JPS6023998B2 - recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material for recording information using a high energy density light beam.

Conventionally, as recording materials using a high energy density light beam such as a laser, there are the following thermal recording materials in addition to photosensitive materials such as silver salts.

In this thermal recording material, the recording layer has a high optical density and absorbs the irradiated high-energy density light beam, causing a local temperature rise and thermal deformation such as melting, evaporation, and aggregation. Then, the irradiated portion is removed, thereby creating an optical density difference with respect to the non-irradiated portion, thereby recording information. Such thermal recording materials generally do not require processing such as development or fixing;
It has the advantages of not requiring darkroom operations because it is not recorded under normal room light, that high-contrast images can be obtained, and that additional information can be recorded (add-on). Generally, the recording method on such thermal recording materials converts the information to be recorded into an electrical time-series signal, and scans the recording material with a laser beam whose intensity is modulated according to the signal. It is often done.

This case has the advantage that recorded images can be obtained in real time. Metals, dyes, plastics, etc. are suitable for the recording layer of such thermal recording materials, and generally inexpensive materials can be used.

Such recording materials are known, for example, from M. L. ``Electron, ion and L'' by Levene et al.
"aser Beam Technology" 11th Symposium Record (1969), Electron
ics magazine (March 18, 1968), p. 50, D. Others
Written by Fune “ Tsume e Mr. 11 System Techn
icalJom Female 1” Magazine Volume 50 (1971) No. 17
Page 61, C. 0. “Science” by Carlson
It is described in vol. 154 (1966), p. 1550, etc. Among them, there are those that use a metal layer as a recording layer, for example, those that use a thin metal film of Bi, Sn, In, etc. on a support, and these can record images with high resolution and have high contrast. It has excellent properties as a thermal recording material. However, with recording materials that use a single metal thin film, the reflectance of the laser beam used for recording is often over 50%, making it impossible to effectively utilize the energy of the laser beam. The light energy is large, and therefore a high-output laser light source is required to record with high-speed scanning, which has the disadvantage that the recording apparatus becomes large and expensive. Therefore, some recording materials with high recording sensitivity are being explored, and one example is the Special Publication No. 46-4047.
No. 9 describes a recording material having a three-layer structure consisting of Se, Bi, and Bo. That is, it is a lamination of thin serpentine films that make noise in order to lower the light reflectance of the thin film made of Se and Bi. However, it is not preferable to use Se or the like because there is a risk of pollution, and the recorded image quality is also not satisfactory. As another example of a recording material provided with an anti-reflection layer, Japanese Patent Application Laid-Open No. 74632/1984 discloses that an anti-reflection layer that absorbs light at the wavelength of the laser beam used for recording is provided on a metal layer. has been done. However, even if an anti-reflection layer is provided, it is extremely difficult to completely eliminate light reflection, and even if light reflection is completely eliminated, laser light irradiation will cause thermal deformation such as melting, evaporation, and aggregation of the metal thin film. Since a large laser light source is required to generate this, a recording material with higher sensitivity is required. An object of the present invention is to provide a highly sensitive recording material for recording with a high energy density light beam such as a laser beam. Another object of the present invention is to provide a highly sensitive recording material with excellent recording image quality and high scratch resistance.

According to the present invention, there is provided a high-sensitivity recording material having a recording layer on a support that includes a metal and a halide that is thermally or photochemically activated by light irradiation and can promote melting, evaporation, or aggregation of the metal. provided. The high-sensitivity recording material of the present invention has a structure in which a laminate or a mixture of a metal and a halide is provided on a support, and a protective layer made of an organic substance is further provided thereon. Supports used in the present invention include plastics such as polyethylene terephthalate, glass, paper,
A general recording material support such as a plate-shaped or foil-shaped metal support may be used.

