JPS6026062A - Paint for film cartridge made of metal - Google Patents

Abstract

PURPOSE:To prevent trouble during photographing by improving the mechanical strength of paint, by using a thermosetting resin compsn. consisting of two specified epoxy resins and an amino resin as a binder. CONSTITUTION:A thermosetting resin compsn. consisting of an epichlorohydrin/ bisphenol type epoxy resin, a polyester-modified epichlorohydrin/bisphenol type epoxy resin and an amino resin is blended as a binder with a paint. Examples of the amino resin are those obtd. by the condensation reaction between a compd. contg. an amino group and an aldehyde, including aniline/formaldehyde resin, urea resin and melamine resin. The titled paint can be prepd. by dissolving said binder compsn. in an org. solvent and dispersing a pigment therein. When a clear paint is desired, no pigment is added.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in paints used in photographic film cartridges.

In particular, a photographic film cassette in which a roll film consisting of a strip of photographic film, such as 16 ml or 55 tsw, is inserted into a cassette as shown in FIG. 1 is widely used. That is, conventionally, in the manufacturing process, the photographic film is cut into strips of a specified length, and then the front end (or rear end) of a cylindrical member is cut as shown in FIGS. 1-a and 1-b. is extended in the tangential direction, the rear end (or front end) is made to protrude along the extended surface of the front end (or rear end), and a light-shielding IJ, )? a cylindrical body plate 2 having a beak-shaped film outlet 4 pasted thereon; a cap 6.6 fitted to both ends of the body plate 2; Flange 7 near the inside of 3
．． 7 and a spool 6 which is rotatably supported by the cap 6.
Most of the film is loaded and sealed onto the winding shaft 8 of the spool 6, and a small portion of the film strip is wound so that the other end Fb of the film strip is exposed through the outlet 4. 0 As the paints used for such photographic film cartridges, conventional paints include paints for the outer surface of the metal body and the inner surface of the metal body with a thermosetting resin composition composed of an alkyd resin and a vinyl resin as an inder. , a paint containing a thermosetting resin composition composed of a polyester resin and a melamine resin as a binder was used for the cap paint.

However, these paints have low mechanical strength, and breakage of the paint occurs during the process of forming the body plate or cap or the process of winding the film, which frequently causes problems when taking photographs.

The first object of the present invention is to provide a paint for metal film cartridges with excellent mechanical strength. Characteristics required for paints for film cartridges include:
In addition to the above (1) mechanical strength, (2) good photographic properties, that is, no adverse effect on the photographic performance of the film. (3) It should have a good appearance, that is, it should have excellent gloss, and in some cases, it should have a variation in color.

etc.

A second object of the present invention is to provide a paint for metal film cartridges with good photographic properties.

Among the paints for film and sotrone, among the above-mentioned properties required for the exterior paint of a metal shell, (3) appearance is particularly important, and in addition to the above-mentioned properties, for the interior paint of a metal shell. (4) It is noted that it has good adhesion to light-shielding materials, and as a cap paint, among the above-mentioned properties, (1) mechanical strength is particularly important.

The purpose of the present invention is to provide a paint for metal film cartridges that places particular emphasis on mechanical strength among the above-mentioned properties, and this purpose is to provide a coating material for a metal film cartridge made of epichlorohydrin bisphenol type epoxy resin, 71? This is achieved by a cap paint for film cartridges characterized by using a thermosetting resin composition comprising a ester-modified epichlorohydrin/bisphenol type epoxy resin and an amino resin as a binder.

The inventors of the present invention have conducted numerous comparative experiments and trial and error, focusing on the above-mentioned characteristics, among metal plate paints that can be used for cans, crowns, etc., or some paints that can be inferred from these paints. Table 1 shows an example of the results of a comparative experiment. That's what happened.

[Photographic characteristics test]

Tin-free steel high-top made by Toyo Steel Co., Ltd.
0.24 il Im thick) using a natural roller coater method and dried in a hot air continuous drying oven to prepare a test piece. Place the test piece in a dark room without exposing it to A.
The film was overlapped with SA400 color negative film, light-shielded and sealed, and left in a 50 tlr thermostatic chamber for 3 days, then exposed and developed. Characteristics were compared with a negative film that had not come into contact with the test piece, and judged based on the following criteria.

