JPS62286735A - Sheet material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention (Field of Industrial Application) The present invention provides a method for temporarily protecting an adhesive sheet.
The present invention relates to a cover sheet material that can be easily peeled off.

In particular, the present invention relates to cover sheet materials used in image transfer methods used primarily for color proofing, displays, and the like.

(Prior art) A photosensitive laminate comprising a release layer made of an organic polymer and a photosensitive resin layer on a temporary support is exposed and developed to form an image on the release layer, and then an image is formed on the release layer. The method of transferring images is known, and is disclosed in Japanese Patent Publications No. 15326-1970 and Japanese Patent Publication No. 49-49.
41 etc. These methods have the advantage that they can be used for both overlay type and subprint type as color proofs, but the process is complicated as adhesive is used each time, and each color is It has the disadvantage that alignment accuracy during transfer is difficult.

As a method to eliminate the complexity of these processes, a method has been proposed in Japanese Patent Application Laid-Open No. 47-1981 in which, after forming an image, the image is brought into close contact with an image-receiving sheet, and the image is transferred onto the image-receiving sheet by applying heat and pressure.
41830, JP 48-93337, and JP 51
-5101. Especially JP-A-51-51'
No. 01 describes a method of providing a single layer of a heat-melting polymer as an adhesive on a permanent support, and Japanese Patent Application Laid-open No. 1983-1999
-41830 also describes a method of directly transferring an image to a permanent support such as art paper or coated paper.

However, these methods have the following drawbacks. One is that the final image will be left and right opposite to the original, and the other is that when heat-melting polymers are used, their melting point is generally high and the transfer temperature is high, so the heat causes the support to The dimensional stability of the image is poor (this results in misalignment of the transfer of each color.Also, when a polymer with a low melting point is used, adhesion after image formation is likely to occur, and scratches may occur. It has disadvantages such as being easy to use. JP-A-59-971
40, as a method to improve the above-mentioned drawbacks, the images of each color are first transferred onto a temporary image-receiving sheet provided with a photopolymerizable image-receiving layer before the images of each color are transferred onto a permanent support. A method is disclosed in which the photopolymerizable image-receiving layer is then retransferred onto a permanent support and further exposed to light over the entire surface to solidify the photopolymerizable image-receiving layer.

With this method, a normal image is created on the mask original, and since an ethylenic polyfunctional top layer is included during transfer,
Although the photopolymerizable image-receiving layer itself is soft and can be transferred at low temperatures, the photopolymerizable image-receiving layer is hardened by exposure afterwards, so it has good adhesion resistance and is resistant to scratches, and most of the above-mentioned drawbacks are avoided. It will be resolved.

On the other hand, in these image transfer methods, when transferring, a transfer material made by overlapping a transfer sheet on an adhesive image-receiving sheet is placed on a metal plate such as aluminum, and a cover sheet is placed over this to remove the protruding adhesive part. There is a method of applying uniform pressure while protecting the cover sheet, and a polymer film such as a polyester film is used as the material for this cover sheet.

(Problems to be Solved by the Invention) However, as in the past, simply using a polymer film as a cover sheet material was insufficient in the following points.

i) When the image-receiving sheet and transfer material are misaligned When removing the cover sheet material from the adhesive transfer material, the transfer material is also lifted at the same time, making it difficult to remove, and in some cases, the transfer material may peel off between the eyebrows, causing the transfer to fail. Something happened.

ii) When the cover sheet material is peeled off from the adhesive transfer material, the film becomes electrically charged and the human body is therefore electrically charged and may receive an unpleasant shock.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a sheet material that can be easily peeled off from an adhesive surface such as a transfer material and that does not suffer from shock due to charging.

(Means for solving problems) Object of the present invention: A support, a conductive layer provided on one side of the support, and a conductive layer provided on one side of the support. or a silicone compound-containing layer provided directly on the support, and the conductive layer has a surface resistance of 10
This was achieved with a sheet material that is less than 13Ω.

The support for the sheet material of the present invention is preferably a chemically and thermally stable flexible substance, specifically a thin sheet of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, etc., or a laminate thereof. Preferably something.