The metals used in the present invention include Mg, Sc, Y, T
i, Zr, Hf, V, Nb, Ta, Cr, Mo, VV,
Mn, Re, Fe, Co, Ni, Ru, Rh, Pb, l
r, Pt, Cu, Ag, Au, Zn, Cd, AI, Ga
, ln, Si, Ce, m, Pb, Po, Sn, As, S
b, Bi, Se, Te, etc., but particularly desirable conditions for the metal used in the present invention are low toxicity, low energy required for melting or evaporation, Low light reflectance, little deterioration over time such as a decrease in optical density during storage, and easy thermal deformation such as melting, evaporation, or aggregation due to thermal or photochemical activation of halides. and that the membrane is easy to manufacture.

The metals that can most effectively carry out the present invention include Mg and Zn.
, N, ln, Sn, and Bi are preferred. These metals may be used alone to form various layers as described below.
Further, various layers may be formed in an alloy state.

Furthermore, in the case of an alloy, it may contain Na, K, and Ca.

These metals can be provided on the support in a layered structure as described below using various methods such as vacuum evaporation, sputtering, ion plating, electroplating, and electroless plating. As a method for forming a layer consisting of two or more metals, an alloy may be vacuum evaporated, or two or more metals may be evaporated simultaneously or separately using separate evaporation sources. The thickness of the metal layer may be any thickness that provides the optical density required for the image.For example, to obtain a transmission density of 2, a metal layer of 300A to 1500A is required, but it may vary depending on the type of metal used. Of course.

Furthermore, when forming a metal layer on a support using methods such as vacuum evaporation, sputtering, and ion plating, the film structure of the metal layer changes depending on the type of support, temperature, degree of vacuum, deposition rate, etc. It is obvious that the film thickness required to obtain the concentration also differs.

On the other hand, the aforementioned halides used in the present invention include:
Zn12, Sb12, Sb15, Cd12, K1, Ag
1, ZrL, Sn12, Sn14, Sr12, Csl,
TI1, W12, TiL, CM, ThL, Pb12, B
Metal iodides such as i13, SbBr3, AgBr, S positive B
r2, CsBr, TIBr, CUBr, NaBr, Pb
Metal bromides such as Br2, NbBr5, mother Br2, CdC
! 2, KC1, AgC1, SnC12, TIC1, Fe
C13, TaC15, C mountain CI, NaC1, PbC12
, NbC13, BaC12 and other metal chlorides, Z cape 2, A
IF3, CrF2, ZrF4, S Misaki 2, TIF, FeF
2, FeF3, CuF, Nap, PbF2, NbF2,
The compound is selected from metal fluorides such as NiF2, BaF2, BiF2, M2, LiF, etc., and these compounds may be used singly or in combination of two or more.

Particularly desirable materials as halides used in the present invention are those that have low toxicity, are easily susceptible to thermal or photochemical activation such as phase change, decomposition, and photoreduction, and are capable of melting, vaporizing, or aggregating the metals mentioned above. It is easy to promote thermal deformation of the membrane, there is little deterioration due to moisture absorption, deliquescence, or reaction with metals, and the membrane is easy to manufacture.

The halide used as the recording material of the present invention is thermally or photochemically activated only when irradiated with a high-energy density light beam, thereby causing thermal effects such as melting, evaporation, or aggregation of the metals mentioned above. Although it is thought to have the effect of promoting deformation and does not act simply as an antireflection layer, it is clear that a lower light reflectance is more desirable in order to utilize light energy effectively.

The halide that can most effectively carry out the present invention is A.
g, A is r, A and 1, Pb12, PbBr2, POC1
2, PbF2, Sn12, SnC12, C mountain, CUBr
, CuC1, K1, KCI, etc. are preferred. These halides may be used alone to form various types of layer relaxation as described below, or two or more halides may be used in combination.

These halides may be provided as a halide layer on the support by the same method as the above-mentioned method for providing the metal on the support, or may be provided as a mixed layer with the metal. The thickness of the halide layer may be selected to be the optimum thickness to most easily cause the metal to undergo thermal deformation such as melting, evaporation, or aggregation by irradiation with a high-energy-density light beam.

The optimum film thickness of the halide layer varies depending on the type of metal, film thickness, etc., but is usually preferably about 50A to 1000A.
In the present invention, the structure of the recording layer containing metal and halide provided on the support can take various forms.

