JPH07309063A - Sheet for ohp - Google Patents

Abstract

PURPOSE:To obtain a sheet for OHP having a hardening film layer made of color dyeing photosensitive resin on a transparent film. CONSTITUTION:When color printing is performed on a sheet for OHP by an ink jet printer, a coat of photosensitive resin film on a transparent film adsorbs a dye in an ink strongly, so that sharp images can be projected without generating blur in the images. In addition, as the resin film layer is cross-linked with light and brought to a three-dimensional state, water resistance is also sufficiently high.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an OHP having good water resistance.
(Overhead projector) seat.

[0002]

2. Description of the Related Art Ink jet printers have low noise,
It has been rapidly spreading in recent years as a high-speed, inexpensive (color) printer. As an ink for an inkjet printer, a water-based ink in which a water-soluble dye is dissolved in a solvent composed mainly of water is used from the viewpoint of safety and recording characteristics. For this reason, as an OHP sheet for an inkjet printer, a sheet is used which is a water-based ink receiving layer obtained by coating a transparent film such as polyester with a hydrophilic resin such as polyvinyl alcohol.

[0003]

It has been pointed out that when a dye solution is jetted onto a conventional OHP sheet coated with a hydrophilic resin, an image bleeds as the dye solution diffuses. This means that a sharp image cannot be projected when magnifying and projecting with OHP. Another drawback is that the water resistance is poor.

[0004]

Means for Solving the Problems As a result of various investigations by the present inventors to develop an OHP sheet in which the above-mentioned drawbacks have been improved, a known method for forming a dye-dyeable photosensitive resin on a transparent film as a base material is known. After coating and drying, it is exposed to light and cured.
When the cured layer (ink receiving layer) was printed with an inkjet printer, it was found that images did not bleed and the water resistance was good, and the present invention was completed. That is, the present invention is
(1) an OHP sheet having a cured film layer of a dye-dyeable photosensitive resin on a transparent film, (2) an OHP sheet of the above (1) in which the dye is a water-soluble dye, and (3) a water-soluble dye An OHP sheet of the above (2) which is an anionic dye,
(4) The OHP sheet of (1), wherein the dye-dyeable photosensitive resin after curing is a resin having a cationic group, (5)
The OHP sheet of (4) above in which the cationic group is a primary amino group or a quaternary ammonium group, and the (4) OHP sheet of (4) above in which the resin is a (meth) acrylate resin or polyvinyl alcohol resin. (7) The OHP of (1) above, wherein the cured film layer has a thickness of 0.1 to 100 μm.
Sheet, for.

The transparent film used in the present invention is
There is no particular limitation, and examples thereof include a polyester film such as PET (polyethylene terephthalate), a polyolefin film such as polyethylene and polypropylene, a polycarbonate film, and a polymethylmethacrylate film. . Its thickness is 10
It is preferably about 100 μm. The size is not particularly limited as long as it can be used for OHP, for example, JIS A column 3
The sizes of No. 4, A-row No. 4, B-row No. 4, and B-row No. 5 are listed.

The dye-dyeable photosensitive resin is, for example, (meth)
A transparent resin such as an acrylate-based resin or a polyvinyl alcohol-based resin, which is cured by an energy ray such as an electron beam or an ultraviolet ray and is dyed with a water-soluble dye such as an anion dye after curing, is preferable. Examples of such a resin include primary amino group to quaternary ammonium group (primary amino group, secondary amino group, tertiary amino group, 4
Resins having a cationic group such as primary ammonium group) before curing, for example, JP-A-62-283339 and JP-A-1.
-198615, JP-A-60-252341, JP-A-56-67309, JP-A-60-129742 and the like, photosensitive resins (compositions), azides which become amino groups by curing treatment A resin having a group such as a group which becomes the cationic group after curing, for example, JP-A-56-673.
The photosensitive resins (compositions) described in Japanese Patent Publication No. 09 and the like are mentioned. Specific examples include the following.

