JPH0413151A - Photosensitive colored image forming material - Google Patents

Abstract

PURPOSE:To obtain sufficient adhesion in vacuum by providing a colored sensitive layer incorporating an o-quinondiazide compound on one side of a supporting body, and forming positive or negative embossed patterns on other side of the supporting body. CONSTITUTION:On one side of the supporting body 1, the colored photosensitive layer incorporating the o-quinondiazide compound is provided and on the other side of the supporting body 1, the positive or negative embossed patterns 6 or 5 are formed. The colored photosensitive layer can be constituted while incorporating the o-quinondiazide compound functioning as a photosensitive body, a binder and the coloring agent. The o-quinondiazide compound is used for forming a so-called positive type photosensitive composition which generally increases the solubility of an exposed part. Besides, as the o-quinondiazide compound, a compound which 1, 2-naphtoquinon diazide-6-sulfonyl chloride is condensed with a hydroxy group and/or an amino group incorporating chemi cal compound, is preferably used. Hence the sufficient adhesion in vacuum is obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to photosensitive colored imaging materials.

[Background of the invention]

BACKGROUND ART Conventionally, photosensitive colored image forming materials, particularly image forming materials containing O-quinonediazide, have been used in various fields, for example, as color proofs for color image proofing.

When a color proof is subjected to image exposure, it is generally supported in vacuum. Vacuum adhesion is usually
The image forming material is closely fixed by vacuum suctioning the back side of the support, that is, the side opposite to the side on which the colored photosensitive layer is formed. However, in the conventional techniques, the vacuum adhesion of the image forming material was not always good, and it sometimes took a long time to reach the required adhesion state.

[Problem that the invention seeks to solve]

As mentioned above, conventional photosensitive colored image forming materials have problems in adhesion when they are vacuum-adhered.

An object of the present invention is to solve the above problems and provide a photosensitive colored image forming material having sufficient vacuum adhesion.

[Means and effects for solving the problems] The object of the present invention is to have a colored photosensitive layer containing a 〇-quinonediazide compound on one side of a support, and a colored photosensitive layer containing a 〇-quinonediazide compound on the entire surface of the other side of the support. This was achieved by means of photosensitive colored imaging materials configured with positive or negative embossed patterns.

As a result of intensive research to achieve the above-mentioned object, the present inventors have found that, among many means for improving adhesion, the above-mentioned positive or negative embossed pattern is applied to the entire surface of the support opposite to the colored photosensitive layer. The present inventors have discovered that the vacuum adhesion of the photosensitive colored image-forming material becomes sufficient by adopting a structure having the following, and have thus completed the present invention. In the present invention, "the entire surface" having an embossed pattern means the entire surface used for adhesion.

In addition, it is known that vacuum adhesion on a smooth surface of the 25th plate (photosensitive lithographic printing plate) is very time consuming, so we proposed applying embossing to improve vacuum adhesion. (Unexamined Japanese Patent Publication No. 53-1)
However, this conventional technique is not necessarily versatile as it is, and cannot be applied directly to, for example, color proofing.

The present invention will be explained in more detail below.

The photosensitive colored image forming material of the present invention has a colored photosensitive layer containing an 0-quinonediazide compound on one side of a support.

The colored photosensitive layer can be constructed by containing an 0-quinonediazide compound that functions as a photoreceptor, a binder, and a coloring agent (pigment, etc.).

The 0-quinonediazide compound is generally used to constitute a so-called positive-positive type photosensitive composition in which the solubility of exposed areas increases. Any arbitrary quinonediazide compound can be used, but specifically,
2-benzoquinonediazide 4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, ■, 2-naphthoquinonediazide 5-sulfonyl chloride, or 1,2-naphthoquinonediazide-
A compound obtained by condensing 6-sulfonyl chloride with a compound containing a hydroxyl group and/or an amino group is preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, hydroxyanthraquinone, bisphenol A1 phenol nopora resin, resorcin benzaldehyde condensation resin, pyrogallol acetone condensation resin, and the like. Examples of amino group-containing compounds include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4-diaminobenzophenone,
Examples include ゜4-diaminodiphenylamine.

Regarding the above 0-quinonediazide compound, J, K
“Light 5-sensitive Sys” by osar
tem” (Wiley & 5ons, New Year
K+ 1965) and Kenichi, Inui, “Photosensitive Polymers” (
Kodansha, 1977) can be followed.

Since the colored photosensitive layer is formed together with the 0-quinonediazide compound, various binders and colorants can be used. For example, various polymer compounds can be used as the binder that functions as a binder in the photosensitive layer. I can do it. For example, as a preferred binder,
Mention may be made of copolymers of vinyl acetate and vinyl versatate. Other preferred binders that can be used in the present invention will be detailed later.

In addition, various pigments etc. can be used as colorants,
These will also be explained in detail later.

The colored photosensitive layer may be composed of two separate layers: a photosensitive layer (for example, consisting of a photoreceptor and a binder) and a colored layer N (for example, consisting of a pigment and a binder). In that case, the layer order is arbitrary.

In a preferred embodiment of the present invention, the colored photosensitive layer on the support is formed on the support via an intermediate layer such as a heat-softening layer or a release layer. In particular, it is preferable to adopt a structure in which a heat-softening layer is formed on the support (preferably a release layer is further formed thereon), and a colored photosensitive layer is formed thereon.