According to the present invention, the recording layer may be composed of a multilayer film of two layers or three or more layers including a metal layer and a halide layer,
Alternatively, a mixed layer in which a metal and a halide physically coexist may be formed.

Further, the recording layer may be formed by combining a mixture of a metal and a halide layer with a metal layer or a halide layer.
The thickness of the mixed layer of metal and halide layer may be sufficient as long as it is thick enough to obtain the optical density required as a recording material.
Naturally, it varies depending on the type and ratio of metal and halide.

For example, in order to obtain a transmission density of 2, if the metal and halide are mixed at a weight ratio of 7:3,
A mixed layer with a thickness of about 0A may be provided. The ratio of metal to halide in the mixed layer varies depending on the types of metal and halide and the film thickness of the mixture, but it is usually preferable that the weight ratio of metal to halide is about 1 to 1. Vacuum deposition, sputtering, ion plating, etc. are used as a method for providing a mixed layer of metal and halide on the support.

For example, a mixed layer can be provided by simultaneously vacuum-depositing a metal and a halide onto a support using separate evaporation sources. By controlling the temperature and charge amount of each evaporation source for the metal and halide layer, the evaporation rate of each layer can be controlled, and a mixed layer of metal and halide in an arbitrary ratio can be provided on the support. When a protective layer is provided on the recording layer made of the metal and halide described above, the durability, mechanical strength, and stability over time of the recording material are dramatically improved.

The protective layer must be transparent to the high energy density light beam used and have high mechanical strength.
It is required to react well with the recording layer, have good coating properties, and be easy to manufacture. Various resins can be used as the protective layer of the present invention, including styrene resins such as polystyrene, styrene-maleic anhydride resin, vinyl acetate resins such as polyvinyl acetate, polyvinyl alcohol phtyral, and polyvinyl formal. , enether methacrylate resins such as polyisobutyl methacrylate and polymethyl methacrylate, amide resins such as polydiacetone acrylamide and polyacrylamide, ethyl cellulose, cellulose acetate lactate,
Selected from cellulose resins such as cellulose nitrate and diacetylcellulose, polyvinyl chloride, polyhalogenated olefins such as chlorinated polyethylene, phenolic resins, soluble polyesters, soluble nylons, gelatin, etc., and copolymers thereof, etc. . These resins can be dissolved in various solvents and applied by known coating methods. There are various solvents that can be used, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, hexane, cyclohexane, ethyl cellosolve, methiclo , benzene, chlorobenzene, methanol, ethanol, butanol, petroleum ether, dimethylformamide, thinner, etc., depending on the resin used.

Various additives such as pigments, matting agents, plasticizers, and lubricants can be added to these resins depending on the purpose. In particular, higher fatty acids having 11 or more carbon atoms, or acid amides Adding about 0.1 to 1 skin t% of is effective in improving the lumbar strength of the recording material. Further, these lubricants such as higher fatty acids or acid amides can be applied to a thickness of 0.001 to 1 mm on the protective layer by a conventional method.

The thickness of the protective layer used in the present invention is selected to be the optimum thickness in consideration of the surface strength, stability over time, recording sensitivity, etc. required for the recording material. preferable. In the present invention, the layer structure of the recording material containing metal and halide provided on the support can take various forms.

The thermal recording material according to the present invention is characterized by improved protection of the recording layer without reducing recording sensitivity, and has the advantage of improved storage stability and significant reduction in scratches during handling.

In particular, when a halide is contained in the recording layer as in the present invention, gas generated by recording laser irradiation accumulates between the protective layer and the recording section, so that the protective layer protrudes and is easily scratched.

For this reason, the addition of higher fatty acids or acid amides is particularly effective in combination with a recording layer containing a halide. Various layer configurations will be explained below using drawings.

1 and 2 are cross-sectional views of recording materials, and throughout each figure, the same reference numerals refer to the same materials. FIG. 1 shows the most typical configuration of a recording material, in which a halide layer 2 is provided on a support 1 with a metal layer 3 sandwiched therebetween.

