Developer agent for positive type photosensitive compound

Information

  • Patent Grant
  • 7157213
  • Patent Number
    7,157,213
  • Date Filed
    Monday, March 1, 2004
    20 years ago
  • Date Issued
    Tuesday, January 2, 2007
    18 years ago
Abstract
There is provided a developer agent for a positive type photosensitive compound having a near infrared wave length region laser sensitive characteristic in which a photosensitive portion of the compound exposed and reacted with a laser of the near infrared wavelength region is enabled to be dissolved in the developer liquid. This developer agent contains a) water; b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, ortho silicate soda, etc., applied as either organic or non-organic alkali capable of becoming a major material; and c) potassium pyrophosphate, tripolyphosphate soda, etc., applied as liquid agent having dampening action for preventing a reduction in pH value.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


This invention relates to a developer agent for a positive type photosensitive compound having a near-infrared wavelength region laser sensitive characteristic in which a photosensitive portion of the compound exposed and reacted with a laser of the near-infrared wavelength region is enabled to be solubilized in the developer liquid.


2. Description of the Related Art


As the prior art positive type photosensitive compound having a near infrared wave length region laser sensitive characteristic in which a photosensitive portion of the compound exposed and reacted with a laser of the near infrared wavelength region is enabled to be dissolved in the developer liquid, it is possible to refer to the following technical documents.

  • [Patent Document 1] Japanese Patent Laid-Open No. Hei 10(1998)-26826
  • [Patent Document 2] Japanese Patent Laid-Open No. Hei 10(1998)-90881
  • [Patent Document 3] Japanese Patent Laid-Open No. Hei 10(1998)-161304
  • [Patent Document 4] Japanese Patent Laid-Open No. Hei 11(1999)-231515
  • [Patent Document 5] Japanese Patent Laid-Open No. Sho 61(1986)-167948


Using of the developer agent commercially available at the market in the practical gravure printing showed that developing of one roll caused the developer agent to deteriorate in quality at once and developing of the second roll and its subsequent rolls could not be performed at all.


In order to apply the developer agent practically to the gravure printing operation, it is desired to have a capability of developing at least about 100 rolls. In addition, it is also desired to have no probability that the developing capability diminishes and the developing operation cannot be carried out due to quite low aging deterioration in the processing capability when a developing operation is carried out after elapsing by 2 to 3 days through one week, and cleaning or washing is carried out again after discharging out all the developing liquid in the developing tank.


SUMMARY OF THE INVENTION

The present invention has been invented in view of the aforesaid circumstances and it is an object of the present invention to provide a developer agent for positive type photosensitive compound having no probability that the developing capability diminishes and the developing operation cannot be carried out when the developing operation is performed after elapsing by 2 to 3 days through one week, and all the developer liquid in a developing tank is discharged and replaced with new liquid because it has a capability of sufficiently developing 100 or more rolls, preferably about 300 to 400 rolls enabled to be practically applied for a process roll for a gravure printing and an aging deterioration in the processing capability is quite low.


The invention described in claim 1 of the present invention provides a developer agent for positive type photosensitive compound having a near-infrared wavelength region laser sensitive characteristic in which a photosensitive portion of the compound exposed and reacted with a laser of the near-infrared wavelength region is enabled to be solubilized in developer liquid, wherein the same is comprised of:

    • a) water;
    • b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapropyl ammonium hydroxide, ortho silicate soda, potassium hydroxide, sodium hydroxide, sal soda applied as either organic or non-organic alkali capable of becoming a major material; and
    • c) either one of or two kinds or more of potassium pyrophosphate, tripolyphosphate soda, hexametaphosphoric soda, triphosphate soda and monophosphate soda applied as liquid agent having dampening action for preventing a reduction in pH value.


EFFECT OF THE INVENTION

In accordance with the developer agent for positive type photosensitive compound of the present invention, original liquid and water are mixed to each other to clean or wash, positive type photosensitive compound is applied to coat on the roll for a gravure printing and to form a coated photosensitive film, near-infrared wavelength region laser is illuminated and radiated, the film is exposed to the laser to draw a positive type latent image, then developing operation is carried out, resulting in that even if 300 or more rolls are processed, it keeps a pH value of 13.0 or more in a stable manner, a clear pattern can be attained in a short period of time, a superior developing state can be realized. Additionally, an aging deterioration in the processing capability is quite low, so that even if the developing operation is carried out after elapsing by 2 to 3 days through one week, there is no probability that the developing capability diminishes, the developing operation cannot be performed and all the developer liquid in the developing tank are discharged out of the tank and replaced with new developer liquid. 500 rolls could be developed and processed after supplementing new rolls corresponding to the number of processed rolls every time the roll was developed with developer liquid of 50 litters because the aging deterioration in the processing capability was quite low.