These supports are subjected to surface treatments such as corona treatment, glow discharge treatment, surface cloaking, and ultraviolet irradiation, or are coated with an undercoat layer in order to increase the adhesion with the silicone compound-containing layer and/or the conductive layer. It is also possible to provide one. Further, fine particles or the like may be kneaded into the support for the purpose of matting the surface, or conductive fine particles or an antistatic agent may be kneaded in advance for the purpose of imparting conductivity. The support used has a thickness of 50μ to 300μ, preferably 75μ to 150μ.

In the present invention, the conductive layer provided on the support can be appropriately selected from known materials, and particularly conductive materials include ZnO1T i O2, Sn 0
2% A R203\T n 203. -3i02,
A method of containing fine particles of a crystalline metal oxide and/or a composite oxide thereof selected from MgO, Bad, and MoO2 is preferable because it exhibits conductivity that is not affected by humidity.Crystals The volume resistivity of the fine particles of a metallic oxide or a composite oxide thereof is preferably 10 7 Ω·cm or less, particularly preferably 10 5 Ω·cm or less.

Moreover, the particle size is 0.01 to 0.7 μ, especially 0.0
It is preferable that it is 2 to 0.5μ.

The method for producing fine particles of conductive crystalline metal oxides and their composite oxides is described in detail in JP-A-56-143430. A method in which metal oxide fine particles are produced by firing and then heat treated in the presence of different atoms to improve conductivity.A second method is a method in which different atoms coexist in order to improve conductivity when manufacturing metal oxide fine particles by firing. A third method is to reduce the oxygen concentration in the atmosphere and introduce oxygen defects when producing metal fine particles by firing.

An example containing a different type of atom is Al for ZnO.

Examples include In, Nb, Ta, etc. for TiO2, and Sb, Nb, halogen elements, etc. for 5n02.

The amount of foreign atoms added is preferably in the range of 0.01 to 30 mo 1%, but is 0.1 to 10 mo.

Particularly preferred is 1%.

The amount of conductive particles used is preferably 0.05 g/m to 20 g/d, particularly preferably 0.1 g/m to Log/%.

The conductive layer according to the present invention includes, as a binder, cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, vinyl chloride,
Styrene, acrylonitrile, vinyl acetate, alkyl (
Homopolymers or copolymers containing alkyl groups C1-C4) acrylate, vinylpyrrolidone, etc., soluble polyesters, polycarbonates, soluble polyamides, etc. can be used. When dispersing the conductive particles in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. Also, adding a binder, crosslinking agent, etc. will not be a problem.

Examples of titanium-based dispersants include titanate coupling agents described in U.S. Pat. No. 4,069,192 and U.S. Pat.
(manufactured by), etc.

Examples of known silane dispersants include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. It is commercially available as a "silane coupling agent" from Shin-Etsu Chemical 411 and other companies.

Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, and epoxy crosslinking agents.

A preferred conductive layer in the present invention can be provided by dispersing conductive fine particles in a binder and providing the support layer, or by subjecting the support to subbing treatment and depositing the conductive fine particles thereon. . In order to prevent electrostatic shock due to charging using the sheet material of the present invention, it is necessary that the surface resistance value of the conductive layer be 10 13 Ω or less, and particularly preferably 10 12 Ω or less.

In the present invention, in order to improve scratch resistance,
Preferably, a hydrophobic polymer layer is further provided on the conductive layer. In this case, the hydrophobic polymer layer may be applied in the form of a solution dissolved in an organic solvent or an aqueous latex, and the coating amount is preferably about 0.05 g/rd to Ig/m in terms of dry weight.

Examples of the hydrophobic polymer include vinyl polymers including cellulose esters (eg, nitrocellulose, cellulose acetate), vinyl chloride, vinylidene chloride, vinyl acrylate, and polymers such as organic solvent-soluble polyamides and polyesters. This layer contains a slipping agent for imparting slipping properties, such as JP-A-55-79.
There is no problem in using organic carboxylic acid amides such as those described in No. 435, and there is no problem in adding a matting agent or the like.

When providing an undercoat layer, Japanese Patent Application Laid-open No. 135526/1983, US Pat. No. 3,143,421, US Pat. No. 3,586,508,
Vinylidene chloride copolymers as described in JP-A No. 2698235 and US Patent No. 3567452, butadiene as described in JP-A-51-114120 and US Pat. No. 3,615,556, etc. Diolefin copolymers, copolymers containing glycidyl acrylate or glycidyl methacrylate as described in JP-A-51-58469, etc., JP-A-48-2
Polyamide/epichlorohydrin resins as described in JP-A No. 4923, maleic anhydride-containing copolymers as described in JP-A-50-39536, etc. can be used.