1. The photosensitive resin described in JP-A-1-198615 is (i) an anion dye dyeable polymer (anion dye dyeable monomer (A) 20 to 70% by weight, a hydrophilic monomer (B) other than (A)). 10-60% by weight, hydrophobic monomer
(C) Copolymer comprising 10 to 50% by weight), (ii) azide-sensitive compound, and (iii) compound having two or more acryloyl groups and / or methacryloyl groups in the same molecule. Is. Specific examples of the resin are described in Examples 1 to 6 of the publication, and the constituent components of the resin and the use ratio thereof are described on pages 2 to 4 and 7 of the publication. 2. The photosensitive resin described in JP-A-60-252341 has the general formula [I]

[0008]

[Chemical 1]

(In the formula [I], R ₁ represents —H, —CH ₃ or —C ₂ H ₅ , X represents —O— or —NH—, n represents an integer of 1 to 3, R ₂ and R ₃ represent an alkyl group having 1 to 4 carbon atoms) and a polymer having a structural unit represented by the general formula [II].

[0010]

[Chemical 2]

(In the formula [II], R ₄ , R ₅ , R ₆
And R ₇ represent —H, —CH ₃ or —C ₂ H ₅ , and m represents an integer of 1 to 3. ) A compound represented by
Or the general formula [III]

[0012]

[Chemical 3]

(In the formula [III], R ₈ , R ₉ and R ₁₀ represent —H, —CH ₃ or —C ₂ H ₅ , and m
Represents an integer of 1 to 3. And a resin composition comprising at least one compound represented by the formula (1). Specific examples of the resin are described in Example 1 of the publication, and constituent components of the resin and the ratio of use are described on pages 2 to 5 of the publication. 3. The photosensitive resin described in JP-A-56-67309 has a structure of the formula [IV] in the polyvinyl alcohol structure.

[0014]

[Chemical 4]

2-Azido-5-nitrophenylcarbonyloxyethylene structure represented by the formula or the formula [V]

[0016]

[Chemical 5]

A resin composition having a 4-azido-3-nitrophenylcarbonyloxyethylene structure represented by: Specific examples of the resin are described in Examples 1 and 2 of the publication, and the constituent components of the resin and the use ratio thereof are described on page 2 of the publication. 4. The photosensitive resin described in JP-A-60-129742 has a structure represented by the general formula [VI] in a polyvinyl alcohol structure.

[0018]

[Chemical 6]

(In the formula [VI], R ₁₁ represents an alkyl group having 1 to 4 carbon atoms, A ⁻ represents an anion) and the general formula [VII].

[0020]

[Chemical 7]

(In the formula [VII], Y represents only a connecting group, R ₁₂ , R ₁₃ and R ₁₄ represent an alkyl group having 1 to 4 carbon atoms, and A ⁻ represents an anion). A resin composition having a structural unit. Specific examples of the resin are described in Examples 4 to 11 of the publication, and constituent components of the resin and the ratio of use are described on pages 3 to 6 of the publication. Among these dye-dyeable photosensitive resins, for example, PC Green FOP
When dyed with a water-soluble dye having a molecular weight of 1000 or more (see below) (the resin thin film having a thickness of 0.6 μm is immersed in a 4% aqueous solution for 15 minutes at room temperature), the transmittance of the dye at the maximum absorption wavelength is It is preferably 5% or less.

To produce the OHP sheet of the present invention,
For example, the following may be done. That is, the photosensitive resin solution is applied onto a transparent film as a base material to give a dry film thickness of 0.1 to 1
The thickness is 00 μm, preferably 0.5 to 60 μm, more preferably 0.5 to 50 μm, still more preferably 1 to 20 μm. Then, after drying at 50 to 150 ° C., the ink receiving layer is formed by irradiating with energy rays such as ultraviolet rays to cure the ink, and the OHP sheet of the present invention is obtained. The ink-receiving layer formed here has a cationic group in its molecular structure, and is strongly adsorbed by an ionic bond with the sulfonic acid group of the dye in the aqueous ink,
It is possible to form a sharp image with little bleeding.
Further, since it is photocrosslinked after coating and has a three-dimensional structure, the water resistance is remarkably good.