Further, FIG. 2 shows a multilayer structure including a metal layer 3 and a halide layer 2. On the other hand, as shown in FIG. 3, a mixed layer 4 containing a metal and a halide may be provided on the support 1.

Alternatively, it may include a layer in which other substances are mixed with a single metal or a combination of two or more metals in order to increase the recording sensitivity.

Particularly desirable conditions for these metals include low toxicity, low energy required for melting or evaporation, and ease of film production, and the most preferred are Sn, Bi, and In. Furthermore, as shown in FIG. 4, it may be of a simple structure in which a metal layer 3 and a halide layer 2 are each provided on the support 1 in a single layer.

In FIG. 4, the light irradiation is normally performed from the side where the recording layer is located, but if the light is irradiated from the support side, the structure shown in FIG. 5 is preferable.

Further, FIGS. 6 and 7 show the recording material of the present invention, which further includes a protective layer 5 on the layer structure shown in FIGS. 3 and 4, respectively.
It has been established.

According to the present invention, a recording material with high scratch resistance, high recording sensitivity, good image quality, non-toxicity, and excellent resistance to high energy density light beams was obtained.

EXAMPLES The present invention will be specifically explained below with reference to Examples. Example 1 On a polyethylene terephthalate support with a thickness of 100 mm, Sn and various halides were vacuum-deposited under vacuum conditions of 5 x 10-5 tons in a layer configuration as shown in Figure 4, and as shown in Table 1. A recording material consisting of the following composition was created.

The film thickness of each layer is set so that the transmission density is in the range of 1 to 2.
was selected to be 350A, and 200 to 400A for the halide.
Recording was performed on these recording materials by scanning an argon ion laser beam (wavelength 5145A) with a maximum output of 2W from the recording layer side with a lens at a scanning speed of about 25mm/sec. Ta.

The above-mentioned recording material was irradiated with varying laser output intensity, and the laser output intensity at which 10 recording spots were obtained was determined, and the relative sensitivity of the recording material was evaluated based on the magnitude of this value. Table 1 shows the type of halide, film thickness,
The value of the laser output intensity required for recording is listed. Table 1 As is clear from this table, the sensitivity of the recording material containing a coarse mixture of halides as described above is about 2 to 4 times higher than that of a single layer of metal (Sn).

In general, with thermal recording materials, if you compare short-time irradiation with high energy density and long-time irradiation with low energy density, it is clear that the former requires less total energy for recording; A so-called reciprocity failure occurs.

The energy required for recording shown in this example was determined by changing the laser beam output intensity while keeping the laser beam spot diameter and scanning speed constant, and the maximum energy required for recording, for example, It is also possible to compare the relative sensitivity of the recording material based on the magnitude of the maximum recordable scanning speed by keeping the output intensity of the laser beam constant and the spot size of the laser beam constant, and changing the scanning speed. If we compare the relative sensitivities using this method, we can see that the difference in relative sensitivity between the cases with and without the halides listed in Table 1 is larger than the 2 to 4 times the value mentioned above. it is obvious.

For example, when we compared the recording sensitivities of sample numbers 1 and 2 in Table 1 with a laser output intensity of 35 skin W and a laser beam with a diameter of 25 mm, we found that sample number 2 was better than sample number 2. It was found that the sensitivity was 8 times or more higher than that of 1. Also, when the laser beam was irradiated from the support side, the sensitivity was higher when using a halide than when using a single metal layer. In the examples described below, the relative recording sensitivity was evaluated based on the minimum laser output intensity required for recording as shown in Table 1.

Example 2 As in Example 1, various metals and halides (Pb12) were laminated on a support, and the relative sensitivity was evaluated in the same manner as in Example 1.

The results are shown in Table 2.

As is clear from Table 2, the sensitivity of the recording material using a halide (Pb12) is higher than that of a single metal layer.

