JPH051155A - Vinyl chloride resin film and vinyl-coated steel plate - Google Patents

Abstract

PURPOSE:To obtain the subject film free from discoloration, deterioration and odor generation even after irradiation with electron ray by compounding a vinyl chloride/ethylene copolymer resin with specific amounts of an epoxidized resin acid monoalkyl ester and a specific plasticizer. CONSTITUTION:The objective film is produced by compounding, as essential components, (A) 100 pts.wt. of a resin component consisting of a vinyl chloride/ ethylene copolymer resin preferably having an average polymerization degree of 600-1,500 and an ethylene content of 0.5-9% with (B) >=7 pts.wt. of an epoxy compound consisting of an epoxidized resin acid monoalkyl ester and (C) >=8 pts.wt. of a phthalate-type and/or trimellitate-type plasticizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a good electron beam resistance,
The present invention relates to a vinyl chloride resin film and a vinyl-coated steel sheet using the same. More specifically, the present invention relates to a vinyl chloride resin film that is used for processing with an electron beam cross-linking adhesive or an electron beam cross-linking pressure-sensitive adhesive, an electron beam curable ink, an electron beam curable surface treatment agent, or the like. Is.

[0002]

2. Description of the Related Art In recent years, the development of adhesives, pressure-sensitive adhesives, inks and the like using electron beam cross-linking type monomers has been rapidly advanced. This method is being applied to various industrial fields because of its advantages such as faster crosslinking speed and no need for heating compared with conventional thermal crosslinking and ultraviolet crosslinking. For example, the conventional manufacturing method of a vinyl-coated steel sheet is roughly divided into a method of applying a vinyl chloride resin paste to a steel sheet and baking or a method of applying an adhesive to the steel sheet and laminating a separately produced vinyl chloride film. However, it has to be passed through a high-temperature heating furnace, so that the productivity is poor, and the embossing diaphragm applied to the film for heating is easily erased. However, after the electron beam cross-linking adhesive was applied to the steel sheet, a separately manufactured vinyl chloride film was laminated and irradiated with an electron beam from the film side, the curing speed was high and the film was not heated, so it was applied to the film. This method of producing vinyl-coated steel sheet by the electron beam irradiation method has attracted attention because it has the advantage that the embossing is clearly retained. However, the vinyl chloride film has a defect that it is easily deteriorated and yellowed when irradiated with an electron beam, which impedes the spread of this method. As a method for preventing this deterioration and yellowing, DOP or DOS as a plasticizer and a dialkyltin mercaptide-based stabilizer as a stabilizer are used in a suspension polymerization vinyl chloride resin as seen in JP-A-62-236733. The method of doing is proposed.

However, although this method certainly causes little deterioration after electron beam irradiation, it has a problem that it produces a mercapto-type odor and is not suitable for indoor use. Therefore, this improvement is desired. Was there.

There are many stabilizers other than tin mercaptide-based ones such as lead-based, cadmium-based, barium-based, calcium-based, and zinc-based stabilizers, and no odor is generated even when irradiated with an electron beam. In the composition, when it is irradiated with an electron beam, it discolors immediately afterwards, or after that, it yellows due to subsequent aging or exposure to a heating atmosphere. In particular, many building materials for indoor interior use have a light tint color tone, and many print patterns also exhibit a design effect due to a delicate combination, so that the change in the color tone of the film greatly affects the design.

Such a problem also occurs when a vinyl chloride film is subjected to secondary processing using an electron beam curing type ink, a surface treating agent, an adhesive or the like.

[0006]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention is to obtain a vinyl chloride film which does not cause discoloration or deterioration even when irradiated with an electron beam and does not generate odor.

[0007]

Means for Solving the Problems The gist of the present invention is to add 100 parts by weight of vinyl chloride-ethylene copolymer resin as a resin component and 7 parts by weight or more of an epoxidized fatty acid monoalkyl ester as an epoxy compound. A vinyl chloride resin film comprising 8 parts by weight or more of a plasticizer selected from one or a combination of two or more acid ester plasticizers or trimellitic acid ester plasticizers as an essential component. Is.