The support may be made of any material, for example preferably polyethylene terephthalate.

More specific examples of the support and the heat-softening layer and release layer formed as necessary will be described later.

Next, in the photosensitive colored image forming material of the present invention, the other side of the support, that is, the side opposite to the side on which the colored photosensitive layer is formed, has a positive or negative embossed pattern on the entire surface thereof. . In the following description, the surface of the other side J of the support may be appropriately referred to as the back surface J.

In the present invention, the embossed pattern refers to a pattern (positive embossed pattern) formed of a plurality of convex protrusions formed on the back surface of the image forming material, or a pattern (negative embossed pattern) consisting of a plurality of concave recesses. , positive and negative embossed patterns may be mixed.

As an embossing technique for forming an embossed pattern on the back surface of the support, any method, for example, various known methods, can be used. For example, to give an example,
As shown in FIG. 1, there is a means for passing a film, which is a support 1, between a rubber roll 2 and an embossing roll 3, thereby forming an embossed pattern. In this case, the height of the unevenness 4 of the embossing roll varies depending on the pressing pressure, but is preferably 5 to 30 μm. Embosses formed on the film surface should be of a height that does not interfere with exposure and transfer. Its height is generally approximately 30 μm or less. The interval α (see FIG. 4(a)) between the embossed patterns is preferably 30 μmm−1p in consideration of the effect of vacuum adhesion.

The pressing pressure varies somewhat depending on the shape of the embossed pattern, but it is sufficient to apply pressure that exceeds the breakdown point of the film technology used as the support, and in that case, the embossed pattern generally does not disappear permanently.

Various embossed patterns can be used, and there are no restrictions on the shape. There is no limitation to the pattern arrangement, and it can be formed, for example, in an embossed pattern as illustrated in FIGS. 4(a) and 4(b).

Note that FIG. 1 is a diagram showing an example of an embossing forming means.

Further, FIG. 2 shows an enlarged sectional view of an example of the image forming material on which a negative embossment 5 is formed, and FIG. 3 shows an enlarged sectional view of an example of the image forming material on which a positive embossment 6 is formed. In each figure, 1 is an image forming material, 2 is a rubber roll, 3 is an embossing roll, 4 is a protrusion, 5 is a negative emboss formed on the back side of the film that is a support, and 6 is a positive emboss. 7 indicates the side on which the colored photosensitive layer is formed.

The colored image forming material of the present invention can contain various dyes and pigments as colorants in the colored photosensitive layer. Various dyes and pigments can be used as desired, but
Particularly, when used for color proofing, pigments and dyes are generally required in the normal colors required therein, ie, yellow, magenta, cyan, and colors matching those of the blank. In addition, blue, green, and red pigments and dyes are sometimes required, such as when used in color filters. Other metal powders, white pigments, fluorescent pigments, etc. can also be used. When the imaging material of the present invention is applied to, for example, a color proof for color image proofing or other colored imaging materials, many pigments and dyes known in the art may optionally be used, such as the following: I can do it. Below are some examples of various pigments and dyes known in the art. Azo type,
These are organic pigments or dyes such as phthalocyanine-based, quinacridone-based, anthraquinone-based, isodigo-based, and methine-based pigments, or inorganic pigments, and some specific examples of these are described below.

(C,1, means color index).