Depending on the combination, there are some that have a high sensitivity of about 1M sound.
In addition to the metals shown in this table, Tj, Cr, Fe, Co
, Ni, Cu, Ag, Ce, Zn, Mn, Mg, Sb,
Similarly, when Pb12 and other halides were combined, the sensitivity was similarly high compared to the case of a single metal layer. Example 3 On a polyethylene terephthalate support having a thickness of 100 mm, metal (Sn or Bi) Pb12 was vacuum-deposited in a configuration as shown in FIG. 3 under conditions of a degree of vacuum of 5×lo-5 Ton.

The mixed layer of metal and Pb12 is created by using two types of evaporation sources, one for the metal (Sn or Bi) and the other for Pb12, and controlling the temperature of each to achieve the desired evaporation rate. At the same time, they were made so as to be attached to a support. The thickness of the mixed layer is 550A to obtain a transmission temperature of 1 to 2.
And so. The ratio of metal (Sn or Bi) to Pb12 in the mixed layer was selected to be 7:3 by weight. The recording material thus obtained does not exhibit interference colors, unlike the two-layer structure of metal and halide described in Examples 1 and 2.

The relative sensitivity of the recording material was evaluated in the same manner as in Example 1. In the case of a mixture layer of Sn and Pb12, Bi and Pb
In the case of a mixed layer with 12, sufficient recording was possible with a laser output intensity of 100 to 125 hW. Furthermore, almost the same sensitivity was exhibited whether the light beam was irradiated from the support side or the recording layer side.

That is, by using the mixed layer, the sensitivity was improved by 2 to 4 times compared to the case of a single metal. Furthermore, even when Pb12 was further laminated at 200A on the mixed layer thus prepared, sufficient recording was possible with 10 plates W at the same time. Example 4 On the same support as in Example 1, metal (Sn or Bi) and Pb12 were vacuum-deposited in the configuration shown in FIG. 1 under a vacuum condition of 5 x 10-5 Torr.

From the support side: Pb1250A, metal 350A, Pb
A recording material having a three-layer structure selected as 12150A was prepared.
Relative sensitivity was evaluated in the same manner as in Example 1. S
In both cases of n and Bi, sufficient recording was possible with a laser output intensity of 100 to 125 hW. Also, as shown in Figure 2, Pb1250A and metal (Sn or Bi)
Similarly, when 200 A is provided alternately on the support, 10
It was possible to record with a laser output intensity of 0 to 125 hW. Example 5 In the same manner as in Example 1, P was deposited on the support as shown in Figure 5.
b12 at 200A, metal (Sn or Bi) at 350A,
A recording material with sequential horizontal layers was prepared.

When sensitivity was evaluated in the same manner as in Example 1,
100 to 125 m when Caesar light is irradiated from the support side
I was able to record it with W. Also, when laser light was irradiated from the recording layer side, the sensitivity was higher than that of a single metal layer. Example
6 On the same support as in Example 1, vacuum degree 5 × 10-5 To
Bi, Sn, and Pb12 were vacuum-deposited in this order under conditions of n.

The relative sensitivity of the obtained recording material was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Table 3 As is clear from this table, it was found that even when the thickness of the metal layer was increased to increase the transmission density to 2 or more, the sensitivity was higher than in the case of a single metal layer.

That is, when a high transmission density is required, a single metal layer requires a very high laser output intensity, but according to the present invention, a recording material with extremely high sensitivity can be obtained.
Example 7 On the various recording layers described in Example 1, 1 g of chlorinated polyethylene (LPA manufactured by Sanyo Kokusaku Pulp), 0.1 g of triphenyl phosphate, and 9 parts of stearic acid amide dissolved in 10 parts of toluene were added. After that, apply it to a thickness of about 0.2 mm, and then add 1 g of stearic acid and 0.0 g of behenic acid. A protective layer was formed by dissolving the solution in 10 μm of n-hexane and applying it to a thickness of about 0.02 μm.

