JPS62249788A - Film for laser recording - Google Patents

Abstract

PURPOSE:To obtain a notable mar resistance and to prevent a cohesion of graphite particles in a recording layer, by providing a protective layer made of fine particles of thermoplastic polyester on the recording layer. CONSTITUTION:A protective layer made of fine particles of thermoplastic polyester is formed on a recording medium layer. It is desirable that the fine particles of thermoplastic polyester have an appropriate softening point ranging 50-300 deg.C and an adequate binding property with the surface of the recording layer as well as with each other. The thermoplastic polyester, such as a copolymer made of terephthalic acid and ethylene glycol or a copolymer composed of terephthalic acid, isophthalic acid, and ethylene glycol, is fine particles preferably of 0.001-100mum paticle diameter. The thickness of the recording medium layer together with the protective layer are desirably in the range of 0.1-2 mum and that of the protective layer is preferably in the range of 0.01-0.3mum ; these values depend on an output of a laser in use and also heat ray absorber loadings.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a laser recording film using a heat mode recording method, and particularly to a laser recording film that has excellent performance as a film for plate making.

In recent years, many methods using laser light have been proposed in fields where high-speed or real-time recording of information is required. This method utilizes the strength and resolution of the optical energy of laser light, and a reward with good light absorption is irradiated with light, and the reward, which is absorbed and heated, is deposited on the image receiving surface by vapor deposition. It is used to record images.

(Prior Art) The present inventors have also found that it is possible to achieve high blackening density with respect to such recording films by using a non-self-oxidizing binder as a binder and further using graphite as heat-absorbing fine particles. Furthermore, by containing a heat ray absorbing agent that has a strong absorption ability in the wavelength range of the YAG laser beam used for recording, it is possible to easily transfer the recording medium to a transfer image receiving surface such as paper or a printing plate, and also to transfer the recording medium to a transparent substrate. It was discovered in 1973 that it was possible to obtain a laser recording film that could produce high-resolution negative and positive images without leaving any residue on the recording medium.
The application was filed as No. 9-41724. However, such a recording layer itself is easily scratched, and since the dry coating film thickness is as thin as approximately α5 μm, scratches occur not only on the surface of the recording layer, but also on the surface of the recording layer.
Easily reaches the surface of the substrate.

Such scratches significantly impair the function of the film as a laser recording film.

As a way to solve this problem, the present inventors created a laser recording film that has remarkable scratch resistance compared to conventional laser recording films by providing a protective layer made of thermoplastic polymer on the recording layer. find out what you can get,
It was previously filed as Japanese Patent Application No. 59-112311.59-185176.

In addition, they discovered that a laser recording film with extremely excellent transferability could be obtained by using a solvent-soluble polyester resin as a protective layer.
I applied as 37.

This laser recording film can produce high-resolution negative and positive images with one exposure to laser light.

Films with images recorded on them can be used as A-body Kid micro-films, photomasks, and other high-density recording media. A transfer image receptor on which a negative (if the film side is positive) can be used as a proof copy, a printed matter, etc.

By selecting the coating method and coating solvent for coating the protective layer, it was possible to prevent any influence on the recording layer, such as dissolution of the recording layer.

By using a coating method such as a fountain method, a fountain reverse method, or a dipping method, stable coating can be performed without damaging the recording layer.

However, if the protective layer is coated using a solvent that has a strong dissolving power for the binder resin in the recording layer (or if the binder resin in the recording layer has good solubility), the effect on the recording layer cannot be completely prevented. , there was a possibility that agglomeration of graphite particles in the recording layer would occur. If aggregation of graphite particles occurs, there is a risk of a decrease in light-shielding properties (decreased blackening density), which will significantly impair the performance of the mask film for laser recording films, especially as a mask film for plate-making. be.

(Means for Solving the Problem) As a result of intensive studies to solve these drawbacks, the present inventors found that by providing fine particles made of thermoplastic polyester on the surface of the recording layer on a transparent substrate, The present inventors have discovered that a laser recording film can be obtained in which the aggregation of graphite particles in the recording layer is reduced compared to the laser recording film described above.

