JPH0665498A - Gelatin-based drawing material - Google Patents

Abstract

PURPOSE: To provide a gelatinous material for drafting, which has excellent physical property and drawing characteristic suitable for absorption of pencil, ink and toner particle.

CONSTITUTION: A drafting material comprises a transparent support and at least one hydrophilic colloidal layer contg. (a) gelatin, (b) one or more silica matting agents, (c) an opacifying agent, preferably titanium dioxide, (d) an epoxysilane compd. (e) a polyurethane latex and (f) a hardening agent. This material can further contain a brightening agent and an antistatic agent. The support material is preferably thermostable polyethylene terephthalate.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to gelatinous drafting materials for use in industrial engineering.

Drawing materials are widely varied such as maps, building construction, public installations (eg gas, water), industrial equipment design, automobiles, airplanes, missiles and various consumer goods such as furniture and toys. Widely used in private or public engineering offices for any purpose.

A significant portion of the market is still occupied by the traditional use of sketch hand drawings.
After the creative design, these sketches are photographic material,
On diazo materials or in large format copiers (eg XEROX Co.
The same drafting film stock can be used as the replication material in the latter case.

In another recent work flow, the creative phase is done on a computer by the so-called Computer Aided Design (CAD), after which the finished drawings are stored in digitized form. In this case, the drafting material is used as a recording material for this digitized information, the output of which is a so-called pen plotter or a so-called laser plotter which operates in a manner similar to laser printers (for example by VERSATEC-XEROX). It is done mechanically by a commercially available VERSATEC device. According to another application, a drafting film can be used as a recording material for an inkjet device. After plotting, the formed drawing can be reproduced by the same means as described above for manual drafting.

Modern drafting materials must comply with the property requirements that they serve both as hand-drawn drafting media and as plotter recording materials.

Firstly, such a material must exhibit sufficient abrasion power to ensure that it takes pencil graphite; it must also exhibit good absorption for drafting inks. On the other hand, the wear force is not good if it is too great to avoid too fast wear of the pencil or nib. In addition, the lines and characters drawn should be easily erased with a regular pencil or ink eraser. In particular,
The appearance of so-called ghost lines during gaming is to be avoided, which consists of the remaining lines that are transparent in transmission and appear dark in reflection. The erased spots on the other hand should be able to be redrawn completely. In other words, the drafting material should withstand several revisions and corrections without being damaged or giving a confused appearance.

Further, the ink spread of newly drawn lines should be limited to a minimum so that sharp lines with no irregular or diffuse edges are created. In this way, high resolution drawings are ensured even after copying.

The drafting material should exhibit some degree of reflection in order to give a clear contrast to the eye. The appearance should be neutral white and uniform.
On the other hand, the material should be sufficiently transparent to allow replication by the method described above.

The drafting film, which acts as a recording material for the pen plotter method, has excellent anti-static properties, especially when the pen of the plotter remains in a fixed position and when the material itself is moved in several successive directions. Demands sex.

When a drafting film is used as a duplication medium in a copying machine or as a recording medium for a laser plotter, the material is exposed to high temperatures due to thermal relaxation of the electrostatic toner image without being damaged or curled or excessively dimensionally changed. You should be able to withstand. In other words, the material needs to be heat stable.

Some drafting films with excellent properties, such as FOLEX C by PHONE-POULENC Co.
o. by OCE Co. by KEUFEL and ESSER C
Materials marketed by o. and by ICI Co. are offered to the market. However, it is clear from their composition, determined by analysis, that their drawing layers are coated from organic solvent media, which usually contain polymethylmethacrylate as a constituent of the abrasion-resistant layer. For companies in the photographic industry, such as the Applicant, this manufacturing method offers two disadvantages. Firstly, coatings from organic solvents require special equipment, which makes them more expensive than conventional coatings from aqueous colloidal solutions. Secondly, the use of organic solvents in the manufacturing process poses environmental pollution problems, requires special attention and makes them more expensive.

It is an object of the present invention to provide a drawing material which can be coated from an aqueous colloidal solution in an economical and environmentally safe manner.

Another object of the present invention is for drafting which is capable of drawing fine ink lines, the drawings of which can be easily duplicated and which can withstand some corrections, but which does not have excessive wear forces. To provide the material.