○・・・・・・・・・・・・No influence on the photosensitive material characteristic curve such as sensitivity and fog.

×・−・・・・・・・・・・・・Those that had a detrimental effect on the photosensitive material characteristic curve due to a decrease in sensitivity and an increase in fog.

[Mechanical strength]

A test piece is prepared in the same manner as the above photographic property test, and the following six items are tested on the test piece.

1) Dynamic friction coefficient measurement using a dynamic slip tester manufactured by Nippon Rigaku Kogyo ■.

Friction body: Chrome-plated iron piece Load: 1200gr Speed: 1200mm/min Temperature during measurement: room temperature, humidity: 42% 2) Bending resistance: DuPont impact tester used, n-slope table, test piece 4c
After bending with rnX 5QnO411 rod, IKP-50α
Processed under certain conditions.

Immerse in copper sulfate/hydrochloric acid mixture for 2 minutes and then wash with water.

Measure the crack length (long). Temperature during processing...116)
Pencil hardness conforms to JIS -5400. Uses Mitsubishi Uni Pencil.

Measurement temperature: room temperature.

4) Adhesion A scratch is made on the coating film in the shape of a substrate using a cutter knife, and the adhesion of the coating film made by Nichino 2 Intezo to the substrate is investigated.

Displayed as peeling %.

5) Cross-cut hardness Measure the maximum load (gr) that the coating film can withstand using a J-5o4404100μ sapphire needle. The end point is when a scratch appears on the surface of the formed coating film.

Measurement temperature: room temperature.

6) Punch out the cap 3 shown in FIG. 1 using a fress machine, mold it, and inspect for damage to the coating film.

Comprehensive judgment was made for the above six test items based on the following criteria.

◎・・・・・・−・・・−・・・Characteristics (1) to (6) are outstanding.

O: - Characteristics (1) to (6) are relatively poor.

x: Characteristics (1) to (6) are relatively poor.

〔exterior〕

A test piece is prepared in the same manner as the above photographic property test, and the outer surface of the test piece is visually inspected for reflection, and judged based on the following criteria.

○・・・−・・−・・・High reflectance, high gloss on the painted surface ◎・・・・・・・・・・・・・High reflectance, especially high gloss on the painted surface Table 1 Comparison of properties of resins for metal paints and inks From the results in Table 1, paints using a thermosetting resin composition consisting of the epichlorohydrin/bisphenol type epoxy resin of the present invention, a polyester-modified epichlorohydrin/bisphenol type epoxy resin, and an amine resin as a binder. It can be seen that (the resin-based paint in the table) is particularly excellent in mechanical strength, and although it has poor adhesive strength, it meets the purpose of the present invention.

A specific example of the epichlorohydrin/bisphenol type epoxy resin used in the present invention is Epikote 100.
7 (trade name, manufactured by Shell Chemical Co., Ltd.), Evicron 9050 (
Product name: Dainippon Ink & Chemicals Co., Ltd.), Ebiko) 1
009 (trade name, manufactured by Shell Chemical Co., Ltd.), and specific examples of polyester-modified epichlorohydrin/bisphenol type epoxy resins include Evicron H-353 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), Eviclon H-1
57 (trade name, manufactured by Dainippon Ink Chemical Industries, Ltd.), etc.

Furthermore, the amino resin used in the present invention is a resin obtained by a condensation reaction between a compound having an amino group and an aldehyde, and includes aniline aldehyde resin, urea resin, melamine resin, etc. Specific examples include butylated urea resin, etc. Resin P-138 (trade name, Dainippon Ink & Chemicals Co., Ltd. M), butylated melamine resin J-830-6OA (trade name, Dainippon Ink & Chemicals Co., Ltd.), benzoguanamine resin L -
128-55B (product name, manufactured by Dainippon Ink Chemical Industries, Ltd.)
etc.

The paint of the present invention is obtained by dissolving the above Ingu composition in an organic solvent and dispersing the pigment (in the case of a transparent paint, no pigment is added).

Next, the present invention will be specifically explained using examples.

In addition, "%" and "parts" in the examples represent "% by weight" and "parts by weight", respectively.