PREFERRED EMBODIMENT OF THE INVENTION

The present invention provides a developer agent for positive type photosensitive compound having a near infrared wavelength region laser sensitive characteristic in which a photosensitive portion of the compound exposed and reacted with a laser of near infrared wavelength region is enabled to be dissolved in developer liquid.


As the positive type photosensitive compound, it is possible to apply compound including alkaline soluble organic high molecular substances having at least one kind of phenolic hydroxyl group such as novolac resin, resol resin, polyphenol resin and copolymer of acrylic acid derivative having phenolic hydroxyl group; and photo-thermal conversion pigment such as organic or non-organic pigment or dye, organic pigment, metal, metal oxide, metal carbide and metal boride and the like having an absorbing band at a part of or all of the near infrared region with a wavelength region of 650 to 1300 nm so as to absorb near infrared rays and converting it into heat. It is preferable that this positive type photosensitive compound contains closeness improving agent.


It is preferable that an inclusion rate of the alkaline soluble organic high-molecular substance in the positive type photosensitive compound is 2 to 98 wt % and it is further preferable that it is 30 to 90 wt %. It is preferable that an inclusion rate of the photo-thermal conversion pigment in the positive type photosensitive compound is 2 to 60 wt % and it is further preferable that it is 3 to 50 wt %.


This positive type photosensitive compound is normally processed to become a positive type photosensitive film having the photosensitive compound layer formed on the surface of the supporting member in such a way that this compound is coated on either a copper plated surface or a copper sulphate plated surface of the process roll for gravure printing of the surface of the supporting member as solution having each of the aforesaid compositions dissolved in solvents such as Cellosolve type solvent, propylene glycol type solvent and the like, thereafter this is heated and dried with a heater or is not heated and not dried with a heater. A rate of application of the solvent in respect to a total amount of photosensitive compound is normally in a range of about 1 to 20 times by a weight ratio.


As the coating method, it is possible to apply a kiss-coating, a dip-coating, a rotary coating, a roll-coatings a wire bar coating, an air knife coating, a blade coating and a curtain coating and the like. A coating amount is preferably in a range of about 3 to 6 μm.


Alkaline soluble organic high molecular substance having phenolic hydroxyl group is a major composition to form a resist, and this is a binder resin having a low adherence to either a copper plating surface or a copper sulphate plating surface, wherein a major chain portion or side chain portion of the molecules is cut by heat, it becomes a low molecule where the alkaline soluble characteristic is further improved and a part of it is makes abilation.


As alkaline soluble organic high molecular substance having a phenolic hydroxyl group, alkaline soluble high molecular substance having a phenolic hydroxyl group described in Japanese Patent Laid-Open No. Hei 11 (1999)-231515 such as novolac resin, resol resin, polyvinylphenol resin and copolymer of acrylic acid derivative having phenolic hydroxyl group and the like can be applied as they are and in particular, novolac resin or polyvinylphenol resin is preferable.


Novolac resin is resin in which at least one kind of phenols is copolymerized with at least one kind of aldehydes or ketons under a presence of acid catalyst. In particular, mixed phenols including m-cresol, p-cresol, 2,5-Xylenol, 3,5-Xylenol and resolcinol; or polycondensation material of mixed phenols including phenol, m-cresol and p-cresol, and formaldehyde, where a weight-average molecular weight (MW) in conversion of polystylene through a gel permeation chromatography measurement is preferably 1,500 to 10,000.


Resol resin is resin similarly polycondensated except the fact that alkaline catalyst is used in place of acid catalyst in polycondensation of novolac resin.


Polyvinyl phenol resin is resin in which either one kind of or two kinds or more of hydroxystylene, for example, are polymerized under a presence of radical polymerization initiator or cation polymerization initiator. It is preferable to apply either a polymerization substance of hydroxystylene having alkyl group with carbon numbers 1 to 4 in a benzene ring as substituent or polymerization substance of hydroxystylene of benzene ring with no substituent.