Lemon Chrome Yellow M35 (C, 1,77603
) Medium chrome yellow (C, r, 776Qo)
Molybdate Orange (C11,77605) Milori Blue 671 (C,1,77510
) Seiki Light Blue (C, 1,74200)
Seiki Light Rose (C, r, 45160:
1) Seiki Light Magenta (C, 1,4517
0:2) Seiryoku Light Blue (c, 1.4
2595:2) Seiriki Light Violet B800 (C, 1, 42535: 2) Seiriki First Lake Renodo CZA665 (C, 1,
15585:1) Seika First Red LR116 (C, 1, 15630:1) Seiriki First Carmine 6B1488 (c, ■, t5
850:1) Seiriki First Red 8040 (C,1,15865:1) Seiriki First Yellow 10GH (C,1,11710) Seiriki First Yellow GH (C,1,11680) Seiriki First Yellow 2015 (C01,11741) Seika First Yellow A-3 (C,1,11737) Seika First Yellow 2300 (C,1,21090) Seika First Yellow 2200 (C,1,21095) Seika First Yellow 2400 (C,1,21105) Seika First Yellow 2600 (C,1,21100) Seika First Yellow 2500 (C,1,21096) Seika First Yellow 2720 (C,I,21108) Seika First Orange 2900 (C,1,21160) Seika First Orange 900 (C,1,21110 ) Seiriki First Orange 3044 (C, 1, 12075) Seiriki First Red 930 (B) (C, 1, 21120) Seiriki First Scarlet G conc (C, 1,
12315) Seika First Carmine 3840 (C,1,12490) Seika First Carmine 3870 (C,1,12485) Seika Fast Carmine RK-1 (C,1,12317) Seika First Violet FR (C,1,12322) Chromofine Blue 4920 (C, 1,7416
0) Chromofine Green 2 (1,0 (C, 1,74260) Chromofine Yellow 5910 (C,!, 2003
5) Chromofine Orange 6726 (C, 1, not 1isted,) Chromofine Blue Lett 6750 (C, 1, not 1isted,) Chromofine Red 6820 (C, 1, 4650
0) Chromofine Violet (C, 1,51319
) Shimla First Yellow 8GTF (C, [21105) Shimla First Yellow 4186 (C, 1,11767) Shimla First Yellow 4193G (C, 1,21
100) Shimla Fast Yellow GHK-N4 (C, 1, 2
1090) Shimla Fast Yellow GTF230T (C, 1,
not 1isted,) Shimla Fast Yellow RF (C, 1, 21096) Shimla Fast Yellow 4181 (c, 1.21108) First Gen Super Yellow GRO (C, [562
80) Shimla Fast Virazolone Orange G (C, 1, 2
1110) Shimla First Orange V (C, 121160) Shimla First Orange 4183H (C, 1, 11
780) Shimla Lake Red Cconc 130 (C, 1, 1
5585:1) Shimla Neotall Red 2BY (C,1,15565:1) Shimla Red 2BS (C, [15865:1) First Gen Super Red 2Y (C,1,73905) First Gen Super Red 7083 Y (C, 1,
46500) Shimla Red 3013 (C, 1,1586
5:2) Shimla Prilliant Carmine 6B246 (C
, r, 15850:1) First Gen Super Magenta R (C,1,73915) First Gen Super Violet RNS (C,1,
5l-319) Fastgen Super Blue 6 (116(c, 1.
69800) First Gen Blue BSF-A (C, 1,74160) First Gen Blue TGR-L (C, 1,74160) First Gen Green S (C1r, 74260
) First Gen Green 2YK (C, 1,74265) Oriental Louis xo-GT (C, 1,11680) manufactured by Dainippon Ink ■
Victoria Pure Blue (C, 1, 42595) Lionor Red 7B4401 (C, r, 15830
) Lionor Red 3901 (C, 1, 12
120> Lionor L/, Do FB5500 (C, 1
, 12490) Lionor Red FBK (C,
1,12490) Nα7100 Lionor Yellow
(C, 1, 21096) Lionor Yellow FCG-3 (C, 1, 21127) Lionor Yellow NBR (C, 1, 21108) Lionor Yellow-1806-G (C, 1, 21127)
Riono J Relendo 28 K (C, 1, 15865
:4) Lionor Yellow K-5G (C, 1, 13
960) Lionol Yellow K-2R (C, r, x3
955) Lionor Yellow FC; G-3 (C, 1,21127) Lionor Blue 7210-V (C, 1,7416
0) Lionor Blue SM (C, 1,741
60) Lionor Blue-FG-7330 (C, 1,
74160) Lionor Blue SP G-8 (C,
1,74160) Lionor Blue E S P -S
(C, 1,74160) Lionor Blue E S
(C, 1,74160) Lionor Green B-2
01 (C, 1,74260) Lionol Green Y-1
01 (C, 1,74260) Lionor Green 6Y-
501 (C, 1,74160) Lionogen Yellow GF (C, 1,70600
) Lionogen Yellow 3G-F (C, 1, not 1isted,) Lionogen Yellow RX -F (C, 1, 66280
) Lionogen Orange R-F (C,1,11780
) Lionogen Orange G R-F (C, 1,7110
5) Lionogen Brown R-F (C, 1, 1251
0) Lionogen Red Y-F (C, 1,465
00) Lionogen Red 6 B -F (C, 1, 4
6500) Lionogen Red G D -F (C,
1,53900) Lionogen Magenta RF (C,
1,73915) Lionogen Violet RL-F (C,1,51319) Lionogen Blue RF (C,1,69800)
Lionogen Blue R3-F (C, 1,69800)
Auramine manufactured by Toyo Ink (C, 1,41000)
Carotene brilliant flavin (C, 1, basic 13) Rhodamine 6 G CP (C, 1,451
60) Rhodamine B (C,1,45
170) Safranin OK 70:100 (C,
1,50240) Erioglaucine X (C,
1,42080) First Black HB (C
, 126150) Henjijin Yellow 4T-564D (C, 1, 21095) Mitsubishi Carbon Black M A-100 Mitsubishi Carbon Black #30, #40, #50 In the practice of the present invention, the content of the colorant in the colored photosensitive layer can be determined in consideration of the target optical density and the removability of the colored photosensitive layer with respect to a developer. In the present invention, the content of the colorant is preferably in the range of 5 to 40% by weight, particularly preferably in the range of 10 to 30% by weight. In carrying out the present invention, two or more types of pigments and dyes used as colorants can be used in combination.

Further, in the colored image forming material of the present invention, the colored photosensitive layer can contain a binder.

Any binder can be used as long as it can function as a binder; for example, a polymer compound that is film-forming and solvent-soluble, and preferably dissolves or swells in an alkaline developer can be used. .

Specific examples of such polymer compounds include the following -
A polymer compound containing a structural unit having an aromatic hydroxyl group represented by formula (1) in its molecular structure can be mentioned.

General formula (1) In the general formula (r), R eyes and R eyes each independently represent a hydrogen atom, an alkyl group, or a carboxylic acid group. R1ff
represents a hydrogen atom, a halogen atom, or an alkyl group; R'' represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group; X represents a divalent organic group connecting a nitrogen atom and an aromatic carbon atom; n represents O or I. Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specific examples of monomers forming the structural unit represented by formula (I) above include N-(4-hydroxyphenyl)-Cj-7crylamide, N-(2-hydroxyphenyl)-( meth)acrylamide, N-(4
-Hydroxynaphthyl) = (meth)acrylamide monomers such as (meth)acrylamide; o-, m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers, etc. . Preferably o-, m- or p-hydroxyphenyl (meth)acrylate monomers, N-
(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth)acrylamide monomer.

