Negative type image recording material and method of...

Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making

Reexamination Certificate

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C430S302000

Reexamination Certificate

active

06214518

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to image recording materials which may be used as planographic printing plate materials, color proofs, photo resists or color filters. More particularly, the present invention relates to negative type image recording materials which can be used as planographic printing plate materials that allow direct plate-making by scanning infrared laser beams based on digital signals from a computer, and the like, and a method of plate making using this negative type image recording material.
2. Description of the Related Art
Recently, as recording light sources of a system for carrying out direct plate making from digital computer data, solid-state lasers and semiconductor lasers emitting infrared rays having wavelengths from 760 nm to 1200 nm have gathered attention since high output and compact lasers of this type are easily available. However, since many of the photosensitive recording materials that are useful in practice are sensitive to wavelengths in the visible range of 760 nm or less, images cannot be recorded with these infrared laser devices. Therefore, there is need formaterials capable of forming images with an infrared laser device.
As for image recording materials that can be used for recording with infrared laser devices, U.S. Pat. No. 4,708,925 discloses recording materials containing an onium salt, a phenol resin, anda spectral sensitizer. However, these image recording materials are of a positive type and not of a negative type as in the present invention and make use of an effect of the onium salt and phenol resin to inhibit dissolution into a developing solution. On the other hand, negative type image recording materials are described, for example, in Japanese Patent Application Laid-Open (JP-A) No. 8-276558. These are recording materials composed of a substance that absorbs light and generates heat, an alkali-soluble resin, and a specific phenol derivative having in the molecule 4 to 8 benzene nuclei. However, though this image recording material can attain high printing durability when sufficient heating is conducted, it provides insufficient sensitivity during laser exposure since reactivity thereof is relatively low. There are various suggestions for increasing the sensitivity of these recording materials; however, means for improving sensitivity generally tended to decrease storage stability of the recording materials. In particular, storage stability in high humidity was problematical. Though it is known that high printing durability can be attained even when a resol resin is used as a cross-linking agent, there was a problem that it was poor in stability over time, like the above-described image recording materials.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a negative type image recording material that allows direct plate making from digital data of a computer and the like by recording using a solid-state laser or semiconductor laser emitting infrared rays, and further reveals high sensitivity with respect to a laser, high printing durability, and excellent storage stability even under high humidity, and a method of plate making using this negative type image recording material.
The present inventors conducted extensive studies focusing on the constituent components of negative type image recording materials, and found that the above-described objects can be achieved by using as a cross-linking agent a mixture of a phenol derivative having a specific functional group, and a polynuclear phenol derivative having a specific structure and/or resol resin, thus completing the invention. Namely, in a first aspect, the present invention relates to a negative type image recording material comprising a compound (A) which is cross-linked with the aid of an acid, a binder polymer (B), a compound (C) which generates an acid upon heating, and an infrared ray absorbing agent (D), wherein the compound (A) which is cross-linked with the aid of an acid is a mixture of a lower molecular weight phenol derivative having a molecular weight of 1000 or less represented by the following general formula (I) with a polynuclear phenol cross-linking agent having in a molecule 3 or more phenol rings having 2 or 3 hydroxymethyl groups on a ring represented by the following general formula (II) and/or resol resin:
wherein, Ar
1
represents an aromatic hydrocarbon ring which may have a substituent; R
1
and R
2
may be the same or different, and represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms; R
3
represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms; m represents an integer of 2 to 4; n represents an integer of 1 to 3; X represents a divalent connecting group, Y represents a monovalent, divalent, trivalent or tetravalent connecting group having an above-described partial structure or a functional group having a terminal hydrogen atom, and Z does not exist when Y is a terminal group, or represents a monovalent, divalent, trivalent or tetravalent connecting group or functional group existing in accordance with the number of the connecting group Y;
wherein, A represents an r-valent hydrocarbon connecting group having 1 to 20 carbon atoms; r represents an integer of 3 to 20; and p represents an integer of 2 to 3.
In a second aspect, the present invention relates to a method of plate making in which a negative type image recording material comprising a substrate carrying thereon a layer comprising a compound (A) which is cross-linked with the aid of an acid, a binder polymer (B), a compound (C) which generates upon heating, and an infrared absorbing agent (D) is irradiated with an infrared laser beam having a wavelength of 760 nm to 1,200 nm to conduct direct plate making, wherein the compound (A) which is cross-linked with the aid of an acid is a mixture of a lower molecular weight phenol derivative having a molecular weight of 1000 or less represented by the following general formula (I) with a polynuclear phenol cross-linking agent having in a molecule 3 or more phenol rings having 2 or 3 hydroxymethyl groups on a ring represented by the following general formula (II) and/or resol resin:
wherein, Ar
1
represents an aromatic hydrocarbon ring which may have a substituent; R
1
and R
2
may be the same or different, and represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms; R
3
represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms; m represents an integer of 2 to 4; n represents an integer of 1 to 3; X represents a divalent connecting group, Y represents a monovalent, divalent, trivalent or tetravalent connecting group having the above partial structure or a functional group having a terminal hydrogen atom, and Z does not exist when Y is a terminal group, or represents a monovalent, divalent, trivalent or tetravalent connecting group or functional group existing in accordance with the number of the connecting group Y;
wherein, A represents an r-valent hydrocarbon connecting group having 1 to 20 carbon atoms; r represents an integer of 3 to 20; and p represents an integer of 2 to 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in detail below.
[(A) Compound which is cross-linked with the aid of an acid]
In the present invention, there is used as a compound which is cross-linked with the aid of an acid, a mixture of a phenol derivative represented by the above-described general formula (I) (hereinafter, referred to appropriately as a lower molecular weight phenol derivative) with a polynuclear phenol cross-linking agent having in a molecule 3 or more phenol rings having 2 or 3 hydroxymethyl groups on a ring represented by the above-described general formula (II) and/or resol resin.
The phenol derivative represented by the general formula (I) will be first described in detail.
In the general formula (I), Ar
1
represents an aromatic hydrocarbon ring which may have a substituent. A benzene ring, naphthalene rin

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