The vinyl chloride-ethylene copolymer resin used in the present invention is a copolymer resin obtained by a polymerization reaction of vinyl chloride monomer and ethylene monomer,
Well-known ones marketed by several companies at present may be used, and those having an average degree of polymerization of 600 to 1500 and an ethylene content of 9% or less are preferable. This selection is based on the amount of plasticizer, processability, and physical properties. If the average degree of polymerization is 600 or less, it is not preferable because the softening temperature of the film is lowered.
Since the melt viscosity decreases, film forming processing becomes difficult.
When the average degree of polymerization exceeds 1500, there is an advantage that the high temperature elasticity of the film increases, but since the molding processing temperature rises and the electron beam resistance tends to decrease due to thermal deterioration, it is necessary to increase the amount of the plasticizer. For example, when the polymerization degree of vinyl chloride-ethylene copolymer resin is 1700, the total amount of the epoxidized fatty acid monoalkyl ester and the plasticizer is 40 to 60 parts by weight, and when the polymerization degree is 2200, 50 to 80 parts by weight. It is preferred to use parts by weight.

When the ethylene content of the vinyl chloride-ethylene copolymer resin exceeds 10%, the softening temperature of the film is lowered and the tackiness of the molten resin is increased, which makes molding difficult, which is not preferable.

Since the vinyl chloride-ethylene copolymer resin is liable to lower the strength and elasticity of the formed film, it is necessary to mix it with the vinyl chloride resin to improve the strength depending on the use of the film. Special attention should be paid in this case. This is because the vinyl chloride-ethylene copolymer resin and the vinyl chloride resin have different melting behaviors, and the electron beam resistance decreases as the amount of the vinyl chloride resin increases.

When a vinyl chloride-ethylene copolymer resin and a vinyl chloride resin are mixed and used, vinyl chloride-
Add 50 parts by weight or less of vinyl chloride resin to 50 to 100 parts by weight of ethylene copolymer resin, and the total amount of both resins is 10
It is preferable to use a vinyl chloride-ethylene copolymer resin having an ethylene content of 3% to 9% and an average vinyl chloride resin polymerization degree of 600 to 1200. . If the ethylene content is less than 3%, the electron beam resistance decreases, and if the average polymerization degree of the vinyl chloride resin exceeds 1200, the unmolded resin particles (fisheye) are likely to occur in the molded film and the processing temperature. As a result, the electron beam resistance decreases due to thermal deterioration. If a vinyl chloride resin having an average degree of polymerization of 600 or less is used, the strength of the film is not improved, and the melting temperature is lowered, so that the moldability is deteriorated.

Examples of the epoxidized fatty acid monoalkyl ester used in the present invention include epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate and epoxidized octyl stearyl. .

The above epoxidized fatty acid monoalkyl ester is blended in one kind or in a combination of two or more kinds, but the blending amount is required to be 7 parts by weight or more. If it is less than 7 parts by weight, discoloration after electron beam irradiation becomes large.

Epoxidized glycerides such as epoxidized soybean oil and epoxidized linseed oil are markedly yellowed after electron beam irradiation, and are easily bloomed, resulting in poor printability.

In the present invention, one or more plasticizers selected from phthalate ester plasticizers or trimellitic acid ester plasticizers must be blended in an amount of 8 parts by weight or more.

Examples of the phthalate ester plasticizer include dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2 ethylhexyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate. Examples of the trimellitic acid ester-based plasticizer include tributyl trimellitate, triisobutyl trimellitate, tri-2-ethylhexyl trimellitate, and trioctyl trimellitate.

As the plasticizer used in the present invention, a phthalate ester-based plasticizer, or a plasticizer other than trimellitic acid ester-based plasticizers, such as adipic acid ester-based plasticizers, sebacate ester-based plasticizers, polyesters A plasticizer or the like may be used in combination, but even in that case, it is necessary to mix 8 parts by weight or more of a phthalate ester plasticizer or a trimellitic acid ester plasticizer.

Examples of the adipic acid plasticizer include di2-ethylhexyl adipate, diisooctyl adipate, diisodecyl adipate and octyldecyl adipate.

Examples of the zebatate ester plasticizer include dibutyl sebacate, di2 ethylhexyl sebacate, and butylbenzyl sebacate.