In the present invention, it is preferable to use as a binder a copolymer of a heptamer forming a structure represented by general formula (1) and the following monomers.

RIS RIS RIS In each of the above formulas, RIS represents a hydrogen atom, an alkyl group, or a halogen atom, and R16 represents an alkyl group, a phenyl group, or a naphthyl group.

When using the above copolymer, the ratio of groups having an aromatic hydroxyl group represented by general formula (1) in the copolymer is preferably 1 to 30 mol%.

The proportion of units formed from the acrylonitriles in the copolymer is preferably 0 to 50 mol%, and more preferably 5 to 40 mol% in consideration of developability. The proportion of structural units formed from the alkyl acrylate i is preferably 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and most preferably 60 to 95 mol%. Give sex.

In addition to the structural units described above, the above-mentioned acrylic acids such as acrylic acid or methacrylic acid may be copolymerized to form structural units in the polymer compound that is the copolymer, for the purpose of finely adjusting the developability.

In this case, the proportion of the copolymer of acrylic acids in the cough polymer compound is 0, considering the development latitude.
-20 mol% is preferred, and 0-10 mol% is most preferred.

The weight average molecular weight of such a polymer compound is preferably from 1,000 to 100,000, more preferably from 1,000 to 100,000, from the viewpoint of developability or resolution when a low alkaline aqueous solution is used as a developer. A range of 30,000 to 30,000 is preferred. These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such polymer compounds include copolymers having the following structure.

(Weight average molecular weight: 1,000-30,000)
i, :m:n=(1-25):(5-40) :(5
0 to 95) Furthermore, in the colored image forming material of the present invention,
As the binder constituting the colored photosensitive layer, a polymer compound having a carboxylic acid vinyl ester polymerized unit shown in the following "Funazura" in its molecular structure can also be preferably used.

RCOOCH=CH2 However, R represents an alkyl group having 1 to 17 carbon atoms.

Any polymer compound having the above structure can be used, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit indicated by -Funazou above, the following examples are preferable. The name and chemical formula are also shown.

■Vinyl acetate CH3CO0C) I=CH2
■Vinyl propionate CHsCHzCOOCH=C
Hz■Vinyl butyrate CH+(CH2)zcO
OcH=clh■Vinyl pivalate (CHs)
3CCOOCH= CHz ■Vinyl caproate C
Hx (CHz)4cOOcH=cHz■Cub IJ/L
/acid I ninyl CHx (CHz)bcOOcH=cHz
■Vinyl caprate CHs (CHz)scOOc
H=cl(z■vinyl laurate CHzCCHz
”)+.C00CH= C) I ■ Vinyl myristate [phase] Vinyl palmitate ■ Vinyl stearate @ Vinyl versatate L R' -C-C00CH= CH2 Z (R1, pZ is an alkyl group, and its carbon number is The sum is 7. In other words, the carboxylic acid vinyl ester monomer is in the form of R'+R""CdL+i). It is more preferable to use a carboxylic acid vinyl ester monomer having 1 to 4 carbon atoms in the main chain of the carboxylic acid. Particularly, Vinyl acetate is preferred.

Note that the above R also includes an alkyl group having a substituent, that is, a vinyl ester of a substituted carboxylic acid is also included in the polymerization unit.

The polymer compound may be a polymer obtained by polymerizing one type of carboxylic acid vinyl ester, a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl esters, or a polymer that can be copolymerized with carboxylic acid vinyl ester. CHs (CHz) + zCOOCH = at any component ratio with the monomer of
CHzC)+3 (CHz) r acOOcH=CH
It may also be a copolymer of zCHz (CHz)+hCOOCH=CHz.

Examples of monomer units that can be used in combination with the polymerized units shown above - on-board include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as diethyl maleate, maleic acid, etc. Diesters of unsaturated dicarboxylic acids such as dibutyl acid, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic dodecyl acid, 2-chloroethyl acrylate,
Phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, etc. (Dα-methylene aliphatic monocarboxylic acid esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, e.g. acrylic Anilides such as anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxydiacrylanilide, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, Vinylidene chloride, vinylidene cyanide, e.g. 1-methyl-1-methoxyethylene, l.

Ethylene derivatives such as 1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrol, N-vinylcarbazole,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylvirolone, and N-vinylpyrrolidone. These vinyl monomers generally exist in a polymer compound with a structure in which unsaturated double bonds are cleaved.

In the present invention, when using the polymer compound represented by the above-mentioned -Funzo, particularly preferred is one having a vinyl acetate polymerization unit in its molecular structure.

Among them, 40 to 95 ivt% of vinyl acetate polymer units
having a number average molecular weight (MN) of 1.000 to 1
00.000, weight average molecular weight (MW) is 5.0
00 to 500.000 is preferred.

More preferably, vinyl acetate polymerized units (especially 40
~95Nt%) and polymeric compounds having carboxylic acid vinyl ester polymerized units with a longer chain than vinyl acetate, particularly those with a number average molecular weight (MN) of 2.000 to 60.
000, weight average molecular weight (MW) is 10,000-15
A value of 0.000 is preferred.

In the case of 2, the monomer that copolymerizes with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer as long as it can form a copolymer, such as the above-mentioned monomers. You can choose any part of your body.