The relative sensitivities of the various recording materials thus obtained were evaluated in the same manner as in Example 1. As a result, the laser output intensity required for recording shown in Table 1 increased by only 25 to 5 W, and the sensitivity was sufficiently high compared to a single metal (Sn) layer. Further, by providing such a protective layer on the recording layer, the surface strength of the surface was significantly improved. Example 8 350% Sn was deposited on a polyethylene terephthalate film with a thickness of 100 m under a vacuum degree of 5 x 10-5 Ton.
A metal layer was formed by vapor deposition of A, and each compound was further vapor-deposited for each sample as shown in Table 4 on top of the metal layer to form a recording layer consisting of two layers.

At this time, the transmitted optical density of each sample was within the range of 1 to 2. The sample at this stage is designated as A, and the samples are designated as Sample A to Sample A6, respectively. Next, for each sample, one piece of chlorinated polyethylene (manufactured by Sanyo Kokusaku Pulp ■, "
LTA-305'', chlorine content 65-6 groove weight%,
The viscosity at 2500 of a wt% toluene solution of 2 is 4~
7cps. ) was applied so that the dry film thickness was 3rm.

The sample at this stage is designated as B, and each sample is designated as Sample B to Sample B8. On the other hand, the above chlorinated polyethylene layer was coated on the other pieces of Sample A to Sample N so that the dry film thickness was 0.6 mm.

The sample at this stage is designated as C, and each sample is designated as sample C, ~ sample C8.
shall be. Furthermore, a piece of sample C was taken, and 1 g of stearic acid and 0.0 g of behenic acid were each taken as organic fatty acids. * was dissolved in 2 hexane and applied to a dry film thickness of 0.051 m. The sample at this stage is designated as D, and each sample is designated as sample D.
．． - Sample D8. An argon ion laser beam (wavelength 5145A) with a maximum output of 2W is focused on each of these journal materials from the recording layer side using a lens to a beam diameter of 25rm, and scanning recording is performed at a scanning speed of 19m/sec. The minimum laser output intensity at which a recording trace with a diameter of 10 rms was formed was determined.

In addition, the film thickness and strength of these samples were measured using “HEmO” manufactured by Shinto Kagaku.
While applying a load using an R ball needle (R = 0.4 fence) using an N-18" membrane surface strength meter, the minimum load that caused a kiss on the surface was taken as an index of membrane strength. The results of these measurements were 4
As shown in the table.

Table 4 As shown in Table 4, samples B to B8 in which a chlorinated polyethylene layer (3 mm) was provided on the recording layer are different from sample A in which only the recording layer was provided, and sample A in which only the recording layer was provided. In comparison, although the film surface strength is considerably improved, the minimum required output of the laser is large.

In other words, the recording sensitivity is significantly inferior. Sample C, in which the chlorinated polyethylene layer was made as thin as 0.61 m,
~Sample C8 was able to maintain the recording sensitivity at approximately the same level as Sample A and ~Sample A8, respectively, but the film surface strength was not as high as Samples B~Samples B3. However, Samples D and D2 according to the present invention maintained the recording sensitivity at the same level as Sample C, and exhibited extremely high film surface strength. Example 9 Example 8 was carried out in exactly the same manner as in Example 8 except that the metal Sn in the metal layer in the recording layer was replaced with Bi, and almost the same results were obtained in each case.

Example 10 A recording layer was prepared by depositing Sn as a metal layer to a thickness of 350A and GeS as a compound layer to a thickness of 200A on a polyethylene terephthalate film with a thickness of 100㎜ under vacuum conditions of 5 x 10-5 Torr. was formed.

The sample at this stage is referred to as sample A. Next, on the two pieces of Sample A, solutions 1 and 2 of the following polymeric substances were applied as organic polymer protective layers to 3 mm and 0.6 m, respectively, to form organic polymer protective layers. Solution ■: 10% toluene solution of polystyrene Solution ■: 10% methyl ethyl ketone solution of polyurethane (Estan 571r, Goodrich Co., USA) These samples are as shown in Table 5.

For Samples C and C2 in Table 6, a solution of 1 g of stearic acid and 0.3 g of behenic acid dissolved in 20 ml of hexane was further applied to give a dry film thickness of 0.05 Am.

The samples at this stage are referred to as sample D and sample D2. For each of the above samples, the minimum laser output intensity and pus surface intensity required for laser recording were measured in the same manner as in Example 8.

