method evaluation.Evaluation result is summarised in the following table 1.

1. solidify the measurement of sensitivity

Not amount (the mJ/cm of sticking required exposure energy of imaging surface will be made after the UV irradiation ²) be defined as curing sensitivity.The sensitivity that less value representation is higher.

2. infiltrative evaluation

According to following standard, make the image that is printed on the commercially available recovery paper accept the perviousness evaluation.

A: the visually impermeable and monomeric smell of noresidue

B: the slight smell that slightly permeates and identify residual monomer

C: printing ink obviously is penetrated into the back side and strong residual monomer smell

3. the printing ink evaluation of on shaggy alumina supporter, sprawling

According to following standard, make the image that is printed on the shaggy alumina supporter accept the evaluation that printing ink is sprawled.In addition, the carrier that uses in herein estimating be prepared as follows described.

A: between consecutive point, do not have and sprawl

B: point is slightly sprawled

C: point sprawls and image obviously fades

The production of-carrier-

Use to form and as described in parenthetic, (comprise Al, Si:0.06 weight %, Fe:0.30 weight %, Cu:0.025 weight %, Mn:0.001 weight %, Mg:0.001 weight %, Zn:0.001 weight %, Ti:0.03 weight % and unavoidable impurities) aluminium alloy prepare fused aluminium, and this fused aluminium is filtered and is molded into by the DC casting ingot of 500 mm thick and 1,200 mm wide.With surface grinding machine the surface of aluminium ingot is divided into the average 10 millimeters degree of depth, and aluminium ingot is continued about 5 hours of heating down at 550 ℃, and be rolled into that it is cooled to back thickness under 400 ℃ the temperature is 2.7 millimeters the plate that rolls.In the continuous annealing machine, roll plate again 500 ℃ of following thermal treatments, and the JIS1050 aluminium sheet of cold rolling one-tenth 0.24 mm thick.The width of average crystal grain and length are respectively 50 microns and 300 microns in the gained aluminium sheet.After aluminium sheet is cut into 1,030 mm wide, make it accept following surface treatment.

＜surface treatment 〉

Carry out following various processing (a)-(j) continuously.Remove the treatment soln that remains on the aluminium sheet in each back of handling by nip rolls, and wash with water.

(a) mechanical surface roughening treatment

With rotation roll shape nylon brush mechanical surface alligatoring aluminium sheet, on the surface of aluminium sheet, use proportion simultaneously and be 1.12 aberration (aberrational) pulp suspension of abrasive (float stone) in water.The mean diameter of abrasive particles is 30 microns, and maximum diameter is 100 microns.Nylon brush is made by 6.10 nylon, and the length of bristle and diameter are respectively 45 millimeters and 0.3 millimeter.Nylon brush is received on the stainless steel tube of 300 millimeters of , in it is embedded in wherein hole.Use three rotating brush.Two distances of carrying between the roller (200 millimeters of ) in brush bottom are 300 millimeters.Brush roll firmly is pressed onto on the aluminium sheet, reaches 7kW or the load before the extrusion roll in the above until the CD-ROM drive motor of rotary brush load.The sense of rotation of brush is identical with the direct of travel of aluminium sheet.The speed of rotation of brush is 200rpm.

(b) alkaline etching is handled

By being that 70 ℃ the concentration that comprises is respectively the caustic soda of 2.6 weight % and 6.5 weight % and aluminum ions aqueous solution spray with temperature, and with 10g/m ²Amount dissolving aluminium sheet, the aluminium sheet that comes etching so to obtain.

(c) decontamination (desmutting) is handled

By being that 30 ℃ the aqueous solution spray that comprises 1 weight % concentration nitric acid (aluminum ion that also comprises 0.5 weight %) makes the aluminium sheet decontamination with temperature, wash with water by spray then.The nitrate aqueous solution that uses in used decontamination is handled is at the waste water that uses the AC electric current to discharge in the electrochemical surface roughening treatment step in aqueous nitric acid.