Copolymers that can be used as polymeric compounds in the present invention are listed below by indicating their heptamer components. However, it goes without saying that the invention is not limited to the following examples.

■Vinyl acetate-acrylic acid ester ■Vinyl acetate-maleate ester ■Vinyl acetate-ethylene ■Vinyl acetate-vinyl carboxylate ester ■Vinyl acetate-styrene ■Vinyl acetate-crotonic acid ■Vinyl acetate-maleic acid ■Vinyl acetate-2-ethyl Hexyl acrylate ■ Acetic acid and Nyl-di-2-ethylhexyl maleate [Phase] Hinyl acetate-Methyl vinyl ether ■ Vinyl acetate - Vinyl chloride @ Vinyl sulfate - N-vinylpyrrolidone @ Vinyl acetate - Vinyl propionate [Phase] Vinyl acetate - Vinyl pivalate ■Vinyl acetate-vinyl versatate [phase] vinyl acetate-vinyl laurate ■vinyl acetate-vinyl stearate ■vinyl acetate-versatate-ethylene [phase] vinyl acetate-vinyl versatate-2-ethylhexyl acrylate [stock ] Vinyl acetate-vinyl versatate-vinyl laurate■vinyl acetate-vinyl versatate-crotonic acid@vinyl propionate-vinyl versatate@vinyl propionate-vinyl versatate-crotonic acid [phase] pivalic acid-stearin Acid vinylomalein In the present invention, a novolac resin can also be used as a binder.

Novolak resins are generally obtained by polycondensation of at least one type of phenol and an active carbonyl compound, and any of these novolak resins can be used.

The above-mentioned phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specific examples of such phenols include, for example:
Phenol, 0-cresol, m-cresol, p-cresol, 3.5-xylenol, 2.4-xylenol, 2.5-xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, alkyl group ( Examples include substituted phenols (having 1 to 8 carbon atoms).

The active carbonyl compounds include, for example, aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Examples of the novolak resin include phenol formaldehyde novolak resin, m-talesol formaldehyde novolak resin, phenol/m-cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, m-cresol/p -cresol/formaldehyde copolycondensate resin,
0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/m-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol -m-cresol/p-cresol/formaldehyde copolycondensate resin, etc. can be mentioned.

A preferred novolac resin is a phenol formaldehyde novolac resin, which has a weight average molecular weight MW of 3500.
~500, and those with a number average molecular weight MN of 1000 to 200 are preferred.

The molecular weight of the polymer compound in this specification, including the molecular weight of the novolak resin, is measured by GPC (gel permeation chromatography). The number average molecular weight MN and weight average molecular weight MW were calculated by smoothing the peaks in the oligomer region by the method described in Morio Takushoku, Tatsuya Miyabayashi, and Masayuki Naka, "Journal of the Chemical Society of Japan," p. aOO, p. 805 (1972). (Connecting the center of the peak and the center of the valley).

In addition, in the novolac resin, pyrolysis gas chromatography (PGC) is used as a method for confirming the quantitative ratio of different phenols used in the synthesis thereof.

The principle of pyrolysis gas chromatography is
The equipment and experimental conditions are, for example, published in the Journal of the Chemical Society of Japan, Takushoku
New Experimental Chemistry Course” Volume 19, Polymer Chemistry (I) 47
The method for qualitative analysis of novolac resins based on pyrolysis gas chromatography is described in pages 4 to 485 (Maruzen, 1978), etc., and the method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in "Analytical Chemistry" No. 18 by Morio Takushoku, Takashi Naka, and Masayuki Naka. vol., pages 47-52 (1969).

In the present invention, the colored photosensitive layer is coated with a novolac resin (component (b)
)) and a polymer compound (referred to as component (c)) having in its molecular structure the carboxylic acid vinyl ester polymerized unit represented by the above-mentioned formula (2),
It is preferable that the content is in a weight ratio range of (b)/(c) = 5/95 to 80/20.

This range is preferable in terms of color reproducibility, thermal deformation (dimensional deviation), and color fastness. Component (b) (c
A particularly preferred ratio of ) is (b)/(c) = by weight
It is in the range of 10/90 to 60/40.

Further, in the present invention, other polymeric compounds that can be used as a binder for the colored photosensitive layer include (meth)
Sulfoalkyl esters of acrylic acid (co)polymers, vinyl acetal (co)M polymers, vinyl ether (co)polymers, acrylamide (co)polymers, styrene (co)polymers, cellulose derivatives, etc. can also be mentioned. .

The thickness of the colored photosensitive layer in the image forming material of the present invention can be appropriately determined depending on the target optical density, the type and content of the colorant used in the colored photosensitive layer, and the like. Within the allowable range, the thinner the colored photosensitive layer is, the higher the resolution and the better the image quality. Therefore,
The film thickness is preferably 0.1 g/rr to 5 g/rrr.
It is usually used within the range of

The colored photosensitive layer of the colored image-forming material of the present invention can generally be formed by coating a colored photosensitive layer coating solution containing a photoreceptor, a binder, and a pigment on a support.