That is, the present invention provides a non-self-oxidizing binder resin, heat-absorbing fine particles that provide high blackening density, and a heat ray absorber that has a strong absorption ability in the wavelength range of the laser light used for recording, on a transparent substrate. The object of the present invention is to provide a laser recording film having a recording layer containing the same, characterized in that a protective layer made of fine particles of thermoplastic polyester is provided on the recording layer.

(Structure of the Present Invention) As a method of recording on the laser recording film of the present invention, a method of recording an image by depositing it on the image receiving surface of an ordinary image receptor 4 as shown in FIG. 2 can be used. can.

It is desirable that the transfer image receptor 4 be mounted in contact with the transfer supply body 2, and if the degree of adhesion is improved by reducing the pressure, the resolution will be even better.

According to this method, a positive image can be obtained on the transfer image receptor 4 and a negative image can be obtained on the transfer supply body 2 in one operation. The negative film can be used as an original film when producing a printing resin plate, and the positive image can be used as a proof copy or a direct printing plate depending on the type of transfer image receptor 4.

The support for the laser recording film of the present invention, especially the laser platemaking film, may be any film that transmits laser light, such as polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polypropylene, polycarbonate, nylon. 6. Films such as polyether Nurphone may be mentioned. In particular, biaxially stretched films of polyethylene terephthalate and polypropylene are preferred because they have excellent transparency, strength, and dimensional stability.

Examples of pigments that absorb heat in the recording medium and those that have high light-shielding properties include graphite. This graphite can be used alone or in a mixture with carbon black or the like. In order to provide a high blackening density in a thin film, the graphite is preferably in the form of fine particles of 2 μm or less. More preferably, a graphite having a particle size distribution in which 50% or more of particles having α4μ or less and 25% or more of particles having α2P or less is suitable.

As the non-self-oxidizing binder in the recording medium, acrylic resins, cellulose derivatives excluding nitrocellulose, phenolic resins, polyvinyl chloride, polyvinyl chloride-vinyl acetate copolymers, etc. can be used. By using a non-self-oxidizing binder resin, the safety concerns during storage and the problems that occur during laser light irradiation of self-oxidizing binder resins such as nitrocellulose are completely eliminated.

The blackening density of the recording medium is α5 or more, preferably 20 or more, in order to provide light-shielding properties. If the blackening density is low, the light-shielding performance as a negative film (original film for plate making) will be poor, and even a positive image will have a weak print. Therefore, the amount of non-self-oxidizing binder resin is 20 to 100 parts of graphite.
It is used in an amount of 100 parts by weight, preferably 50 parts by weight or less.

Examples of the heat ray absorbent contained in the recording layer of the present invention include compounds represented by the following general formula (1) or (2).

General formula I; (where R is hydrogen or a lower alkyl group, X is a hexafluoroarsenate ion, a hexafluoroantimonate ion,
It is an anion selected from the group consisting of fluoroborate ion and perchlorate ion, and m is 0 or an integer of 1,2.

Ar represents H◎Ga' or =C)-, and n is 1 or 2
f) If m is an integer of 2, A indicates =mouth=.

Examples of this general formula include hexafluoroantimony of bis(p-diethylaminopheny7I/)(N,N-bis-(1)-diethylaminopheny/I/)-p-aminopheny/l/)aminium. acid salt, hexafluoroarsenate, perchlorate or fluoroborate, N,
Hexafluoroantimony rHIm, hexafluoroarsenate, perchlorate or fluoroborate of N,N',N'-tetrakis(p-diethylamine), bis(p-diethylamine);
-diglopiμaminophenyl) (N%N-bis-(p
-diglobi p aminopheni 1v) -1-aminopheni μ
] Hexafluoroantimony 112% of Ataminilum,
Hexafluoroantimonate of hexafluoroarsenate, perchlorate or fluoroboric acid 4, N%N%N', N'-tetrakis(p-dipropyμaminophene/v)-I)-benzoquinone-bisimmonium , hexafluoroborate, perchlorate or fluoroborate,
N,N,N',N'-tetrakis (p-digtylaminophenyl electronium hexafluoroantimonate, hexafluoroarsenic acid melon, perchlorate or fluoroborate, bis(p-digtylaminophenyl) hexafluoroantimonate, hexafluoroarsenate, perchlorate or fluoroborate of p-aminophenylcoaluminium (thylaminophenyllaminophenyl), N,
N, N'1. - Hexafluoroantimonate, hexafluoroarsenate, perchlorate, or fluoroborate of N/-tetrakis-(p-digtylaminophenyl)-p-benzoquinone-bisimmonium.