(d) electrochemical surface roughening treatment

Then, by applying 60-Hz AC voltage electrochemistry continuous surface alligatoring aluminium sheet.The electrolyte solution that uses is the aqueous solution of the nitric acid (also comprising the aluminum ion of 5g/L and the ammonium ion of 0.007 weight %) that comprises 10.5g/L, and fluid temperature is 50 ℃.Under the duty ratio (duty ratio) in the current transitions period and 1: 1 of from 0 to 0.8 millisecond of peak value TP, use trapezoidal alternating-current and use carbon dioxide process carbon electrode to carry out the electrochemical surface roughening treatment as counter electrode.The supplementary anode that uses is a ferrite.Current density is 30A/dm to the maximum ², and when using aluminium sheet as anode, the total amount that applies electric current is 220C/dm ²Shunting is from the one part of current (5%) of power supply and give supporting electrode.

Subsequently, wash aluminium sheet with water by spray.

(e) alkaline etching is handled

By with 32 ℃ comprise that concentration is respectively the caustic soda of 26 weight % and 6.5 weight % and aluminum ions aqueous solution spray and with 0.50g/m ²Amount dissolving aluminium sheet come the etching aluminium sheet, and use the AC electric current in the above-mentioned stage, removing what produce in the electrochemical surface roughening treatment mainly is the stain of aluminium hydroxide and the edge section of dissolving bit, thereby makes the edge section level and smooth.Subsequently, wash aluminium sheet with water by spray.

(f) decontamination is handled

By being that 30 ℃ the aqueous sulfuric acid that comprises 15 weight % (aluminum ion that also comprises 4.5 weight %) spray makes the aluminium sheet decontamination with temperature, wash with water by spray then.The aqueous nitric acid that uses in decontamination is handled is from the waste water in the step of using the electrochemical surface roughening treatment in aqueous nitric acid of AC electric current.

(g) electrochemical surface roughening treatment

By applying 60-Hz AC voltage electrochemistry continuous surface alligatoring aluminium sheet.The electrolyte solution that uses is that temperature is the aqueous hydrochloric acid (aluminum ion that also comprises 5g/L) of 35 ℃ 5.0g/L.Under the duty ratio in the current transitions period and 1: 1 of from 0 to 0.8 millisecond of peak value TP, use trapezoidal alternating current and use carbon dioxide process carbon electrode to carry out the electrochemical surface roughening treatment as counter electrode.The supplementary anode that uses is a ferrite.Current density is 25A/dm to the maximum ², and when using aluminium sheet as anode, the total amount that applies electric current is 50C/dm ²Subsequently, wash aluminium sheet with water by spray.

(h) alkaline etching is handled

By with 32 ℃ comprise that concentration is respectively the caustic soda of 26 weight % and 6.5 weight % and aluminum ions aqueous solution spray and with 0.12g/m ²Amount dissolving aluminium sheet come the etching aluminium sheet, and mainly be the stain of aluminium hydroxide and the edge section of dissolving bit, thereby make the edge section level and smooth by using the AC electric current in the above-mentioned stage, remove what in the electrochemical surface roughening treatment, produce.Subsequently, wash aluminium sheet with water by spray.

(i) decontamination is handled

By being that aqueous sulfuric acid (aluminum ion that also the comprises 0.5 weight %) spray of 60 ℃ 25 weight % makes the aluminium sheet decontamination with temperature, wash with water by spray then.

(j) anodic oxidation treatment

Anode alumina plate in anodic oxidation equipment (length of first and second electrolysis cells: 6 meters, the length of first and second power subsystem: 3 meters, and the unitary length of first and second power electrodes: 2.4 meters).The electrolyte solution of supplying with first and second electrolysis cells is a sulfuric acid.Electrolyte solution is that temperature is the aqueous sulfuric acid (aluminum ion that also comprises 0.5 weight %) of 20 ℃ 50g/L.Then, wash aluminium sheet with water by spray.So the final quantity of the oxide skin of preparation is 2.7g/m ²

4. the adhesivity evaluation of surface coarsening alumina supporter

Prepare two support samples that obtain above with printed images, the sample that does not have a cut with cut sample with 100 square parts of images that printing surfaces form by interval on vertical and horizontal direction with 11 lines according to JIS K5400 with 1 millimeter; On each printing surface, paste Cellotape  and peel off fast with the angles of 90 degree; And according to residual and unpeeled printed images of following standard evaluation or square parts of images.