The present invention also applies to JP-A-56-82504, JP-A-56-143443, JP-A-57-104931, JP-A-57-118242, JP-A-58-62647, JP-A-60-258541, etc. The conductive layers shown can also be used as appropriate.

If the conductive layer is contained in the same or different plastic raw material as the support film and coextruded at the same time as the support film, a conductive layer with excellent adhesiveness and scratch resistance can be easily obtained. Therefore, in this case, there is no need to provide the above-mentioned hydrophobic polymer layer or undercoat layer, and this is a particularly preferred embodiment of the conductive layer in the present invention.

In the present invention, in order to easily peel off the sheet material from the transfer material, a layer containing a silicone compound is provided as a release layer on one surface of the sheet material. This layer may be provided on top of the conductive layer.

The silicone compound used for eyebrows containing the silicone compound of the present invention has a 5i-0- bond in the main chain and has an organic group R on silicon. The monofunctional type and the trifunctional type have the composition -〇-3i-〇-, and the organic group R is a hydrogen atom, a methyl group, a phenyl group,
There are vinyl groups, ethyl groups, etc., and flexibility, durability, etc. can be controlled by the type and ratio of organic groups and the degree of reticulation. Silicone compounds are supplied on the general market by hydrolyzing chlorosilane and then dehydration condensation, or by ring-opening polymerization and dissolving the initial condensation +)J in a suitable solvent. This compound can be crosslinked and cured by using it in combination with a catalyst or a curing agent, or by heating it. rack + f
,, ) There are two types: condensed type and addition type, and the condensed type IPi format is as follows: i) SiOH + CHB RoOjin i-1~5
i-0-person 1- iii) SiOH+H〇-person i- 1~5i-0-person 1- chant iv) S i OH↓Roai- j.

□～5iO-5i- ; etc., and as an addition type cross-linking form;
-CH2-3i~ etc.

The releasability of silicone is thought to be due to its non-polar nature and the non-adhesion of the methyl group of the hydrophobic group.

Such silicone compounds are available as silicone varnish types such as KS-700, KS-701, and KS- manufactured by Shin-Etsu Chemical.
707, Pan Glaze manufactured by Toray Silicone
Glaze) 620. K manufactured by Shin-Etsu Chemical as a solution type
S-705F, KS-709, KS-770S (?
73M671 from Ren Toshiba, Syloff 23 from Toray Silicon, Silotex 32 from Fuji Polymer, and KM-763 from Shin-Etsu Chemical as an emulsion type, and M-764B from Shin-Etsu Chemical.

5yloff 22.5ylof made by Toray Silicon ■
f 25, 5irotex 30E manufactured by Fuji Polymer ■
, 5irotex 31E, etc. can be used.

The thickness of the silicone layer is preferably 0.01μ to 2μ, more preferably 0.02μ to 0.5μ.

For coating the conductive layer and the silicone compound-containing layer, conventional methods such as roller coating, air knife coating, gravure coating, bar code coating, curtain coating, etc. can be adopted.

Regarding image transfer materials, Japanese Patent Publication No. 46-15326, Japanese Patent Publication No. 49-441. JP-A-47-41830, JP-A-4
8-93337, JP-A-51-5101, JP-A-59-
97410 and the like can be used.

(Effect of the invention) When a transfer material is sandwiched between the sheet material of the present invention and a metal plate and heat transfer is performed, the sheet material and the transfer material can be easily separated after transfer, so that work efficiency is greatly improved. Not only that, but there is no charging phenomenon, so electrostatic shock during handling can be prevented.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 The following sheet materials a to h were prepared as cover sheet materials used in the transfer operation.

[Method for producing sheet material for cover sheet] Silicone KS-700 manufactured by Shin-Etsu Chemical ■ was applied to one side of a 100μ PET heath with a thickness of 0.05μ and heated at 130'C for 2 hours. The silicone compound-containing layer was formed by drying and curing for minutes.