Here, an organic solvent can be used as a solvent to constitute the coating liquid. In carrying out the present invention, any organic solvent can be used as the colored photosensitive layer coating solution, and for example, all of the various known organic solvents can be used. Examples of organic solvents that can be used include hydrocarbons such as n-hexane, cyclohexane, n-pentane, benzene, toluene, and xylene, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and t-'7. Alcohols such as methyl alcohol, 5ec-butyl alcohol, isobutyl alcohol, n-butyl alcohol, 1-pentanol, 2-pentanol, ■-hexanol, acetone, cyclohexanone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone , ketones such as methyl-n-butyl ketone and methyl isobutyl ketone, diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monoethyl ether, and other esters such as methyl lactate, ethyl lactate, methyl propionate, methyl butyrate, and ethyl acetate. Nitriles such as acetonitrile, propionitrile, etc., 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, methylene chloride, chloroform, carbon tetrachloride, etc. Among these, those preferably used are: These include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones, and esters, and particularly preferred are cyclohexanone, toluene, and methyl lactate.

When carrying out the present invention, plasticity and coating properties improvers and the like may be added to the colored photosensitive layer, if necessary.

As the coating agent, various low-molecular compounds such as phthalic acid esters, triphenyl phosphates, and maleic acid esters are used.As the coating agent, surfactants such as fluorine surfactants, ethyl cellulose polyalkylene ether, etc. are used. Examples include representative nonionic surfactants.

When constituting the image forming material of the present invention, the colored photosensitive layer can be divided into two layers: a colored layer made of a colorant and a binder, and a photosensitive layer made of a photosensitive composition. In this case, it does not matter which layer is placed on the support side.

The colored imaging materials of the present invention can be embodied as color proofs.

In this case, the colored photosensitive layer of the colored image-forming material is removed in an imagewise manner by development following imagewise exposure to form a colored image.

Although any support can be used to constitute the image forming material of the present invention, a transparent support is preferably used. As the transparent support, a polyester film, particularly a two-wheel stretched polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film, polyethylene film,
Polypropylene film, polyethylene film, etc. can be used.

Direct imaging materials can be used to transfer images to a receiving material. At this time, in order to efficiently transfer the image onto the material to be transferred and to facilitate peeling off the support after image transfer, a release layer (a release layer is used to remove the surface of the support) between the support and the colored photosensitive layer is used. It is preferable to provide an intermediate layer such as a heat softening layer or a heat softening layer.

The release layer is made of, for example, silicone resin, fluororesin, polyethylene, polypropylene ethylene-α-olefin copolymer, propylene-α-olefin copolymer, ethylene-propylene copolymer, engineered ethylene-propylene-diene copolymer, Ethylene-acrylic acid copolymer, ethylene-
It can be formed from polyamide resins such as vinyl acetate copolymers, ionomer resins, waxes, nylons, and copolymerized nylons.

Furthermore, silicone resin or fluororesin may be added to melamine resin or polyacrylate urethane resin.

In addition, polypropylene film, polyethylene film, etc. exhibit good mold release properties without special mold release treatment, so in a preferred embodiment, the film is thinner than the thickness of the support.
A polypropylene layer or a polyethylene layer can be provided as a release layer.

The method for forming a polypropylene layer or polyethylene layer on a support is as follows: (1) A solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. After applying these adhesives on a support and drying with hot air or heating, a polypropylene film or a polyethylene film is overlaid and laminated by pressing under heat.
So-called dry lamination method; (2) Using a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and acrylic ester, polyamide resin, petroleum resin, rosin, wax, or a mixture thereof as an adhesive, these adhesives After applying the material onto a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc. while keeping it in a molten state by heating it as it is,
The so-called hot-melt lamination method, in which polypropylene or polyethylene films are immediately laminated together and laminated by heating at a high temperature if necessary and then cooling; (3) The polypropylene or polyethylene is kept in a molten state and extruded. This is the so-called extrusion lamination method, in which the film is extruded into a film using a machine, and while it is still in a molten state, a support is bonded and laminated; Using a machine, with molten polypropylene or polyethylene, by molding - times,
Examples include a so-called coextrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film.

The thickness of the release layer is suitably in the range of 0.01 to 30 μm, particularly preferably in the range of 0.1 to 5 μm.

Next, the thermally softened layer will be described.

The thermosoftening layer has a property of softening at the temperature during thermal transfer, and can be formed from a thermoplastic resin. The thermoplastic resin has a softening point of 130°C to 150°C.
Preferably. The softening point temperature referred to here is VI
This is the value shown by the CAT softening point or the ring and ball method. In the present invention, specifically, the following resins can be mentioned as preferred resins.

Polyolefins such as polyethylene and polypropylene.

Ethylene copolymers such as ethylene and vinyl acetate, ethylene and acrylic ester, and ethylene and acrylic acid.

PVC.

Vinyl chloride copolymers such as vinyl chloride and vinyl acetate.

Polyvinylidene chloride.

Vinylidene chloride copolymer.

polystyrene.

Styrene copolymers such as styrene and maleic anhydride.

Polyacrylic acid ester.

Polyester resin.

Polyurethane resin.

Acrylic ester copolymers such as acrylic ester and vinyl acetate.

Polymethacrylic acid ester.

Methacrylate ester copolymers such as methyl methacrylate and vinyl acetate, and methyl methacrylate and acrylic acid.

Polyvinyl acetate.

Vinyl acetate copolymer.

Vinyl butyral resin.

Polyamide resins such as nylon, copolymerized nylon, and N-alkoxymethylated nylon.

synthetic rubber.

Petroleum resin.

Chlorinated rubber.

Polyethylene glycol.