Yet another object of the present invention is to provide a drafting material that is heat stable for applications where high temperatures occur.

Other objects of the invention will be apparent from the following description.

The objects of the present invention are: (a) gelatin; (b) one or more silica matting agents; (c) opacifying agents; (d) epoxysilane compounds; (e) polyurethanes; (f) hardeners. It is achieved by providing a drafting material comprising at least one hydrophilic colloid layer containing a and a transparent support.

Although the separate use of these components in hydrophilic coating layers is known, the present invention surprisingly provides this drawing layer with its excellent physical strength, which can be drawn repeatedly. In this particular combination, which makes it suitable for correction work. The hydrophilic layer can be coated on one side or both sides of the support.

Preferably the transparent support is an organic polymer resin,
For example, polyethylene terephthalate. The support is preferably subjected to a thermal relaxation treatment for drafting film applications where high temperatures may occur.

The gelatin used in the drafting layer of the present invention can be lime-treated or acid-treated gelatin. Such gelatin can be produced, for example, by Academic Press 19
Published in 1977, edited by AG Ward and A. Courts, The S
Cience and Technology of Gelatin, pages 296 and 297. Gelatin can exhibit a low or high isoelectric point. It can belong to the low or high viscosity class. The gelatin used in the colloidal drawing layer of the present invention is preferably a mixture of low viscosity and high viscosity, and the latter is present in a large amount. It is such a mixture which gives the layers the best mechanical strength and a fast reaching post-coating final cure. The dry coverage of gelatin in drafting layer is in the range of 1.0g / m ² ~10g / m ² are preferred,
The range of 1.5 to 3.0 g / m ² is the most preferable.

The use of silica matting agents in drafting materials is
For example, US-P 3370951, US-P 436623.
9, US-P4588673 and US-P461092.
4 are well known to those skilled in the art. Silica can belong to the crystalline or amorphous type. Mixtures of both types are particularly preferred in the practice of the present invention. The crystalline silica preferably exhibits an average particle size of 1-5μ. The crystalline type gives the layer its matte appearance and its minimal wear power ensuring good entrapment of pencil graphite. It is preferably added to the coating solution as a gelatinous dispersion giving a preferred concentration range in the dry layer of 1.0 to 5.0 g / m ² . The presence of amorphous silica is believed to be beneficial to the retouched and modified pencil ink, and gumming the layer
) Make it more suitable for post-rewriting. Amorphous silica, like crystalline ones, is preferably from 0.2 to
Add as a gelatinous dispersion giving a concentration in the dry layer of 2.0 g / m ² .

As is the case in many industrial applications, it is preferred to use titanium dioxide as an opacifying agent.
The rutile type crystal modification produces a slight yellowish blue color in the dry drafting layer due to the small absorption of blue light just above 400 nm. Therefore, when using rutile silicon dioxide, it is recommended to include a small amount of blue dye in the layer in order to readjust the hue to neutrality. Therefore it is preferred to use titanium dioxide in the anatase crystal modification, which is almost completely white and does not require dye color correction. The pigment is 0.
It is preferable to add it at a concentration of ^{2 to} 0.4 g / m ² , so that the transmittance of the coating material on both sides is MACBETH TD 904.
It is between 30 and 50% as measured by a spectrophotometer.

Epoxysilane is incorporated in the gelatinous drawing layer. Particularly preferred epoxy silane (DOW CORNING
Type DC6040 manufactured by Co. is represented by the following formula (E-1):

[0023]

[Chemical 1]

Epoxysilanes improve the physical strength of dried hydrophilic drafting layers. It has been experimentally demonstrated that the resistance to damage from repeated gumming was significantly improved by the incorporation of epoxysilane, which is true not only for dry but also for wet ink gumming. The epoxysilane is preferably added to the coating solution as an alcohol solution. Its concentration in the layer is preferably comprised between 0.1 and 0.4 g / m ² .