Photothermal conversion pigment has an absorbing region at a part of or an entire near-infrared wavelength region of 650 to 1300 nm, a characteristic for absorbing a laser beam in the near-infrared wavelength region and providing a thermal decomposition and contributes to a low molecular formation of alkaline solubilization and ablasion caused by thermal cutting of molecules in alkaline soluble organic high-molecular substance having the aforesaid phenolic hydroxyl group.


As photothermal conversion pigment, the photothermal conversion pigment described in Japanese Patent Laid-Open No. Hei 11 (1999)-231515 such as organic or non-organic pigment or dyestuff, organic pigment, metal, metal oxide, metal carbide, metal boride and the like having an absorbing region at either a part of or an entire near-infrared region of 650 to 1300 nm can be applied fully as they are, and so-called cyanine type pigment in a broad sense or the like can be applied as a representative one in which complex rings including nitrogen atom, oxygen atom or sulfur atom and the like are coupled with polymethine (—CH═)n, and more practically, quinoline type (so-called cyanine type), indole type (so-called indocyanine type), benzothiazole type (so-called thiocyanine type), iminocyclohexadiene type (so-called polymethine type), pyrylium type, thiapyrylium type, squarylium type, chroconium type, and azulenium type can be applied and in particular, it is preferable to apply quinoline type, indole type, benzothiazole type, iminocyclohexadiene type, pyrylium type, thiapyrylium type.


The developer agent of the present invention includes a) water; b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapropyl ammonium hydroxide, ortho silicate soda, potassium hydroxide sodium hydroxide, sal soda applied as either organic or non-organic alkali capable of becoming a major material; and c) either one of or two kinds or more of potassium pyrophosphate, tripolyphosphate soda, hexametaphosphoric soda, triphosphate soda and monophosphate soda applied as liquid agent having dampening action for preventing a reduction in pH value.


Surface active agent and developing promoter agent can be added in their appropriate rate.


As this water, either distilled water or tap water can be used.


PREFERRED EMBODIMENT OF THE INVENTION

Preferred embodiments in Tables 1 to 15 and the comparative example in Table 16 were carried out such that a process roll was fixed to a photosensitive film coating device (manufactured by Think Laboratory Co., Ltd.) installed in a coating chamber kept at a humidity of 40%, a positive type photosensitive compound (manufactured by Mitsubishi Chemical Co., Ltd.) was coated on the roll, then it was dried up to 130° C., a positive type photosensitive film was formed in such a way that its residual solvent might become 2% or less and its film thickness might become about 2 to 3 μm, a laser with a wavelength of 830 nm was illuminated, radiated to cause the film to be exposed, a positive type latent image was drawn on it and the tested roll was made and a development was carried out.


Original liquid of developer agent for positive type photosensitive compound with a rate of composition indicated in each of the preferred embodiments in the tables was made, water and the original liquid was applied to clean the tank with a rate of 3:1 so as to cause the tank in the developing device to become full (50 litters), a developing was carried out at 25° C., and a presence or non-presence of the residual substance, aging capability and developing processing capabilities were checked. The developing processing capability was calculated through a conversion of area after performing an entire developing operation for a non-exposed roll.




















TABLE 1







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*EEm-
*Em-



bdmt 1
bdmt 2
bdmt 3
bdmt 4
bdmt 5
bdmt 6
bdmt 7
bdmt 8
bdmt 9
bdmt 10



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



hosphate soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



monophosphate













soda



potassium













pyrophosphate



tripoly-













phosphate soda



hexamethaphos-













phate soda



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
o



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing







Δ
Δ
Δ



capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls


Δ: 300 rolls
























TABLE 2







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 11
bdmt 12
bdmt 13
bdmt 14
bdmt 15
bdmt 16
bdmt 17
bdmt 18
bdmt 19
bdmt 20



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-













hosphate soda



monophosphate
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



potassium













pyrophosphate



tripoly-













phosphate soda



hexamethaphos-













phate soda



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
o



characteristic
residual
residual
residual
residual ual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls

