On the other hand, 65 parts by weight of stannic chloride hydrate and 2. 1.5 parts by weight of antimony trichloride was dissolved in 1.000 parts of ethanol to obtain a homogeneous solution. An IN sodium hydroxide aqueous solution was added dropwise to this solution until the pH of the solution became 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The resulting coprecipitate was placed in 5Q'C for 24 hours to obtain a reddish brown colloidal precipitate.

A reddish-brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions.

100 parts by weight of the colloidal precipitate from which excess ions had been removed was remixed with 1,000 parts by weight of water and sprayed into a formation furnace heated to 650°C to obtain bluish fine particles with an average particle size of 0.1511. .

The above conductive fine particles were mixed with the following recipe in a paint shaker (n
Toyo Yokozai Seisakusho! ! 1) was dispersed for 5 hours.

200 parts by weight of the above-mentioned tetraelectric fine particles Saran F-31010- (vinylidene chloride copolymer, trade name of Asahi Dow) 150 ffif 2 parts methyl ethyl ketone A coating solution having the following formulation was prepared using this dispersion, and a silicone compound-containing layer was prepared. The buffy coating was applied to the back side of the film at a coating amount of 1.3 g/rd and dried at 130° C. for 2 minutes.

15 parts by weight of the above dispersion Saran F-3103 Methyl ethyl ketone 100 Cyclohexanone 20 llm-cresol 5 Further, on this layer, apply a solution with the following formulation so that the buffing coating amount is 0.2 g/rrf. It was dried at 130°C for 1 minute.

Cellulose triacetate 1ffii 1 part Methylene dichlorite 60 Ethylene dichloride 40 Erucic acid amide
0.01 The surface resistance value of this cover sheet was measured using an insulation resistance measuring device (GvE-3o type manufactured by Yorodende Co., Ltd.) and found to be 7×1 Or 3 Ω at 25° C. and 25% RH.

With ``Nariba'' engineering! Sample (a) was prepared in exactly the same manner as sample (a), except that the amount of conductive particles was reduced so that the surface resistance of the bag was 1010Ω.
b) was produced.

The surface resistance of the conductive layer is 101 by reducing the amount of conductive fine particles.
Sample (c) was prepared in exactly the same manner as in the case of sample fat, except that the coating was applied so that the resistance was 1Ω.

The surface resistance of the conductive layer was reduced to 101 by reducing the amount of conductive fine particles.
Sample (d) was prepared in exactly the same manner as the sample (al) except that the coating was applied so that the resistance was 2Ω.

The surface resistance of the conductive layer was reduced to 101 by reducing the amount of conductive fine particles.
Sample (e) was prepared in exactly the same manner as sample +a+, except that the coating was applied so that the resistance was 3Ω.

f) - The surface resistance of the conductive layer is reduced to 101 by reducing the amount of conductive fine particles.
A sample (sample Cf) was prepared in exactly the same manner as in the case of al, except that the coating was applied so that the resistance was 4Ω.

-4()-1 A comparative sample (g) was prepared by providing only the same silicone compound-containing layer as the sample (a) without providing a conductive layer.

A comparative sample (h) was prepared by providing only the same conductive layer as in sample ia) without providing the silicone compound-containing layer of sample ia).

[Preparation of image receiving sheet material]

Polyethylene terephthalate film (thickness 71008
m) was prepared, and coating solutions A and 13 having the following compositions were sequentially applied onto the film to form an image receiving sheet material with an adhesive surface and having a dry film thickness of 20 μm and 1.5 μm, respectively. Created.

15g (ff
i ffi ratio ethylene 81%, vinyl acetate 19%) (
Mitsui Polychemical DM “Nivafrenox #410) Chlorinated polyethylene 0.073g (Yamaba Kokusaku Valve 1 Yokoi “Superchron 907L’rA’”) Fluorine surfactant 0.25g (3M “Florado FC-430”) )toluene
L OOcc1 Polyvinyl 7-tyral 4g (Denki Kagaku Kogyo [1-fiber “#2000-L”) Fluorine fiber culm surface activation 1 0.05g (3M “Florado FC-430” methanol)
5Qcc methyl ethyl ketone
20CC Methyl cellosolve acetate 20CC [Creation of a transferable image] First, a gamma solution having the following composition was prepared as a liquid for forming a peeling layer.