Still another essential component in the colloidal drafting layer used in the present invention is polyurethane, preferably an aliphatic anionic polyurethane dispersion. A particularly preferred polyurethane for use according to the invention is commercially available under the tradename IMPRANIL 43056 manufactured by BAYER Co. The polyurethane is added to the coating solution as an aqueous latex dispersion. This polyurethane counteracts the wear effect of the silica matting agent in the drawing layer and is used to adjust the wear force to the optimum value. Further, it has been experimentally shown that the polyurethane latex is very important for suppressing the ghost line as described above. To be effective,
Polyurethane is about 20-40 dry weight of hydrophilic drafting layer
Must account for%.

Gelatin binders in photographic materials are suitable hardeners such as those of the epoxide type, those of the ethyleneimine type, those of the vinyl sulfone type such as 1,3-vinylsulfonyl-2-propanol, chromium salts such as chromium acetate and Chromium alum, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylol urea and methylol dimethylhydantoin, dioxane derivatives such as 2,3-
Dihydroxy-dioxane, active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids such as mucochloric acid and mucins. It can be cured with cophenoxycyclo acid. These hardeners can be used alone or in combination. Binders are also fast-reacting hardeners (so-called instant hardeners) such as those described in US Pat. No. 4,063,952, eg carbamoylpyridinium salts, and European Patent Application No. An onium compound as described in 90.201850.6 can also be cured.

The preferred hardener for the hydrophilic gelatinous drafting layer is 1,3,5-triacryloyl-hexahydro-s-triazine, which has the formula (H-1):

[0028]

[Chemical 2]

However, for the particular use of the drafting material as a primer for the production of another material of the wash-off material, special attention must be paid to the choice of curing agent, because in this case In the wash-off layer, which should be cured only image-wise by curing development,
This is because the curing agent is not allowed to diffuse from the undercoat. In this case, instant curing agents such as carbamoylpyridinium salts are preferred.

The gelatinous drawing layer may further contain a whitening agent. By virtue of its whitening effect, such compounds enhance the visible contrast when assaying the figure. Preferred compounds are represented by formula (B-1) below:

[0031]

[Chemical 3]

The gelatinous drawing layer may further contain one or more antistatic agents, preferably incorporated into the subbing layer.

The drafting material of the present invention may further contain various kinds of surfactants. Suitable surfactants include saponins,
Alkylene oxides such as polyethylene glycol,
Polyethylene glycol / polypropylene glycol condensation product, polyethylene glycol alkyl ether or polyethylene glycol alkyl aryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or alkylamide, silicone-polyethylene oxide adduct, glycidol derivative, polyhydric alcohol Nonionic surfactants such as fatty acid esters and alkyl esters of saccharides; anionic surfactants containing acid groups such as carboxy, sulfo, phospho, sulfuric acid or phosphoric acid ester groups; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulphates or phosphates, alkylbetaines and amine-N-oxides; and alkylamine salts, aliphatic, aromatic or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic Formulas include cationic surfactants such as ring-containing phosphonium or sulfonium salts. Such surfactants can be used for various purposes, for example as coating aids, as antistatic compounds or as compounds which improve lubricity.

The hydrophilic layer of the drafting material of the present invention may further contain various other additives such as additives and plasticizers for improving dimensional stability. Additives suitable for improving the dimensional stability of photographic materials include water-soluble or slightly soluble synthetic polymers such as alkyl (meth) acrylates, alkoxy (meth) acrylates, glycidyl (meth) acrylates, (meth) Polymers of acrylamide, vinyl ester, acrylonitrile, olefin and styrene, or acrylic acid, methacrylic acid, α,
There are dispersions of copolymers with β-unsaturated dicarboxylic acids, hydroxylalkyl (meth) acrylates, sulfoalkyl (meth) acrylates, and styrenesulfonic acid.

The support of the drafting material of the present invention is a transparent organic resin support such as cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film,
Polycarbonate film, polyvinyl chloride film,
Alternatively, it is preferably a poly-α-olefin film such as a polyethylene or polypropylene film.
In a preferred embodiment, the support is transparent polyethylene terephthalate, the thickness of which can be varied depending on the particular application of the drafting film. Most preferred are at least three different thickness sets, 75μ, 100μ and 125μ respectively. The polyethylene terephthalate support is preferably provided with a subbing layer to ensure good adhesion of the hydrophilic drawing layer.

The polyethylene terephthalate support is subjected to thermal relaxation treatment so that it can withstand the high temperatures during thermal fixing. This is accomplished by incorporating a controlled shrinkage process during online production of the support.