The water-soluble dye for dyeing the dye-dyeable photosensitive resin is preferably an anionic dye. Examples of anionic dyes include acid dyes, direct dyes, reactive dyes, etc., and acid dyes are particularly preferable. Specific examples of applicable anionic dyes include CI Acid Yellow 3, 17,
Same 38, Same 40: 1, Same 42, Same 44: 1, Same 49, Same 61, Same 65, Same 67, Same 72, Same 79, Same 110, Same 114, Same 116, Same 117, Same 119, Same. 121, 127, 129, 135, 141, 143, 155, 158, 161, 194, 204, 207, 220, 232, 235, 241 and C.
I.Orange10、19、33、50、56、6
7, 80, 108, 122, 142, 16
6, the same 130, CIAcid Red 1, the same 6, the same 9, the same 14,
Ibid 18, ibid 35, ibid 37, ibid 42, ibid 50, ibid 52, ibid 57, ibid 73, ibid 87, ibid 88, ibid 89, ibid 92, ibid 9
7, 106, 111, 114, 118, 12
8, same 134, same 138, same 143, same 143: 1, same 145, same 158, same 183, same 186, same 211, same 214, same 215, same 217, same 219, same 225, same 226, same 249, 254, 256, 257, 259, 260, 261, 263, 266, 274, 276, 278, 289, 299, 301, 303, 307, 307, 315, 316, 317, 336, 337, 341, 355, 357, 359, 362, 366, 383, 399, 405, 407, 414, 416 , 426, CIAcid Violet 21, 42, 43, 4
7, ibid 48, ibid 49, ibid 54, ibid 97, ibid 102, CI
Acid Blue 7, same 9, same 15, same 22, same 23, same 2
5, same 40, same 45, same 47, same 59, same 61: 1, same 62, same 78, same 80, same 83, same 90, same 104, same 109, same 112, same 127, same 127: 1. , 12
9, the same 138, the same 140, the same 203, the same 204, the same 20
7, 227, 228, 232, 247, 26
0, 264, 277, 278, 280, 28
3, 290, 333, 343, CIAcid Green
3, 5, 5, 22, 25, 27, 28, 41,
CIAcid Black1, 26, 31, 31, 48, 50,
Same 52, Same 52: 1, Same 58, Same 60, Same 63: 2, Same 64, Same 107, Same 109, Same 110, Same 112, Same 1
13, Same 118, Same 140, Same 155, Same 170, Same 1
72, 177, 187, 188, 194, 2
07, 222, CIDirect Yellow 12, 86, 87, 130, 142, CIDirect Orange 26,
39, CIDirect Red2, 23, 24, 31,
Ibid 39, ibid 54, ibid 79, ibid 83: 1, ibid 89, ibid 22
4, the same 225, the same 226, the same 227, the same 242, the same 24
3, CIDirect Blue 106, 108, CIDirect B
lack17, same19, same22, same51, same62, same91,
112, 117, 118, 122, 132,
146, 154, 159, 169, 173,
CIReactive Yellow 84, 102, CIReactive O
range 1, same 4, CIReactive Red 5, same 8, same 43
And dye for color filter PC Y manufactured by Nippon Kayaku Co., Ltd.
ellow 42P, PC Red 21P, PC Red 136P, P
C Red 137P, PC Magenta 10P, PC Blue 43
P, PC GreenFOP, PC Green100P, PC Cya
Examples include n 2P and the like.