Dishhada 1 and 1 Ekuku alcohol-soluble polyamide 7.2g (CM
'-8000: East tide * > η: 23C, I)
S, (20°C' i 0 W t % methanol ref volume, 'night) Polyhydroxystyrene 1,8 g (Resin M: average molecular weight: s, so.

(manufactured by Maruzen Sekiyu) 400 g of methanol 100 g of methyl cellosolve
008m) and dried to obtain a dry film thickness of 0.5
A release layer of μm was provided.

On the other hand, for the purpose of forming negative-positive type images, four colors of photosensitive resin, yellow (Y), magenta (M), cyan (C), and blue/7li (B), are used as coating liquids for forming photosensitive resin layers. Solutions were prepared to have the compositions shown in Table 1 below.

Next, these 4
The photosensitive solution of each color was applied and dried to obtain a dry film thickness of 2.
A 4 μm photosensitive resin layer was provided.

Separately, a coating solution for forming a protective layer with the following composition was prepared, and this coating solution was applied to each color of photosensitive resin layer and dried.
A protective layer with a dry thickness of 1.5 μm was provided.

Tan 11 Ri Naru 1 Bancho Polyvinyl Alcohol 60g (GL
-05, manufactured by Nippon Gosei Kagaku Kogyo ■) Water
970g methanol
30g was prepared in this way, 4 layers consisting of the support, release layer, photosensitive resin layer and protective layer in this order.
A color photosensitive transfer sort (negative colored photosensitive sheet) was produced.

The photosensitive transfer sheets of each of the four colors were overlapped with the corresponding mask using a resistor bin, and imagewise exposed from a distance of 50 cm using a 2 Kw ultra-high pressure mercury lamp. The exposed transfer sheet was developed using a developer having the following composition at a temperature of 35° C. for 10 to 20 seconds to obtain a four-color color proofing sheet with halftone dot images on the peelable M layer.

1 Yingqiu Na2CO3 15g Butyl Cellosolve 1g Water

11 Next, first, the black color proofing sheet is accurately overlapped with the image receiving sheet using register pins so that the image side is in contact with the image receiving layer of the image receiving sheet material. 8B
-550-80, manufactured by Taisei Shoji ■) at a pressure of 2 bars, a roller temperature of 120°C, and a laminator speed of 900 mm.
Lamination was performed under the condition of /min. Peel off only the support of the color proofing sheet from the release layer and transfer the black image onto the image receiving sheet.Then, repeat the same operation for the remaining three color proofing sheets to print black, cyan, and magenta. An image receiving sheet was obtained on which halftone images were transferred and formed in the order of , yellow.

Next, a color test sheet for the sub-print method was produced in the following manner using the image-receiving sheet having the transferred images of the four colors described above.

The image-receiving sheet having the transferred images of four colors was superimposed on white art paper so that the image-receiving layer side was in contact with the sheet, and then lamination was performed under the same conditions as described above.

Next, when this image-receiving sheet and white art paper are peeled off, the peeled layer and image area remain on the white art paper that was peeled off at the second layer and image area, without further matting the surface. An image very similar to the printed material was obtained.

Using the various cover sheets described above, the transfer operation to the image-receiving sheet was repeated, and the releasability and presence or absence of electric shock were examined by the following method. The results are shown in Table 2.

[Evaluation method of mold releasability]

Make sure that a part of the image receiving sheet is in direct contact with the cover sheet,
The transfer operation was repeated 100 times, and the weight at the time of peeling was measured. If the peel is lighter than IQOg with a width of 5 cm, it is considered "good", and if it is heavier than this, it is considered "good".

[Presence or absence of electric shock]

Transfer work was performed in a constant temperature and humidity room at 20% RH and 120°C.
The peeling speed was 20 cm/sec, and an electric shock and screams were observed when peeling.

Table 2 The results in Table 2 demonstrate that the cover sheet material of the present invention having a 4-volt surface resistance of 10 13 Ω or less has good mold releasability and electric shock resistance.

Claims (1)

[Claims] 1) Consisting of a support, a conductive layer provided on at least one surface of the support, and a silicone compound-containing layer provided on one surface of the support on the conductive layer or on the support, and A sheet material characterized in that the surface electrical resistance of the conductive layer is less than 10^1^3Ω.