TABLE 3







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 21
bdmt 22
bdmt 23
bdmt 24
bdmt 25
bdmt 26
bdmt 27
bdmt 28
bdmt 29
bdmt 30



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-













hosphate soda



monophosphate













soda



potassium
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-













phosphate soda



hexamethaphos-













phate soda



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
o



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing







Δ
Δ
Δ



capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls


Δ: 300 rolls
























TABLE 4







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 31
bdmt 32
bdmt 33
bdmt 34
bdmt 35
bdmt 36
bdmt 37
bdmt 38
bdmt 39
bdmt 40



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-













hosphate soda



monophosphate













soda



potassium













pyrophosphate



tripoly-
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



phosphate soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



hexamethaphos-













phate soda



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls

























TABLE 5







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 41
bdmt 42
bdmt 43
bdmt 44
bdmt 45
bdmt 46
bdmt 47
bdmt 48
bdmt 49
bdmt 50



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-













hosphate soda



monophosphate













soda



potassium













pyrophosphate



tripoly-













phosphate soda



hexamethaphos-
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



phate soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls

























TABLE 6







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 51
bdmt 52
bdmt 53
bdmt 54
bdmt 55
bdmt 56
bdmt 57
bdmt 58
bdmt 59
bdmt 60



























b
tetramethyl

4.6











ammonium

wt %



hydroxide



tetrabutyl


4.6










ammonium


wt %



hydroxide



tetrapropyl



4.6









ammonium



wt %



hydroxide



benzyltriethyl




4.6








ammonium




wt %



hydroxide



benzyltrimethyl





4.6







ammonium





wt %



hydroxide



orthosilicic






4.6






soda






wt %



potassium







4.6





hydroxide







wt %



sodium








4.6




hydroxide








wt %



sal soda









4.6













wt %


c
tri-
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2



hosphate soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



monophosphate
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2



soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



potassium
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-













phosphate soda



hexamethaphos-













phate soda



Total amount
100
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good
good



capability



**Processing







Δ
Δ
Δ



capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls


Δ: 300 rolls























TABLE 7







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 61
bdmt 62
bdmt 63
bdmt 64
bdmt 65
bdmt 66
bdmt 68
bdmt 69
bdmt 70


























b
tetramethyl

2.4










ammonium

wt %



hydroxide



tetrabutyl


2.4









ammonium


wt %



hydroxide



tetrapropyl



2.4








ammonium



wt %



hydroxide



benzyltriethyl




2.4







ammonium




wt %



hydroxide



benzyltrimethyl





2.4






ammonium





wt %



hydroxide



orthosilicic
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4



soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



potassium






2.4





hydroxide






wt %



sodium







2.4




hydroxide







wt %



sal soda








2.4












wt %


c
tri-
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



hosphate soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



monophosphate












soda



potassium












pyrophosphate



tripoly-












phosphate soda



hexamethaphos-












phate soda



Total amount
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good



capability



**Processing






Δ
Δ
Δ



capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls


Δ: 300 rolls























TABLE 8







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 71
bdmt 72
bdmt 73
bdmt 74
bdmt 75
bdmt 76
bdmt 78
bdmt 79
bdmt 80


























b
tetramethyl

2.4










ammonium

wt %



hydroxide



tetrabutyl


2.4









ammonium


wt %



hydroxide



tetrapropyl



2.4








ammonium



wt %



hydroxide



benzyltriethyl




2.4







ammonium




wt %



hydroxide



benzyltrimethyl





2.4






ammonium





wt %



hydroxide



orthosilicic
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4



soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



potassium






2.4





hydroxide






wt %



sodium







2.4




hydroxide







wt %



sal soda








2.4












wt %


c
tri-












hosphate soda



monophosphate












soda



potassium
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-












phosphate soda



hexamethaphos-












phate soda



Total amount
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good



capability



**Processing






Δ
Δ
Δ



capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls


Δ: 300 rolls























TABLE 9







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 81
bdmt 82
bdmt 83
bdmt 84
bdmt 85
bdmt 86
bdmt 87
bdmt 89
bdmt 90


























b
tetramethyl

2.4










ammonium

wt %



hydroxide



tetrabutyl


2.4









ammonium


wt %



hydroxide



tetrapropyl



2.4








ammonium



wt %



hydroxide



benzyltriethyl




2.4







ammonium




wt %



hydroxide



benzyltrimethyl





2.4






ammonium





wt %



hydroxide



orthosilicic






2.4





soda






wt %



potassium
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4



hydroxide
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



sodium







2.4




hydroxide







wt %



sal soda








2.4












wt %


c
tri-












hosphate soda



monophosphate












soda



potassium
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-












phosphate soda



hexamethaphos-












phate soda



Total amount
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No



characteristic
residual ual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls
