The polyester plasticizer is a dicarboxylic acid having two bonding groups (carboxyl groups) capable of bonding to alcohols such as adipic acid, sebacic acid and phthalic acid, and polyhydric alcohols such as propylene glycol and ethylene glycol. Polymer (eg, average molecular weight 500-5000)
The end is blocked with a monohydric alcohol or a carboxylic acid.

Although it is not clear what the plasticizer does in the course of the deterioration of the vinyl chloride resin due to the electron beam, in the study by the present inventor, phthalic acid was added together with the epoxidized fatty acid monoester and the stabilizer. Ester plasticizers,
It was found that the incorporation of the trimellitic acid ester plasticizer prevents the deterioration. Unlike the deterioration due to heat or the deterioration due to ultraviolet rays, the deterioration due to the electron beam instantaneously undergoes dehydrochlorination, decomposition and crosslinking at room temperature to generate radicals and polyenes. Therefore, it is speculated that the dispersion state of the resin, the epixy compound, the plasticizer, the stabilizer, etc. at room temperature of the formed film influences the electron beam resistance, and the plasticizer acts as a stabilizing medium. .

The phthalate ester-based plasticizer or trimellitic acid ester-based plasticizer must be blended in an amount of 8 parts by weight or more, and if the amount is less than 8 parts by weight, discoloration after electron beam irradiation is significantly deteriorated.

The amount of plasticizer should be adjusted depending on the application. In the case of vinyl coated steel film, the total amount of epoxidized fatty acid monoester and plasticizer should be 15 parts by weight or less.
45 parts by weight is preferred.

When the amount is less than 15 parts by weight, cracking occurs when a vinyl-coated steel sheet laminated with a metal plate for a steel sheet is bent by press molding. If it is more than 45 parts by weight, it is easily soiled and easily scratched.

The vinyl chloride resin film according to the present invention contains, in addition to the above-mentioned components, stabilizers, stabilizing aids, processing aids, lubricants and fillers which are usually used in the production of vinyl chloride. Alternatively, an ultraviolet absorber or a coloring agent may be included depending on the application.

The compound which can be used as a stabilizer includes
12 to 22 carbon atoms whose metals are barium, calcium and zinc
One or more selected from fatty acid metal soaps, among which, barium-zinc or calcium-
A combination system of zinc is preferable.

Specific examples of the compound include barium stearate, calcium stearate, zinc stearate,
Examples thereof include barium laurate, zinc laurate, barium ricinoleate, and zinc oleate. Diarnoalkyl tin mercaptide and dibutyl tin malate are not preferable because they easily generate an odor. Even if they are used, they should be used in combination with other stabilizers and the compounding amount should be 0.5 parts by weight or less. Of course, for applications where odor does not matter (for example, outdoor decorative sheets), 2.0 to 4.0 parts by weight will give good performance. Cadmium-based and lead-based stabilizers can also be used, but they are not preferable because they pose a problem of environmental toxicity.

Examples of the stabilizing aid include triphenyl phosphite, dioctyl phenyl phosphite, diphenyl isodecyl phosphite, dioctyl acid phosphite and the like. These stabilizing aids can be used alone or in combination of two or more kinds.

The lubricants and processing aids vary depending on the film forming equipment (calender, extruder, etc.), so appropriate amounts should be added according to the processing equipment. As a lubricant, a polyethylene wax lubricant, a fatty acid ester lubricant, an acrylic oligomer lubricant of about 0.1 to 1.0 part, and as a processing aid, an ethylene vinyl acetate copolymer resin,
About 1 to 10 parts by weight of acrylic resin can be used.

As the filler, talc and aluminum hydroxide are preferable, and calcium carbonate-based ones tend to turn yellow and should be added only in a small amount.

Next, a method of manufacturing the vinyl-coated steel sheet according to the present invention will be described. As the thin metal original plate for the vinyl-coated steel plate, a galvanized steel plate, pretreatment cold-rolled steel plate such as chromate treatment and pickling, various plated steel plate, stainless steel plate and the like whose surface is mechanically polished and phosphoric acid-treated are used. An electron beam curable adhesive is applied to the surface of the metal original plate, a vinyl chloride film produced according to the present invention is laminated on the applied surface, and an electron beam is irradiated from the top surface of the metal original plate and the vinyl chloride film. Adhere the system film. In order to improve the adhesive strength, the metal original plate may be preliminarily applied with a primer treatment, for example, a high-molecular polyester primer and baked.