Polyvinyl alcohol hydrozine phthalate.

cellulose derivative, cellulose acetate phthalate,
Cellulose acetate succinate.

Sheratsk.

wax.

The heat-softening layer can be provided on the support using a known method.

The thickness of the thermally softened layer is suitably in the range of 1 to 50 μm, particularly preferably in the range of 5 to 30 μm.

The release layer can be provided on the heat-softening layer by coating a solution or emulsion of the release layer resin dissolved in an organic solvent on the heat-softening layer, or by applying a polypropylene film or a polyethylene film. Examples include a method of laminating a film onto a heat-softening layer.

The image forming material of the present invention can be exposed and developed to form an image area, and at least the formed image area can be transferred to a transfer material to obtain a transferred image.

For example, when the method is implemented as a multicolor image forming method, the basic methods can be roughly divided into the following methods (1) and (I[).

(T) A first colored image-forming material having a colored image-forming layer for the first color on the support is superimposed on the transfer material, at least the colored image-forming layer is transferred to the transfer material, and the support is peeled off. Next, image exposure is performed through a first color film original corresponding to the first color, and then development processing is performed to form a colored image of the first color on the transfer material.

Next, a second colored image-forming material having a colored image-forming layer of a second color different in tone from the first color (both colored image-forming layers are placed on the first-colored colored image layer on the transfer material). alignment image of the second color film original that corresponds to the second color (generally called a registration mark image is used)
is registered with the first color registration mark image, image exposure is performed through the second color film original, followed by development processing to obtain a two color matched image on the transferred material. Thereafter, similar processing is performed for the third and fourth colors to obtain a multicolor image.

This method is known from Japanese Patent Publication No. 47-27441, Japanese Patent Publication No. 56-501217, etc.

Nl) A first color colored image is formed on a first color colored image forming material, at least the colored image is transferred to a transfer material, and the support is peeled off. Further, after forming a second color colored image on the second color colored image forming material, while registering the second color register mark image formed accordingly with the first color register mark image on the transfer target material. , transferring a second color colored image onto the first color colored image and peeling off the support to obtain a two color matched image. Similarly, colored images of the third color and the fourth color are also transferred onto the transfer material to obtain a multicolor image. In some cases, this multicolor image may be indirectly transferred onto another transfer material,
Multicolor images may also be obtained.

This type of method is disclosed in Japanese Patent Application Laid-open Nos. 47-41830, 59-97140, 60-23649 and US Pat. No. 3,775,113.

Imaging materials are typically exposed imagewise through a color separation mask or the like and then developed to form an image.

At this time, an embodiment may be adopted in which only the image portion from the image obtained on the support is directly transferred and laminated onto the transfer material. That is, in one preferred embodiment, only the colored image layer that substantially forms the image is transferred and laminated.

In this case, in order to efficiently transfer the image onto the surface to be transferred and to facilitate peeling off the support after image transfer, the surface of the support may be subjected to a release treatment using an appropriate oil-repellent substance as described above, or
Alternatively, it is preferable to provide a release layer on the support.

The image-forming material of the present invention can be exposed to appropriate light depending on the colored photosensitive layer, particularly depending on the photoreceptor, and then developed to obtain an image. Any developer can be used as long as it has a developing action to develop the material to be processed. Preferably, a developer containing an alkaline agent and an anionic surfactant is used.

Usable alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

Sodium or ammonium salts of secondary or tertiary phosphates, sodium metasilicate, sodium carbonate.

Inorganic alkaline agents such as ammonia, (2) Mono-, di-, or trimethylamine, mono-, di-,
or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropylamine, ethyleneimine.

Examples include organic amine compounds such as ethylenediimine.

In addition, as anionic surfactants that can be used, (1)
Higher alcohol sulfate esters (e.g., sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfuric acid alkyl sulfate, etc.), (2) Salts of aliphatic alcohol phosphate esters (e.g.,
Sodium salt of cetyl alcohol phosphate ester, etc.) (3) Alkylaryl sulfonate salts [eg, dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt.

dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (5) Sulfonic acid salts of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) ) and 6) Formaldehyde condensates of alkylnaphthalene sulfonates (for example, formaldehyde Wt compounds of sodium dibutylnaphthalene sulfonate, etc.).

The alkaline agent and anionic surfactant can be used in any combination.

〔Example〕

Examples of the present invention and comparative examples will be described below.

It should be noted that, as a matter of course, the present invention is not limited only to the embodiments described below, but can take various forms.

Example 1 A polyethylene terephthalate film with a thickness of 75 μm was used as a support, and this was pressed between a rubber roll and an embossing roll (roll embossing: cylindrical pattern with a height of 13 μm and a distance of M5-1 and a surface area of about 0.2 m+”). An emboss was formed on the polyethylene terephthalate film by passing it through the polyethylene terephthalate film.The surface opposite to where the emboss was formed (the surface on which the colored photosensitive layer was to be formed) was made as smooth as possible.The processing equipment was, for example, The one shown in FIG. 1 described above can be used.

On the embossed polyethylene terephthalate film, an ethylene-vinyl acetate copolymer (trade name: Evaflex, manufactured by DuPont Mitsui Chemicals) was applied to a thickness of 30 g by extrusion lamination, thereby forming a heat-softening layer. A support having the following was created.

Colored photosensitive layer dispersions of the following four colors were applied to the support having a heat-softening layer obtained above to a dry film thickness of 1 μm, dried, and embossed. A colored imaging material was prepared.