The results are shown in Table 6. Table 5 Examples
11 Stearic acid amide dissolved in turpentine oil was applied onto sample B2 in Example 10 so that the dry film thickness was 0.05 mm.

As a result of testing similar to Example 8 on this sample,
The minimum required power for laser recording was 275 mW, and the film surface strength was 1.5k9. That is, as is clear from a comparison with the case of sample D2 in Example 8, even when higher fatty acid amide was used instead of stearic acid etc., the same results as with higher fatty acids were obtained. Example 12 For Sample C and Sample C7 in Example 8, a composition with the following formulation was applied in place of the chlorinated polyethylene layer serving as a protective layer, and the other conditions were the same as in the case of Sample C and Sample C7. Created recording materials.

Recipe Chlorinated polyethylene Akebono (same as Example 1) Methyl ethyl ketone 50 g Methyl cellosolve acetate 50 g Stearic acid 30 mg These samples were tested in the same manner as in Example 8, and the same results as in Example 8 were obtained. Ta.

That is, in the sample of this example corresponding to sample C, the recording laser output requires 12 W and the film surface strength is 1.5k9, and in the sample of this example corresponding to sample C7, the recording laser output requires 225 hW. The film surface strength is 1.5k9. In this way, even if a higher fatty acid amide is used instead of a higher fatty acid, and even if a higher fatty acid or the same amide is contained in the protective layer instead of coating the higher fatty acid on the protective layer, the same effect can be obtained. was recognized. Example 13
Even when stearamide was used in place of the stearic acid used in Example 12, exactly the same effect as in Example 12 was obtained.

Furthermore, when a similar protective layer is provided on the recording layer of the various recording materials described in Examples 2 to 6, the laser output intensity required for recording increases by only 25 to 5 hW, compared to the case of a single metal layer. The sensitivity was sufficiently high.

Furthermore, when the recording traces of the recording material of the present invention were observed under magnification using a scanning electron microscope, it was found that the recording layer in the area hit by the laser beam spot was completely removed, or that the recorded spot was completely removed. It was confirmed that small particles were agglomerated around the periphery.

Therefore, according to the present invention, a high-sensitivity recording material with high contrast and excellent image quality was obtained. Embodiment 1 A metal selected from Sn, Bi, and ln and a halide that can be thermally or photochemically activated by light irradiation and promote thermal deformation such as melting, evaporation, or aggregation of the metal on a support. In a recording material in which a recording layer containing 11 or more carbon atoms or a higher fatty acid containing 11 or more carbon atoms is provided in or on the protective layer containing an organic polymer as a main component. A recording material characterized by the presence of amamide.

Embodiment 2 A metal selected from Sn, Bi, and ln and a metal that is thermally or photochemically activated by light irradiation to promote thermal deformation such as melting, evaporation, or aggregation of the metal are placed on a support. o Genide, Ag1, AgBr, A, 1, Pb12, PbBr2
, PbC12, PbF2, Sn12, SnC12, C mountain, C light, CuC1, K1, KCI, etc., and a protective layer containing an organic polymer as a main component is provided thereon. 1. A recording material comprising a higher fatty acid or a higher fatty acid amide having 11 or more carbon atoms in or on the protective layer.

[Brief explanation of the drawing]

1 to 5 are diagrams showing the structure of a recording material, and FIGS. 6 and 7 are sectional views showing the layer structure of the recording material obtained by the present invention. In the figure, 1 is a support, 2 is a halide layer, 3 is a metal layer,
4 represents a mixed layer of metal and halide, and 5 represents a protective layer. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7

Claims (1)

[Claims] 1. A recording layer containing a metal and a halide that can be thermally or photochemically activated by light irradiation and promote thermal deformation such as melting, evaporation, or aggregation of the metal is provided on a support,
A recording material on which a protective layer mainly composed of an organic polymer is provided, characterized in that a higher fatty acid or a higher fatty acid amide having 11 or more carbon atoms is present in or on the protective layer. Recording materials.