Example 1 Epichlorohydrin bisphenol type epoxy resin manufactured by Shell Chemical Co., Ltd., Epikote 100,725 parts, M polyester modified epichlorohydrin manufactured by Dainippon Ink Chemical Co., Ltd.
Bisphenol type epoxy resin Evicron H-353 (
10 parts of non-volatile content 40%) and 5 parts of butylated urea resin P-138 (non-volatile content 60%) manufactured by Dainippon Ink and Chemicals, 10 parts of Kijirole, 5 parts of n-citanol, 5 parts of butyl cellosolve, and diacetone alcohol. 2 (1) A solvent consisting of 20 parts of cellosolve acetate was stirred and mixed in a tank equipped with a high-speed stirrer, then transferred to a tank equipped with a dispersion stirrer for adjustment and dispersion, and passed through a filter to obtain a transparent paint.

Example 2 9050.20 parts of Ebichlorhyphorus P-phosphorus/bisphenol type epoxy resin Ebichlor, manufactured by Dainippon Ink Chemical Industry Co., Ltd.
Dainippon Ink & Chemicals Co., Ltd. polyester modified Ebichlorhi P phosphorus-bisphenol type epoxy resin Epiclon H
-353 (40% non-volatile content) 10 parts, Kijiroll 10
parts, n-citanol 5 parts, butyl cellosolve 10 parts, diacetone alcohol 20 parts, cellosolve acetate 15 parts
The solution was dissolved in a tank equipped with a high-speed stirrer, and then transferred to a tank equipped with a dispersion stirrer.
5 parts of non-volatile content (60%) and 5 parts of cardin black were added and mixed with stirring, kneaded using a sand mill, further stirred and dispersed in a tank equipped with a dispersion stirrer, and passed through a filter to prepare a black paint. .

Example 6 1009.20 parts of Cie/'Kaf Co., Ltd. Ebi Chlorhi IF Phosphorus/bisphenol type epoxy resin Ebiko), Polyester modified Ebi Chlorhime P Phosphorus/bisphenol type epoxy resin Epicron H- manufactured by Dainippon Ink Chemical Industry Co., Ltd.
157 (non-volatile content 40%) 5 parts Woxyrol 10 parts, n
- Dissolved in a tank with a high-speed stirrer using a solvent consisting of 10 parts of butanol, 10 parts of butyl cellosolve, 15 parts of diacetone alcohol, and 10 parts of cellosolve acetate, transferred to a tank with a dispersion stirrer, and further 4-zoguanamine manufactured by Dainippon Ink Chemical Industries, Ltd. 5 parts of resin L-128-55B (non-volatile content 55%) and 5 parts of cardin black were added and mixed with stirring, then kneaded using a sand mill, and then further mixed with a resin in an rv' chamber equipped with a dispersion stirrer. Then, 10 parts of silica was added, stirred and dispersed, and passed through a filter to prepare a black paint.

The black paint described in Example B was applied to one side of a stain-free steel plate (0.241111 thickness) made by Toyo Kohan Co., Ltd. using a natural roller coater method to coat 90±101.
719/100 cm" and dried in a hot air continuous drying oven for 10 minutes under 200 tons. The other side was coated with the black paint described in Example 2 using the same natural roller coater method in a coating of 90±10 cm". Painted with 100crn and dried in a hot air drying oven at 200C for 10 minutes, and then coated the same surface with the transparent paint described in Example 1 as a gloss varnish using the same natural roller coater method at 60±5cm/1.
00crn'' and dried in a hot air drying oven at 170C for 10 minutes.Then, it was punched and formed into a P-nut shape to form a cap whose inner surface was coated with the black paint described in Example B. When a film cartridge as shown in the figure was prepared, improved performance as shown in Table 1 was confirmed.

Figures 1 and 2 are cross-sectional views taken along the line I--A in Figure 2A.

1...-Torone, 2...Torso, 3...Gap, 6...Suzor.

Claims (1)

[Claims] Epichlorohydrin bisphenol type epoxy resin,
A paint for a metal film trone, characterized in that the binder is a thermosetting resin composition comprising a polyester-modified epichlorohydrin/bisphenol type epoxy resin and an amino resin.