A: in the band stripping test, do not have printed images to peel off

B: light spalling in the band stripping test, but when not cutting the printing ink face, almost do not peel off

C: under two kinds of conditions, all use Cellotape  tape stripping image easily

5. printing durability evaluation

In Heidel KOR-D machine, use the alumina supporter of the surface coarsening that is loaded with the image for preparing above to form image continuously, and determine the relative populations (with respect to printing 150 times) of printable paper with the magenta ink 1 that obtains among the embodiment 1 as printing plate.The printing durability that bigger value representation is higher.

6. the evaluation of stability in storage

The printing ink of preparation is placed on 75%RH and stores 3 days 60 ℃ times, under injection temperature, measure ink viscosity then.The increase of ink viscosity is represented with the viscosity ratio of (storing the back)/(before storing).Think that viscosity does not have to change and viscosity ratio has good preservation stability near 1.0 printing ink, and think that viscosity ratio is lower than 1.5 printing ink and has stability in storage.

Provided the evaluation structure of gained in the following table 1.

Table 1

	Magenta ink number	Solidification rate (mJ/cm ²)	Perviousness	Printing ink is sprawled	Adhesivity	Printing patience	Stability in storage
	Magenta ink number	Solidification rate (mJ/cm ²)	Perviousness	Printing ink is sprawled	Adhesivity	Printing patience	Stability in storage	Embodiment
1	1	70	A	A	A	150	1.2	Embodiment
1	1	70	A	A	A	150	1.2	Embodiment 2	2	80	A	A	A	140	1.2
Embodiment 3	3	70	A	A	A	150	1.2	Embodiment 2	2	80	A	A	A	140	1.2
Embodiment 3	3	70	A	A	A	150	1.2	Embodiment 4	4	80	A	A	A	150	1.2
Embodiment 5	5	80	A	A	A	150	1.2	Embodiment 4	4	80	A	A	A	150	1.2
Embodiment 5	5	80	A	A	A	150	1.2	Embodiment 6	6	40	A	A	A	150	1.2
Comparing embodiment 1	7	250	C	C	C	70	1.4	Embodiment 6	6	40	A	A	A	150	1.2
Comparing embodiment 1	7	250	C	C	C	70	1.4	Comparing embodiment 2	8	300	C	C	C	60	1.2

Embodiment 7

((LED) forms image by photodiode)

Except using the magenta ink 1 for preparing among the embodiment 1 and using the diode (UV-LED) of emission UV-light to replace by Integration Technology Co., Ltd. outside the metal halide lamp VzeroO85 of Zhi Zaoing, according to carrying out the ink jet image record with embodiment 1 similar methods.

In the present embodiment, use the NCCUO33 that makes by Nichia Corp. as UV-LED.This LED comprises the single chip of the UV-light that produces wavelength 365nm and when passing through the electric current of about 500mA, launches the light of about 100mW from chip.With a plurality of this chips of 7 millimeters be spaced, and on the surface of recording medium (hereinafter to be referred as medium), obtain 0.3W/cm ²Power.Change from the speed that can transmit by medium to time of exposure and time shutter under the droplets of ink and the delivery direction of ink gun and the distance the LEDs.In the present embodiment, after ink deposition, expose about 0.5 second the time.

According to setting, can adjust the exposure energy that shines on the medium at 0.01-15J/cm for the distance and the medium transfer rate of distance medium ²Value in the scope.

Comparing embodiment 3

(forming image) by photodiode (LED)

Except the magenta ink 1 that the magenta ink 7 that uses preparation in comparing embodiment 1 replaces using among the embodiment 7, according to carrying out the ink jet image record with embodiment 7 similar methods.

(evaluation of ink jet image)

According to embodiment 1-6 and comparing

embodiment

1 and 2 in identical method, for the various picture appraisals that aforesaid method forms according to the present invention solidify required sensitivity, in commercially available recovery paper perviousness, printing ink on shaggy alumina supporter sprawl, adhesivity, printing patience and stability in storage.Evaluation result provides in table 2.