The electron beam curable adhesive may be selected from well-known ones already on the market, for example, vinyl chloride-vinyl acetate copolymer, polyurethane, etc., containing acrylic acid ester type oligomer and monomer as main components. An electronically curable adhesive containing as a resin component can be used. The irradiation dose of the electron beam is 10 Mrad, and sufficient adhesive strength can be obtained. Since this method does not require a heating furnace as in the conventional method, the fine embossed diaphragm provided on the film does not disappear and a vinyl-coated steel sheet having a high designability can be obtained. Further, since the heating step and the cooling step are unnecessary, the adhering speed is fast, and the starting and stopping of the apparatus are easy, the productivity is good and the method is industrially excellent.

[0033]

EXAMPLES Next, the effects of the vinyl chloride resin film of the present invention will be shown by specific embodiments of the present invention and comparative examples. However, the present invention can be widely applied, and is not limited to these. Absent.

Examples 1 to 12 and Comparative Examples 1 to 10 Weighing and mixing according to the formulations shown below, setting the test roll to the temperature shown in Table 1 and kneading for 10 minutes to prepare a 0.1 mm thick white film. , This film is a curetron electron beam irradiation device (Nisshin High Voltage Co., Ltd. 200keV, 20mA)
Was irradiated with 5 Mrad and the yellowing of the film was investigated by the following test.

Compound resin ┐ Epoxy compound ─ ┼ ─ As shown in Table 1 Plasticizer ─ ┘ Stabilizer ─ ─ ─ ┬ ─ Barium-zinc composite liquid stabilizer (* 1) ─ 1.2 parts by weight ├ ─ Barium stearate ────────── 0.3 parts by weight └─Zinc stearate ──────────── 0.5 parts by weight Colorant (white) ─── TiO ₂ (* 2) ─── ───────── 5.0 parts by weight * 1 ADEKA STAB AC-186 manufactured by Asahi Denka Co., Ltd. * 2 Taipaque R-550 manufactured by Ishihara Sangyo Co., Ltd.

Test items 1. Yellowing after electron beam irradiation: The change in color tone (yellowing) of the film before electron beam irradiation and the film after electron beam irradiation was examined. ◎: No change (color difference ΔE = 1.0 or less) ○: Slightly yellowed (color difference ΔE = 1.1 to 5.0) △: Yellowed (color difference ΔE = 5.1 to 10.0) ×: Remarkably yellowed (color difference ΔE = 10.1 or more) 2 ． Discoloration after heating ………………………………………………………………………………………………………………………………………………………………………………………………………………………… of of the film was heated in an oven for 24 hours at 120 ° C. ◎: No change (color difference ΔE = 1.0 or less) ○: Slight yellowing (color difference ΔE = 1.1 to 5.0) △: Yellowing (color difference ΔE = 5.1 to 10.0) ×: Remarkably yellowing (color difference ΔE = 10.1 or more)

[0037]

[Table 1]

* 3 Polyvinyl chloride resin manufactured by Kureha Chemical Industry Co., Ltd. average degree of polymerization = 1300 * 4 Polyvinyl chloride resin manufactured by Kureha Chemical Industry Co., Ltd. average degree of polymerization = 1000 * 5 Chloride manufactured by Tosoh Corporation Vinyl ethylene copolymer resin average degree of polymerization = 1300 Ethylene content = 1% * 6 Tosoh Corporation vinyl chloride ethylene copolymer resin average degree of polymerization = 1000 Ethylene content = 1% * 7 Sekisui Chemical Co., Ltd. ) Made vinyl chloride ethylene copolymer resin average degree of polymerization = 1350 ethylene content = 4% * 8 Sekisui Chemical Co., Ltd. made vinyl chloride ethylene copolymer resin average degree of polymerization = 1050 ethylene content = 4% * 9 Sekisui Chemical Co., Ltd. vinyl chloride ethylene copolymer resin average degree of polymerization = 1050 Ethylene content = 8% * 10 Sekisui Chemical Co., Ltd. vinyl chloride ethylene copolymer resin average degree of polymerization = 1050 Eth Ren content = 9% * 11 Asahi Denka Kogyo KK Epoxidized fatty acid alkyl ester molecular weight = 356 * 12 Asahi Denka Kogyo epoxidized fatty acid octyl ester molecular weight = 409 * 13 Asahi Denka Kogyo Epoxidized soybean oil molecular weight = approx. 1000 * 14 Asahi Denka Kogyo Co., Ltd. epoxy resin (polymer of epichlorohydrin and bisphenol A) * 15 Di2ethylhexyl phthalate * 16 Trioctyl trimellitate * 17 Di2ethylhexyl adipate * 18 Asahi Denka Kogyo Co., Ltd. adipic acid-based polyester plasticizer with a molecular weight of about 2000 * 19 Tricresyl phosphate * 20 Kureha Chemical Co., Ltd. polyvinyl chloride resin Average degree of polymerization = 750