The gelatinous layer may be provided with a protective layer, but this is not necessary, when present, the protective layer comprises colloidal silica which is advantageous for further suppressing ghost lines when gumming. It is preferably contained.

The gelatinous drawing layer can be coated on only one side of the support, but is most preferably applied on both sides.

The following examples illustrate the invention but do not limit it.

Example 1

The coating solution was made as follows. 6 at 40 ° C
To 25 ml of deionized water was added 25 g of high viscosity seed gelatin and the mixture was stirred until dissolved. 25 g of low viscosity seed gelatin and 25.1 g of crystalline silica particles having an average diameter of 2μ were added. Low viscosity gelatin 0.56
g and 10 g of a dispersion containing 3.75 g of titanium dioxide in the anatase modification. Further average particle diameter 3.7μ
75 g of 11.25% dispersion containing 8.4 g of amorphous silica with 5.0 g of low viscosity seed gelatin and 4.1 g of polyethylethacrylate. After dissolution of the dispersion, epoxy silane (DOW CORNING type DC
6040: 10% ethanol solution 40 of compound E-1)
ml was added and the mixture was stirred for 30 minutes. As a wetting agent,
8 ml of a 9% water / ethanol (80/20) solution of the commercially available surfactant UL TRAVON W and 2 ml of a 5% aqueous solution of a polyethylene oxide surfactant containing a perfluorinated alkyl group were used. As a curing agent, a 2% solution of 1,3,5-triacryloyl-hexahydro-s-triazine (Compound H-1) (methanol / water: 70/30)
100 ml was added. As a whitening agent, 0.75 ml of a 6% aqueous solution of compound B-1 (see description) was used. Finally, 75 ml of 45% by weight polyurethane latex (trade name of BAYER, IMPRANIL 43056) was added. The pH of the mixture was adjusted to 8.0 with a small amount of sodium hydroxide solution. Then, the volume was adjusted to 1 liter with deionized water.

The solution thus prepared was applied to one side of a 100 μm thick transparent polyethylene terephthalate base, 7.
Coating was performed by the slide hopper coating method at a coating amount of 31 g / m ² . The base was provided with a base coat layer containing 80% by weight of a co (vinylidene chloride / methacrylate / itaconic acid; 80/10/2) copolymer and 20% by weight of colloidal silica. On top of the basecoat layer was provided a basecoat layer containing about 50% gelatin, about 50% colloidal silica and a small amount of polymethylacrylate spherical beads. After coating, the hydrophilic colloid drawing layer was dried by a conventional method. 1
After 4 days, this material underwent several standard physical and graphic tests. Adhesion to the support was all good. The density of the pencil and ink lines was sufficient, in the latter case no line expansion occurred. The optical density of the layer was about 0.30.
The ghost line didn't appear when I gammed.

Example 2

Both sides of the support were coated with the same hydrophilic colloid coating solution as in Example 1. Excellent physical and drafting properties were obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etienne Van Tiro, Septerrato, Mortzel, Belgium 27 In Agfa Gewert Namrze, Bennnotchapp (72) Inventor, Hartwig Andre, Septert, Belgium 27 Agfa Gewert Namrose Rose Bennault Chap

Claims (8)

[Claims] 1. (a) gelatin; (b) one or more silica matting agents; (c) opacifying agents; (d) epoxysilane compounds;
(e) Polyurethane; (f) A drafting material comprising at least one hydrophilic colloid layer containing a curing agent and a transparent support. 2. The drafting material of claim 1, wherein the opacifying agent is titanium dioxide. 3. The drafting material according to claim 2, wherein the titanium dioxide is anatase crystal modification. 4. The drafting material according to claim 1, wherein the silica matting agent comprises a mixture of crystalline silica and amorphous silica. 5. The drafting material according to claim 1, wherein the hydrophilic colloid layer further contains a whitening agent. 6. The drafting material according to claim 1, wherein the support is a polyethylene terephthalate support. 7. The drafting material of claim 6, wherein the polyethylene terephthalate support has been subjected to a thermal relaxation treatment. 8. The drafting material according to claim 1, wherein the hydrophilic colloid layer is coated on both sides of the support.