Table 2

	Magenta ink number	Solidification rate (mJ/cm ²)	Perviousness	Printing ink is sprawled	Adhesivity	Printing patience	Stability in storage
	Magenta ink number	Solidification rate (mJ/cm ²)	Perviousness	Printing ink is sprawled	Adhesivity	Printing patience	Stability in storage	Embodiment
7	1	50	A	A	A	130	1.2	Embodiment
7	1	50	A	A	A	130	1.2	Comparing embodiment 3	7	200	A	A	A	50	1.2

When comparing between the situation of the diode of launching UV-light in the situation and the use as shown in table 2 of use UV lamp as shown in table 1, use the situation of the diode of emission UV-light to have higher sensitivity as can be seen, and when being used for making printing plate, form image with higher printing patience (printing resistance) for x ray exposure x.

Comparing embodiment 4

Except the following comparative compound 2 that uses 11 weight parts replaces being used as the compound (a-1) of polymerizable compound in the magenta ink 1 of preparation in embodiment 1 of 11 weight parts, according to magenta ink 1 similar methods preparation red ink 9.The magenta ink 9 that is obtained has relatively poor solidification rate and high viscosity.The solidification rate and the viscosity of measured magenta ink 9 are as shown in table 3.Give the solidification rate and the viscosity of the magenta ink 1 of preparation among the embodiment 1 in the table 3.Viscosity is to use B-type viscometer (LVDV-I, by Brookfield Engineering Laboratories produce) to record under 20rpm and 20 ℃.

Comparative compound 2

Table 3

	The magenta ink numbering	Solidification rate (mJ/cm ²)	Viscosity (mPa)
	The magenta ink numbering	Solidification rate (mJ/cm ²)	Viscosity (mPa)	Embodiment 1	1	70	25
Comparing embodiment 4	9	120	90	Embodiment 1	1	70	25

Embodiment 8

500 milliliters of three-necked bottles that are equipped with prolong and two dropping funnels are provided.KOH solution, 4.99 gram (14.7 mmole) Tetrabutyl amonium bromide and 200 milliliters of hexanes of in these 500 milliliters of three-necked bottles, adding 100 grams, 50 weight %.In addition, use cooling bath that mixture is cooled to 0 ℃.34.85 gram (0.3 mole) 3-ethyl-3-oxetane methanol are placed in the dropping funnel, and 45.87 gram (0.33 mole) 2-bromotrifluoromethane methyl ethers are placed in another dropping funnel, and since two funnels while and dripping lentamente.After 1 hour, dropping liquid is finished, and does not carry out any variation, continues to stir 30 minutes.Then, with mixture heating up to room temperature, and restir 1 hour.Use oil bath that outside temperature is increased to 80 ℃, and continue again to stir 4 hours.After reaction is finished, water and saturated brine purging compound, dry on sal epsom, filter then.Concentrated filtrate on evaporimeter.Use the spissated filtrate of silica gel column purification (developping agent solution: hexane/ethyl acetate=9/1).Obtain the required compound 1 (having following structure) of 13.14 grams thus.The structure of compound 1 by ¹H-NMR confirms.Compound 1 ¹H-NMR figure provides in Fig. 1.

Embodiment 9

The 1 liter of three-necked bottle that is equipped with prolong and two dropping funnels is provided.KOH solution, 5.1 gram (15.0 mmole) Tetrabutyl amonium bromide and 400 milliliters of hexanes of in this three-necked bottle of 1 liter, adding 200 grams, 50 weight %.In addition, use cooling bath that mixture is cooled to 0 ℃.34.85 gram (0.3 mole) 3-ethyl-3-oxetane methanol are placed in the dropping funnel, and 95.1 gram (0.33 mole) Diethylene Glycol ethyltoluene sulfonyl ether are placed in another dropping funnel, and since two funnels, drip simultaneously and lentamente.After 1 hour, dropping liquid is finished, and does not carry out any variation, continues to stir 30 minutes.Then, with mixture heating up to room temperature, and restir 1 hour.Use oil bath that outside temperature is increased to 80 ℃, and continue again to stir 4 hours.After reaction is finished, water and saturated brine purging compound, dry on sal epsom, filter then.Concentrated filtrate on evaporimeter.Use the spissated filtrate of silica gel column purification (developping agent solution: hexane/ethyl acetate=9/1).Obtain the required compound (a-1) (having following structure) of 5.0 grams thus.The structure of compound (a-1) by ¹H-NMR confirms.Compound (a-1) ¹H-NMR spectrum provides in Fig. 2.