General formula ■; (where G is hydrogen, alkyl group, halogen group, M is nickel, cobalt, palladium, platinum, m is an integer of -1 or -2, A is monovalent when m is -1) (It is a divalent cation when m is -2.) An example of a compound represented by the general formula (■) is bis(1-mercapto-2-naphtholate)nicke/L/(II)tetra -n-butylammonium. The amount of the heat ray absorber added is preferably in the range α01 to 200 parts by weight, particularly 0.1 to 100 parts by weight, based on 100 parts of graphite.

When the fine particles of thermoplastic polyester, which is a feature of the present invention, are irradiated with laser light from the transparent substrate side, they are softened by heat generation in the recording layer, and are transferred together with the recording layer to the transfer image receptor.

It is desirable that the thermoplastic polyester fine particles have an appropriate softening point in the range of 50°C to 300°C, preferably 70'c to 230°C.

Further, it is desirable to have appropriate binding properties with the surface of the recording layer and between particles. Thermoplastic polyesters include copolymers of terephthalic acid and ethylene glycol, copolymers of terephthalic acid, isophthalic acid, and ethylene glycol, terephthalic acid, isophthalic acid,
Examples include copolymers of ethylene glycol and neopentyl glycol, and copolymers of terephthalic acid and triethylene glycol. The particle size of the thermoplastic polyester fine particles is preferably α001μ to 100μ,
It is desirable to have a particle size of α01 to 1μ.

Fine particles of thermoplastic polyester are used as water-soluble or oil-soluble emulsions.

Particularly in the case of water-soluble products, since no organic solvent is used, there is no toxicity or
There are no problems in recovering the solvent.

The thickness of the recording medium layer and the thickness of the protective layer are determined by the output of the laser beam used, pp! Although it is influenced by the amount of the line absorber added, the range of α1 to 2μ for the recording medium layer and the protective layer is good, and preferably α2 to α5P.
(“The thickness of the protective layer is preferably in the range of 0.01 to 0.3μ, preferably 0.05 to 0.15μ.”) Coating methods include barcode coating, spin coating, dip coating, air knife coating, or roll coating. In the court, fountain method,)
Methods such as the 7-unten reverse method can be applied.

As the transfer image receptor, general paper, plastic film, synthetic paper (white pigment dispersed in plastic film), anodized aluminum, copper-clad laminate film, etc. are used.

When using general paper, plastic film, synthetic paper, etc., it can be used as a proof copy or printed matter, and when using anodized aluminum with copper-clad laminated film, it can be used as an etching resist for making printed wiring boards. .

Effects of the Invention) The setting of the protective layer composed of fine particles made of thermoplastic polyester in the present invention exhibits remarkable scratch resistance without impairing the high resolution of the laser recording film, and also reduces graphite in the recording layer. A high blackening density could be maintained even after the protective layer was applied without causing particle aggregation.

Therefore, the performance of the laser recording film as a mask film, particularly as a mask film for plate making, could be improved.

(Example) The present invention will be described below with reference to Examples. All parts in the examples represent parts by weight.

Example 1 Using a graphite dispersion consisting of the following formulation 1,
Coat the barcode on μ polyester film,
It was dried at 90°C to form a recording layer.

A liquid mixture consisting of Formulation 2 was coated on this recording layer by dip coating and dried at 90°C to form a protective layer, thereby obtaining a laser recording film.