TABLE 10







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt 91
bdmt 92
bdmt 93
bdmt 94
bdmt 95
bdmt 96
bdmt 97
bdmt 98
bdmt 100


























b
tetramethyl

2.4










ammonium

wt %



hydroxide



tetrabutyl


2.4









ammonium


wt %



hydroxide



tetrapropyl



2.4








ammonium



wt %



hydroxide



benzyltriethyl




2.4







ammonium




wt %



hydroxide



benzyltrimethyl





2.4






ammonium





wt %



hydroxide



orthosilicic






2.4





soda






wt %



potassium







2.4




hydroxide







wt %



sodium
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4



hydroxide
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



sal soda








2.4












wt %


c
tri-












hosphate soda



monophosphate












soda



potassium
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-












phosphate soda



hexamethaphos-












phate soda



Total amount
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls
























TABLE 11







*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt



101
102
103
104
105
106
107
108
109


























b
tetramethyl

2.4










ammonium

wt %



hydroxide



tetrabutyl


2.4









ammonium


wt %



hydroxide



tetrapropyl



2.4








ammonium



wt %



hydroxide



benzyltriethyl




2.4







ammonium




wt %



hydroxide



benzyltrimethyl





2.4






ammonium





wt %



hydroxide



orthosilicic






2.4





soda






wt %



potassium







2.4




hydroxide







wt %



sodium








2.4



hydroxide








wt %



sal soda
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4




wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


c
tri-












hosphate soda



monophosphate












soda



potassium
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-












phosphate soda



hexamethaphos-












phate soda



Total amount
100
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good
good



capability



**Processing
Δ
Δ
Δ
Δ
Δ
Δ
Δ

custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls





















TABLE 12







*Em-
*Em-
*Em-
*Em-
*Em-
*Em-



bdmt
bdmt
bdmt
bdmt
bdmt
bdmt



111
112
113
114
115
116























b
tetramethyl

2.4







ammonium

wt %



hydroxide



tetrabutyl


2.4






ammonium


wt %



hydroxide



tetrapropyl



2.4





ammonium



wt %



hydroxide



benzyl-




2.4




triethyl




wt %



ammonium



hydroxide



benzyl-





2.4



trimethyl





wt %



ammonium



hydroxide



ortho-
1.2
1.2
1.2
1.2
1.2
1.2



silicic
wt %
wt %
wt %
wt %
wt %
wt %



soda



potassium
0.6
0.6
0.6
0.6
0.6
0.6



hydroxide
wt %
wt %
wt %
wt %
wt %
wt %



sodium
0.6
0.6
0.6
0.6
0.6
0.6



hydroxide
wt %
wt %
wt %
wt %
wt %
wt %



sal soda








c
tri-
1.2
1.2
1.2
1.2
1.2
1.2



hosphate
wt %
wt %
wt %
wt %
wt %
wt %



soda



mono-









phosphate



soda



potassium
3.6
3.6
3.6
3.6
3.6
3.6



pyro-
wt %
wt %
wt %
wt %
wt %
wt %



phosphate



tripoly-









phosphate



soda



hexa-









methaphos-



phate soda



Total amount
100
100
100
100
100
100



including
wt %
wt %
wt %
wt %
wt %
wt %



water


Re-
Developing
No
No
No
No
No
No


sults
characte-
re-
re-
re-
re-
re-
re-



istic
sid-
sid-
sid-
sid-
sid-
sid-




ual
ual
ual
ual
ual
ual



Aging
good
good
good
good
good
good



capability



**Processing









capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


◯: 600 rolls




















TABLE 13







Embodiment
Embodiment
Embodiment
Embodiment
Embodiment
Embodiment



121
122
123
124
125
126























b
tetramethyl