So the of the present invention novel trimethylene oxide that obtains has excellent reactivity, and can be used as the polymerizable components in the curable compositions, and it uses with cationic polymerization initiators.This curable compositions can advantageously be applied to printing ink, tackiness agent, coating agent of ultraviolet curing etc.

In order to set forth and to illustrate, provided the above stated specification of embodiment of the present invention.These explanations are non-be exclusiveness or limit the invention to disclosed exact form.Significantly, many modifications and variations will be tangible for those skilled in the art.In order to explain principle of the present invention and practical application thereof best, select and illustrated embodiment, thereby make others skilled in the art understand the present invention at the various embodiments and the various variation of the concrete application that is fit to be considered.Scope of the present invention is limited by following claim and Equivalent thereof.

All documents, patent application and the technological standard of mentioning in this specification sheets all is incorporated herein for referencial use, and each independent document, patent application and technological standard are for referencial use just as specifically and separately quoting.

Claims

1. curable compositions, it comprises following compound: described compound has single comprising by the part-structure of 4 Yuans cyclic ethers of following general formula (I) expression or more Yuans cyclic ethers with by the part-structure of following general formula (II) expression:

Wherein in general formula (II), R ¹Expression alkylidene group, ring alkylidene group or arylidene, and n represents the integer of 1-8.

2. the curable compositions of claim 1, the part-structure of its formula of (I) expression is the trimethylene oxide structure with three carbon atoms, and in the part-structure by general formula (II) expression, R ¹Be alkyl, and n represent the integer of 2-4 with 1-4 carbon atom.

3. the curable compositions of claim 1, it further comprises the compound that is selected from epoxy compounds, Vinyl Ether compound and oxetane compound, and described oxetane compound is not included in the compound of part-structure of described part-structure with general formula (I) expression and general formula (II) expression.

4. the curable compositions of claim 1, it further comprises by the acidic compound of radiation exposure.

5. the ink composite that comprises the curable compositions of claim 1.

6. the ink composite of claim 5, it further comprises tinting material.

7. the ink composite of claim 6, wherein said tinting material is pigment or oil-soluble colourant.

8. the ink composite of claim 7, the oxidizing potential of wherein said oil-soluble colourant is more than or equal to 1.0V (SCE relatively).

9. the ink composite of claim 5, wherein said ink composite is used for ink-vapor recording.

10. ink jet recording method, it comprises: the ink composite that sprays claim 5 by ink jet recording device on recording medium; Solidify the ink composite of ejection then by the irradiation of dynamic rays.

11. the ink jet recording method of claim 10, wherein said dynamic rays is the ultraviolet ray of sending from photodiode, the ultraviolet peak wavelength of described photodiode emission in the 350-420nm scope and its maximal illumination on the recording medium surface be 10-2,000mW/cm ²

12. pass through the printing material of the ink jet recording method record of claim 11.

13. produce the method for planographic printing plate, it comprises the ink composite that sprays claim 5 on carrier; Solidify the ink composite of ejection then by the irradiation of dynamic rays, thereby form hydrophobic image.

14. pass through the planographic printing plate that the method for the production planographic printing plate of claim 13 is produced.

15. the compound of representing by following logical formula V:

16. the compound of claim 15, wherein in logical formula V, R ^1AExpression has the alkyl of 1-4 carbon atom, R ^3AExpression has the alkyl of 1-4 carbon atom, and R ^4AExpression has the alkyl of 1-4 carbon atom.