These dyes are usually used as a pigment component of ink for ink jet printers. In this case, an ink is prepared by using these dyes alone or as a mixture, and as a solvent for the ink, water or an aqueous solution of an organic solvent that can be mixed with water is used. Examples of the organic solvent include methyl alcohol, ethyl alcohol, butyl alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The dye concentration in the ink is preferably 0.5 to 20%, and particularly preferably 1 to 10%.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 CFR-3 (manufactured by Nippon Kayaku Co., Ltd.), which is a highly dyeable photosensitive resin liquid of the type described in JP-A-1-198615, was applied to a polyethylene terephthalate film having a thickness of 100 μm by a bar coater. After drying at 100 ° C. for 3 minutes, it was exposed and cured through a belt conveyor type UV irradiator. The exposure amount was about 150 mJ / cm ² . The ink receiving layer was light yellow white transparent and had a thickness of 10 μm. On the OHP sheet thus obtained, 4% aqueous solution of PC Cyan 2P (manufactured by Nippon Kayaku Co., Ltd.), 3% ethyl cellosolve aqueous solution of PC Magenta 10P (manufactured by Nippon Kayaku Co., Ltd.), PC as ink
Color printing was performed with an ink jet printer (manufactured by Sharp) set with a 3% aqueous solution of Yellow 42P (manufactured by Nippon Kayaku Co., Ltd.) and a 4% ethyl cellosolve aqueous solution of PC Black 142P (manufactured by Nippon Kayaku Co., Ltd.). , High density and extremely clear images were obtained. When this color OHP sheet was set in a commercially available OHP device and projected on a screen, a clear color image was projected. Further, when this color OHP sheet was immersed in water at 60 ° C. for 5 minutes, no ink bleeding was observed.

Example 2 CFR-5 (manufactured by Nippon Kayaku Co., Ltd.), which is a highly dyeable photosensitive resin of the type described in JP-A-1-198615, was formed into a polyethylene terephthalate film having a thickness of 100 μm with a roll coater. The composition was applied, dried at 100 ° C. for 3 minutes, exposed through a belt conveyor type UV irradiator and cured. The exposure amount was about 150 mJ / cm ² . This ink receiving layer was colorless and transparent and had a thickness of 8 μm. The OHP sheet thus obtained was color-printed with an inkjet printer in the same manner as in Example 1, and a clear image was obtained.

Example 3 A transparent OHP sheet is obtained by the same procedure as in Example 1 using a highly dyeable photosensitive resin of the type described in JP-A-60-252341 manufactured by Chisso Corporation.

Example 4 For transparent OHP, the same operation as in Example 1 was carried out using SPPL (manufactured by Toyo Gosei Co., Ltd.), which is a highly dyeable photosensitive resin of the type described in JP-A-60-129742. Got the sheet.

Example 5 Using a 10% aqueous solution of a highly dyeable photosensitive resin of the type described in JP-A-56-67309 manufactured by Sekisui Chemical Co., Ltd., the same operation as in Example 1 was carried out to obtain a transparent OHP. Get a sheet for.

[0030]

When color printing is performed on the OHP sheet of the present invention with an ink jet printer, the photosensitive resin film coated on the transparent film strongly adsorbs the dye in the ink, so that there is no blurring of the image and it is sharp. Images are projected. Further, since the resin film layer is photo-crosslinked and three-dimensionalized, the water resistance is sufficiently high.

Claims (7)

[Claims] 1. An OHP sheet having a cured film layer of a dye-dyeable photosensitive resin on a transparent film. 2. The OHP according to claim 1, wherein the dye is a water-soluble dye.
Sheet. 3. The water-soluble dye is an anionic dye.
OHP sheet. 4. The OHP sheet according to claim 1, wherein the dye-dyeable photosensitive resin after curing is a resin having a cationic group. 5. The OHP sheet according to claim 4, wherein the cationic group is a primary amino group or a quaternary ammonium group. 6. The OHP sheet according to claim 4, wherein the resin is a (meth) acrylate resin or a polyvinyl alcohol resin. 7. The OHP sheet according to claim 1, wherein the cured film layer has a thickness of 0.1 to 100 μm.