2.4







ammonium

wt %



hydroxide



tetrabutyl


2.4






ammonium


wt %



hydroxide



tetrapropyl



2.4





ammonium



wt %



hydroxide



benzyltriethyl




2.4




ammonium




wt %



hydroxide



benzyltrimethyl





2.4



ammonium





wt %



hydroxide



orthosilicic
1.4
1.4
1.4
1.4
1.4
1.4



soda
wt %
wt %
wt %
wt %
wt %
wt %



potassium









hydroxide



sodium









hydroxide



sal soda
1.0
1.0
1.0
1.0
1.0
1.0




wt %
wt %
wt %
wt %
wt %
wt %


c
tri-
1.2
1.2
1.2
1.2
1.2
1.2



hosphate soda
wt %
wt %
wt %
wt %
wt %
wt %



monophosphate









soda



potassium
3.6
3.6
3.6
3.6
3.6
3.6



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-









phosphate soda



hexamethaphos-









phate soda



Total amount
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good



capability



**Processing









capability





Note:


**Processing capability


◯: 600 rolls






















TABLE 14







*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt
*Embdmt



131
132
133
134
135
136
137
138

























b
tetramethyl











ammonium



hydroxide



tetrabutyl











ammonium



hydroxide



tetrapropyl











ammonium



hydroxide



benzyltriethyl











ammonium



hydroxide



benzyltrimethyl











ammonium



hydroxide



orthosilicic
5.6
5.6
5.6
5.6
6.8
6.8
6.8
6.8



soda
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



potassium
2.0
2.0
2.0
2.0







hydroxide
wt %
wt %
wt %
wt %



sodium
2.0
2.0
2.0
2.0







hydroxide
wt %
wt %
wt %
wt %



sal soda




3.0
3.0
3.0
3.0








wt %
wt %
wt %
wt %


c
tri-
1.2



1.2






hosphate soda
wt %



wt %



monophosphate

1.2



1.2





soda

wt %



wt %



potassium
3.6
3.6
3.6
3.6
3.6
3.6
3.6
3.6



pyrophosphate
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



tripoly-


1.2



1.2




phosphate soda


wt %



wt %



hexamethaphos-



1.2



1.2



phate soda



wt %



wt %



Total amount
100
100
100
100
100
100
100
100



including water
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %


Results
Developing
No
No
No
No
No
No
No
No



characteristic
residual
residual
residual
residual
residual
residual
residual
residual



Aging
good
good
good
good
good
good
good
good



capability



**Processing
Δ

custom character


custom character


custom character

Δ

custom character


custom character


custom character




capability





Note:


*“Embdmt” is an abbreviation of Embodiment.


**Processing capability


Δ: 300 rolls



custom character : 100 rolls



















TABLE 15







Embodi-
Embomi-
Embodi-
Embodi-



ment 141
ment 142
ment 143
ment 144





















b
tetramethyl







ammonium



hydroxide



tetrabutyl







ammonium



hydroxide



tetrapropyl







ammonium



hydroxide



benzyl-







triethyl



ammonium



hydroxide



benzyl-







trimethyl



ammonium



hydroxide



ortho-
4.8
4.8





silicic
wt %
wt %



soda



potassium


3.6
3.6



hydroxide


wt %
wt %



sodium


3.6
3.6



hydroxide


wt %
wt %



sal soda


2.4
2.4






wt %
wt %


c
tri-
1.2

1.2




hosphate
wt %

wt %



soda



mono-







phosphate



soda



potassium
3.6
4.8
3.6
4.8



pyro-
wt %
wt %
wt %
wt %



phosphate



tripoly-







phosphate



soda



hexa-







methaphos-



phate soda



Total amount
100
100
100
100



including
wt %
wt %
wt %
wt %



water


Re-
Developing
No
No
No
No


sults
character-
resid-
resid-
resid-
resid-



istic
ual
ual
ual
ual



Aging
good
good
good
good



capability



**Processing

custom character


custom character


custom character


custom character




capability





Note:


**Processing capability



custom character : 100 rolls

























TABLE 16







***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.
***Cmp.



Embdmt
Embdmt
Embdmt
Embdmt
Embdmt
Embdmt
Embdmt
Embdmt
Embdmt
Embdmt



1
2
3
4
5
6
7
8
9
10



























b
tetra-

9.6











methyl

wt %



ammonium



hydroxide



tetra-


9.6










butyl


wt %



ammonium



hydroxide



tetra-



9.6









propyl



wt %



ammonium



hydroxide



benzyl-




9.6








triethyl




wt %



ammonium



hydroxide



benzyl-





9.6







trimethyl





wt %



ammonium



hydroxide



ortho-






9.6






silicic






wt %



soda



potassium







9.6





hydroxide







wt %



sodium








9.6




hydroxide








wt %



sal soda









9.6













wt %


c
tri-













hosphate



soda



mono-













phosphate



soda



potassium













pyro-



phosphate



tripoly-













phosphate



soda



hexa-



methaphos-













phate soda



Total



amount
100
100
100
100
100
100
100
100
100
100



including
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %
wt %



water


Re-
Developing
Resid-
Resid-
Resid-
Resid-
Resid-
Resid-
Resid-
Resid-
Resid-
Resid-


sults
character-
ual
ual
ual
ual
ual
ual
ual
ual
ual
ual



istic



Aging
bad
bad
bad
bad
bad
bad
bad
bad
bad
bad



capability



**Processing
X
X
X
X
X
X
X
X
X
X



capability





Note:


***“Cmp. Embdmt” is an abbreviation of Comparative Embodiment.


**Processing capability


X: a few rolls





Claims
  • 1. A composition for gravure printing comprising a positive type photosensitive compound for gravure printing having a photosensitive portion exposed and reacted with a near-infrared wavelength region laser, and solubilized in a developer liquid, wherein said developer liquid is comprised of: a) water;b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, beuzyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapropyl ammonium hydroxide, potassium hydroxide, sodium hydroxide, applied as either organic or non-organic alkali capable of becoming a major material; andc) either one of or two kinds or more of hexametaphosphoric soda, triphosphate soda and monophosphate soda applied as liquid agent having dampening action for preventing a reduction in pH value;wherein said developer liquid comprises a pH value of 13.0 or more.
  • 2. A method of developing a photosensitive film comprising coating a positive type photosensitive compound for gravure printing on a roll for gravure printing to form a coated photosensitive film,exposing said photosensitive film to a near-infrared wavelength region laser to draw a positive type latent image, anddeveloping the photosensitive film using a developer liquid, wherein said developer liquid is comprised of:a) water;b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapropyl ammonium hydroxide, potassium hydroxide, sodium hydroxide applied as either organic or non-organic alkali capable of becoming a major material; andc) either one of or two kinds or more of hexametaphosphoric soda, triphosphate soda and monophosphate soda applied as liquid agent having dampening action for preventing a reduction in pH value;wherein said developer liquid comprises a pH value of 13.0 or more.
  • 3. The composition according to claim 1, which comprises monophosphate soda.
  • 4. The method according to claim 2, which comprises monophosphate soda.
  • 5. A composition for gravure printing consisting essentially of a positive type photosensitive compound for gravure printing having a photosensitive portion exposed and reacted with a near-infrared wavelength region laser, and solubilized in a developer liquid, wherein said developer liquid is comprised of: a) water;b) either one of or two kinds or more of tetramethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapropyl ammonium hydroxide, potassium hydroxide, sodium hydroxide applied as either organic or non-organic alkali capable of becoming a major material; andc) either one of or two kinds or more of hexametaphosphoric soda, triphosphate soda and monophosphate soda applied as liquid agent having dampening action for preventing a reduction in pH value;wherein said developer liquid comprises a pH value of 13.0 or more.
US Referenced Citations (10)
Number Name Date Kind
3264104 Maximilian Aug 1966 A
4259434 Yamasue et al. Mar 1981 A
4356254 Takahashi et al. Oct 1982 A
4716098 Mack et al. Dec 1987 A
5155012 Joerg et al. Oct 1992 A
6100016 Denzinger et al. Aug 2000 A
6140291 Bolkan et al. Oct 2000 A
6201110 Olsen et al. Mar 2001 B1
6258764 Gorlin Jul 2001 B1
20020039703 Hotta et al. Apr 2002 A1
Foreign Referenced Citations (3)
Number Date Country
0843214 May 1998 EP
1356928 Oct 2003 EP
05-088377 Apr 1993 JP
Related Publications (1)
Number Date Country
20050191585 A1 Sep 2005 US