Four colored photosensitive layer dispersions were prepared as follows.

Color sensation Cyan 1.2-naphthoquinonediazide-4-sulfonic acid-p-cresol formalin ester polymer 2.31g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 15.3
6g Cyanine Blue 4920 (manufactured by Dainichiseika) 1.1g
Cyclohexanone 71.47 g
1.2-naphthoquinone diazide-4 sulfonic acid-p-cresol formalin ester polymer Vinyl acetate-vinyl versatate (80,720 parts by weight) copolymer (49.7% methanol solution) Seiryoku Fast Carmine 1483 (large (manufactured by Nissei Ka) Cyclohexanone yellow 1.2-naphthoquinonediazide-4-sulfonic acid-P-cresol formalin ester polymer Vinyl acetate rubersatin citrate (80: 20 parts by weight) copolymer (49.7% methanol solution) ) Seiryoku Fast Yellow H-7055 (manufactured by Dainichiseika) Cyclohexanone 2.37g 15.36g 1.1g 71.47g 2.37g 15.36g 1.1g 71.47g 1.2- Naphthoquinone diazide-4-sulfonic acid-P-cresol formalin ester polymer 2.19 g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 14.2
1 g Carbon black M A-100 (manufactured by Mitsubishi Kasei) 1.85 g
Cyclohexanone 72.05 g
A color separation mesh positive film of each color is superimposed on the polyethylene terephthalate film side of the four-color colored image forming material obtained as above, that is, the side opposite to the side on which the colored photosensitive layer is formed (back side of the support), When the vacuum was applied,
Compared to colored image forming materials that are not embossed, the time required for vacuum adhesion was reduced by 50%.

Example 2 Ethylene-vinyl acetate copolymer (trade name: Ehaflex, manufactured by DuPont Mitsui Chemicals) was coated on a polyethylene terephthalate film with a thickness of 75 μm to a thickness of 30 μm using an extrusion lamination method, and then heat softened. A support having layers was prepared.

The above-mentioned polyethylene terephthalate support with a heat-softened layer created in advance was placed between a rubber roll and an embossing roll (emboss: height 13 μm, distance 5 mm, interval surface area approximately 0.2 nn).
n'' cylindrical pattern) while applying pressure to form an emboss on the polyethylene terephthalate film (ie, on the side opposite to the side having the heat softening layer) as in Example 1.

The same colored photosensitive layer dispersions of the four colors used in Example 1 were applied onto the embossed and heat-softened support obtained above to give a dry film thickness of 1 μm. After that, it was dried.

In this way, embossed colored image forming materials of four colors were prepared.

When color separation mesh positive films of each color were superimposed on the polyethylene terephthalate film surface of the four-color colored image-forming material obtained above and vacuum-adhered, the results were compared with the colored image-forming material without embossing. As a result, the time required for vacuum adhesion was reduced by 20 to 50%.

Example 3 Ethylene-vinyl acetate copolymer (trade name: EVAFREX, manufactured by DuPont Mitsui Chemicals) was coated on a polyethylene terephthalate film with a thickness of 75 μm to a thickness of 30 μm using an extrusion lamination method, and a heat softening layer was formed. A support having the following was created.

A colored photosensitive layer dispersion of the same four colors as in Example 1 was applied onto the support having a heat-softening layer obtained above to a dry film thickness of 1 u.
After applying each coat to a thickness of m, it was dried.

As in Example 1, the thus obtained colored image-forming materials of four colors, each having a colored layer formed in advance, were treated as follows.
Rubber roll and embossing roll (emboss: height 13μm
, a distance of 511 II, and a cylindrical pattern with an interval of 0.2 mm in terms of surface area) while applying pressure to form an emboss on the colored image forming material of the four colors.

When color separation mesh positive films of each color were superimposed on the polyethylene terephthalate film surface of the four-color colored image-forming material obtained above and vacuum-adhered, the results were compared with the colored image-forming material without embossing. As a result, the time required for vacuum adhesion was reduced by 50%.

Example 4 In Example 1, the height of the embossing to be formed was 20 μm.
And so. Other than that, the procedure was carried out in the same manner as in Example 1. In this example, the time required for vacuum adhesion was reduced by 60% compared to a colored image forming material that was not embossed.

Comparative Example 1 The same procedure as Example 1 was carried out, but the height of the embossing to be formed was changed to 2.
It was set as μm. In this case, the time required for vacuum adhesion did not change much, and was only shortened by about 10% at most, compared to a colored image forming material that was not embossed.

〔Effect of the invention〕

As mentioned above, the colored image forming material of the present invention has the effect of having sufficient vacuum adhesion.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an example of an emboss forming means, and FIG.
FIG. 3 is an enlarged cross-sectional view of an example of an image forming material on which negative embossing is formed. FIG. 3 is an enlarged cross-sectional view of an example of an image forming material on which positive embossing is formed. FIGS. 4(a) and 4(b) are diagrams showing examples of embossed patterns. 1... Image forming material, 2... Rubber roll, 3...
Emboss roll, 4...Protrusion, 5...Negative emboss, 6...Positive emboss. Figure 3

Claims (1)

[Claims] 1. A photosensitive colored image-forming material having a colored photosensitive layer containing an o-quinonediazide compound on one side of a support, and a positive or negative embossed pattern on the entire surface of the other side of the support.