Description of Examples 1 to 12 and Comparative Examples 1 to 10 (1) All the films using the vinyl chloride-ethylene copolymer resin show little yellowing even when heated after electron beam irradiation. However, the compounding using the vinyl chloride resin causes a large change in color after heating (Examples 1 to 6 and Comparative Examples 1 to 3). (2) The compounding without using the epoxidized fatty acid monoalkyl ester as the epoxy compound has a large coloring after heating. Epoxidized soybean oil and epoxidized linseed oil do not improve yellowing even if the blending amount is increased (Comparative Examples 3 to 7). (3) As a plasticizer, a phthalate ester plasticizer DO
The compounding of P with TOTM as a trimellitic acid ester plasticizer does not cause yellowing (Examples 1 to 10). (4) Yellowing is less in the case of blending 10 parts of DOP and 10 parts of adipic acid ester plasticizer, and the blending of 10 parts of DOP and 10 parts of polyester plasticizer. But D
Those in which 5 parts by weight of OP or 5 parts by weight of TOTM and 20 parts by weight of a polyester-based plasticizer or a phosphoric acid ester-based plasticizer are mixed have large yellowing (Examples 11 and 12 and Comparative Examples 8 and 9). (5) Yellowing is less in the case of blending 7 parts by weight or more of the epoxidized fatty acid monoalkyl ester. However, yellowing was large at 5 parts by weight (Examples 8 and 9 and Comparative Example 10).

Examples 13 to 21 and Comparative Examples 11 to 18 After weighing and mixing with the following ingredients, the test rolls are shown in Table 2.
The processing temperature was set to 1, and after kneading for 10 minutes, a white film having a thickness of 0.1 mm was prepared and evaluated in the same manner as in Example 1.

Compound resin ┐ Epoxy compound ─ ┼ ─ As shown in Table 2 Plasticizer ┘ Stabilizer ─ ─ ─ ┬ ─ Barium-zinc composite liquid stabilizer (* 1) ─ 1.2 parts by weight ├ ─ Barium stearate ─ ─ ─────── 0.3 parts by weight └─Zinc stearate ─────────── 0.5 parts by weight Colorant (white) ──── TiO ₂ (* 2) ────── ───── 5.0 parts by weight Test items Same as Examples 1-12 and Comparative Examples 1-10

[0042]

[Table 2]

Description of Examples 13 to 21 and Comparative Examples 11 to 18 (1) In a composition in which a vinyl chloride-ethylene copolymer resin and a vinyl chloride resin are mixed, the content of ethylene and the degree of polymerization of the vinyl chloride resin are It is necessary to pay attention to and to mix. In a mixture of a vinyl chloride-ethylene copolymer resin having an ethylene content of 4% to 8.7% and a vinyl chloride resin having an average degree of polymerization of 750 and 1000, the vinyl chloride resin is used in an amount of 40 parts by weight or less of electron beam. There is little coloring even after heating after irradiation,
If it is 50 parts or more, the coloring becomes large (Examples 13 to 21, Comparative Examples)
11-14). (2) Discoloration after heating is large in the case of a mixture in which a vinyl chloride-ethylene copolymer resin having an ethylene content of 4% and a vinyl chloride resin having an average degree of polymerization of 1300 are mixed (Comparative Example 1
5,16). (3) Even if a vinyl chloride resin having an average degree of polymerization of 750 is used, yellowing due to heating after electron beam irradiation occurs in the case of a mixture containing a vinyl chloride-ethylene copolymer resin having an ethylene content of 0.5%. Is large (Comparative Examples 17 and 18).