Formulation 1 Graphite 100 parts Ethyl cellulose 36 parts Ethyl acetate/Lt 1224 parts Binu (p-diethylaminophenyl/l/) 6.8 parts [N%N-
Bis-(p-diethylaminopheny/L')-1)-aminophenyl]aminium hexafluoroantimonate formulation 2 Polyester aqueous dispersion 100 parts (Pyronal MD-1200 manufactured by Toyobo ■) Water
200 parts Example 2 A coating solution consisting of formulation 3 was applied to the recording layer coated in Example 1 using Diffug Coat, and dried at 90°C.
Prescription 3 to form a protective layer and obtain a laser recording film Polyester aqueous dispersion 100 parts (NOF V77-CP-PETAIn) Water 200 parts Comparative Example Prescription on the recording layer coated in Example 1 A coating solution consisting of 4 was applied to form a protective layer to obtain a comparative laser recording film.

Formulation 4: 100 parts of solvent-soluble polyester (“Vylon 200” manufactured by Toyobo Co., Ltd.) 900 parts of methyl ethyl ketone Nd focused on
:YAG laser light (wavelength IQ 64nm, output 10W,
It is also shown in Table 1.

Table 1 Note 1) Blackening density - 4 of (O/O); O = Incident light intensity - Transmitted light intensity Note 2) The scratch resistance test of Examples was carried out by the following method.

As shown in FIG. 3, a film consisting of a support 1, a recording layer 2, and a protective layer 3 is cut into 101×1 (1 m) pieces, a piece of paper with an area of 1 d is placed on the coated surface, and while applying a load of 7, it is horizontally
Move cm. After that, check the moved part for any damage. An experiment was conducted while applying a load, and the value of the load when the recording layer was scratched was evaluated as the scratch resistance of the protective layer using the following criteria.

A: The recording layer is not scratched under a load of 500g.

B: The recording layer was not scratched under a load of 250 g.

C: Scratches occur under a load of 50g.

Note 3) YAG laser imaging test results Nd = The evaluation was the maximum score when the following nine types of patterns with different line widths were recorded using a YAG laser imaging tester.

[Brief explanation of drawings]

Fig. 1 1... Support 2 - Recording layer 3... Protective layer Fig. 2 1... Support 2... Recording layer (transfer supply body) 3... Protective layer 4... Transfer image receptor 5 Laser light Figure 3 1...Support 2...Recording layer 3...Protective layer 6...Paper 7...Load Patent applicant: Daicel Chemical Industries, Ltd.
Understand 4 = BAW 堝 Proceedings of the Amendment dated July δ, 1985 ＼ List of I- 1. Indication of the case 1985 Patent Application No. 93264 2. Name of the invention Laser recording film 3. Make the amendment Relationship with the case Patent applicant zip code 590 Address 1 Teppocho, Sakai City, Osaka Name
(290) Daicel Chemical Industries, Ltd. Representative name: Yoshifumi Kubota 4, Agent: Rh<3-8-1 Seki, Chiyoda-ku, Tokyo Toranomon Mitsui Building Daicel Chemical Industries, Ltd. Patent Department Telephone: (507) 3246-8-5 , Date of amendment order: June 4, 1985 (Date of dispatch: June 24, 1986) 6. Brief explanation of drawings in the accompanying specification of the amendment 7, Contents of the amendment 1) Memorandum No. M On page 19, line 7, “Figure 1” should be corrected to “Figure 1 is a cross-sectional view of the laser recording film of the present invention.” 2) On page 19, line 11, “Figure 2” should be corrected to “Figure 2 is a cross-sectional view of the laser recording film of the present invention.” "Schematic sectional view of a recording device using film". 3) ``Figure 3'' on line 17 of the same page is corrected to ``Figure 3 is a diagram showing the measurement method for the scratch resistance test.''

Claims (1)

[Claims] A recording medium layer consisting of a non-self-oxidizing binder, a highly light-shielding pigment that absorbs heat, and a heat ray absorber that has a strong absorption ability in the wavelength range of the laser light used for recording was provided on a transparent substrate. 1. A laser recording film, characterized in that a protective layer made of thermoplastic polyester fine particles is provided on the recording medium layer.