Examples 22 to 25 and Comparative Examples 19 to 22 Weighing and mixing according to the following formulations, kneading with a test roll for 10 minutes, forming a film having a thickness of 0.1 mm, and using a press machine set at 170 ° C. The film was finely embossed. The following electron beam curable adhesive is applied to a separately prepared treated steel plate (plate thickness: 5 mm) (application thickness: 10 μm), and the film prepared above is pressure-bonded and laminated with a rubber roller, and this sample is cured with atron electron beam. The irradiation device radiates an electron beam of 10 Mrad from the film side to bond the steel plate and the film,
A vinyl chloride coated steel sheet was created.

Film compounding resin ─ ┐ Epoxy compound ─ ┼ ─ As shown in Table 3 Plasticizer ┘ Stabilizer ─ ─ ─ ┬ ─ Barium-zinc composite liquid stabilizer (* 1) ─ 1.2 parts by weight ├ ─ Barium stearate ────────── 0.3 parts by weight └─Zinc stearate ──────────── 0.5 parts by weight Colorant (white) ──── TiO ₂ (* 2) ── ───────── 5.0 parts by weight

Adhesive formulation Isobornyl acrylate 40 parts 2-Hydroxyethyl acrylate 25 parts Epoxy ester 3002A * 21 15 parts Denka vinyl # 1000A * 22 10 parts Dismocor 130 * 23 10 parts * 21 Kyoeisha Yushi-Kagaku Kogyo Co., Ltd. Epoxy acrylate * 22 Denki Kagaku Kogyo Co., Ltd. Vinyl chloride vinyl acetate copolymer * 23 Sumitomo Bayer Urethane Co., Ltd. linear polyurethane resin

Test items 1. Boiling water test: The prepared vinyl-coated steel sheet is immersed in boiling water for 6 hours, then taken out and allowed to stand at room temperature for 18 hours. This was repeated 20 times as one cycle, and the yellowing state before and after the test was examined. Evaluation ○: Slightly yellowed (color difference ΔE = 1.1 to 5.0) Δ: Yellowed (color difference ΔE = 5.1 to 10.0) ×: Remarkably yellowed (color difference ΔE = 10.1 or more) 2. Weather resistance… Accelerated weather resistance tester (manufactured by Suga Test Instruments Co., Ltd.) Sunshine weatherometer WEL-SUN
−DC type black panel temperature 63 ° C. A sample after a continuous test for 500 hours was taken to examine the yellowing state. Evaluation ◎: No change (color difference ΔE = 1.0 or less) ○: Slight yellowing (color difference ΔE = 1.1 to 5.0) Δ: Yellowing (color difference ΔE = 5.1 to 10.0) 3. Bending test: The vinyl coated steel sheet was bent 180 degrees with the vinyl film side facing outward, and the surface condition of the bent portion was observed. Evaluation ○: No abnormality ×: Whitening 4. Stain test: Apply white petrolatum mixed with 10% carbon black powder to vinyl coated steel sheet and leave it for 24 hours. After that, wipe the petrolatum with a compress and measure the change in glossiness (60 ° C) before and after the test. Evaluation ◯: Retention rate of glossiness of 85% or more ×: Retention rate of glossiness of 85% or less

[0048]

[Table 3]

Examples 26 to 28 and Comparative Examples 23 to 24 Weighing, mixing and kneading with a test roll for 10 minutes to prepare a base film having a thickness of 0.1 mm and a transparent film having a thickness of 0.05 mm, and the base film After printing an abstract pattern with a gravure printing machine, a transparent film was overlaid on this film, and laminate embossing was performed with a press machine to prepare a decorative sheet with a total thickness of 0.15 mm. Compounded clear film resin: Plasticizer as shown in Table 4 Stabilizer as shown in Table 4 Colorant the same as in Example 1 None Base film VE-L * 7: 100 parts by weight D-55 * 11: 10 parts by weight DOP: 20 parts by weight Stabilizer: The same colorant as in Example 1: The same test method as in Example 1 The design sheet after electron beam irradiation (5 Mrad) was placed in an oven 85
Test result of examining change in design of printed design after heating at ℃ × 30 hours-Table 4

[0050]

[Table 4]

Description of Examples 22 to 25 and Comparative Examples 19 to 22 (1) Vinyl coated steel sheets made from the film produced by the composition according to the present invention have boiling water test, weather resistance, bending workability and stain resistance. It was good (Examples 22 to 25). (2) However, in the formulation using a vinyl chloride resin as the resin, yellowing was large in the boiling water test (Comparative Examples 19 to 2).
0). (3) When the total amount of the epoxidized fatty acid monoalkyl ester and the plasticizer was 10 parts by weight, the film was hard and whitening occurred during bending (Comparative Example 21). (4) A compound containing 50 parts by weight of the epoxidized fatty acid monoalkyl ester and the plasticizer was easily soiled (Comparative Example 2).
2).

Description of Examples 26 to 28 and Comparative Examples 23 to 24 (1) The decorative films laminated and embossed with the transparent film of the present invention have little yellowing even after heating, and changes in print design are observed. There wasn't. However, with the formulation not according to the present invention, the clearness of the print design was lost due to yellowing of the transparent film (Examples 26 to 28, Comparative Example 23).
~twenty four).

[0053]

As described above, the present invention is based on 100 parts by weight of vinyl chloride-ethylene copolymer resin, 7 parts by weight or more of an epoxidized fatty acid monoalkyl ester as an epoxy compound, and a phthalate ester type resin. Since the plasticizer or the trimellitic acid ester plasticizer is blended as an essential component with 8 parts by weight or more of a plasticizer selected in combination of one or two or more, the film is irradiated with an electron beam. It was also confirmed that there was no yellowing, and there was no deterioration yellowing in the practical tests (heating, boiling water, weather resistance) after irradiation. In the present invention, there is no limitation in the application because a commonly known general stabilizer can be used without using a conventionally known tin mercaptide-based stabilizer, and as a result, excellent electron beams can be obtained. It is now possible to obtain processed products that make the most of their characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 27/06 LES 9166-4J // C08L 27:06 (72) Inventor Kenji Koshiishi Ichikawa City, Chiba Prefecture 1 at Shinshin Steel Co., Ltd., New Material Research Center, 7th Takatani Shinmachi Co., Ltd. (72) Inventor: Tagao Tomoe Susumu, 1 at Nisshin Steel Co., Ltd. Coat Center (7), 7th Takaya Shinmachi Co., Ltd., Ichikawa City, Chiba Prefecture Kenichi Masuhara 1st day, 7th Takatani Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd.

Claims (4)

[Claims] 1. A resin component containing 100 parts by weight of vinyl chloride-ethylene copolymer resin, 7 parts by weight or more of an epoxidized fatty acid monoalkyl ester as an epoxy compound, and a phthalate ester-based plasticizer or trimellitic acid ester-based resin. A vinyl chloride resin film, characterized in that 8 parts by weight or more of a plasticizer selected from the plasticizers or a combination of two or more plasticizers is added as an essential component. 2. The vinyl chloride-ethylene copolymer resin has an average degree of polymerization of 600 to 1500 and an ethylene content of
0.5 to 9%, The vinyl chloride resin film according to claim 1, characterized in that 3. As a resin component, (a) vinyl chloride-ethylene copolymer resin is 50 to 100 parts by weight, (b) vinyl chloride resin is 50 parts by weight or less, and the total amount of these resins ((a)
+ (B)) is added in a proportion of 100 parts by weight, and the ethylene content of the vinyl chloride-ethylene copolymer resin is 3% to 9%.
And the vinyl chloride resin has an average degree of polymerization of 600 to 1200, wherein the vinyl chloride resin film according to item 1. 4. The total amount of epoxidized fatty acid monoalkyl ester as an epoxy compound and a plasticizer is 15 to 45.
The vinyl-coated steel sheet, wherein the vinyl chloride resin film according to item 1 is bonded to a thin metal original plate, which is parts by weight.