JPH0952995A - Vinyl chloride-based resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin film, excellent in stable continuity for a long period in producing and processing films, having a suitable contrast ratio and useful as a surface decorative material by using a stabilizer without containing Cd, Pb and Cr as a stabilizer for the vinyl chloride-based resin film. SOLUTION: This vinyl chloride-based resin film is obtained by adding (B) 5-25 pts.wt. plasticizer (e.g. a phthalic acid ester such as di-2-ethylhexyl phthalate), (C) 1-5 pts.wt. epoxy compound (e.g. an epoxidized soybean oil), (D) 0.5-30 pts.wt. titanium oxide, (E) <=0.2 pt.wt. carbon black, (F) 0.1-10 pts.wt. iron oxide (preferably Fe00H and/or Fe2 O3 ) and (G) 0.5-5 pts.wt. hydrotalcite- based compound based on (A) 100 pts.wt. vinyl chloride-based resin thereto and further adding (H) a stabilizer without containing Cd and Pb (e.g. a Ba/Zn- based stabilizer, a Ca/Zn-based stabilizer or an Mg/Zn-based s-tabilizer) to the resultant mixture. The film preferably has 0.05-0.1mm thickness and 0.5-3 contrast ratio.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin film used as a cosmetic film used as a surface decorative material such as furniture material.

[0002]

2. Description of the Related Art A cosmetic film is used as a surface decorative material for various materials. Therefore, in order to obtain an excellent surface design, cosmetic printing is applied to the surface of the film to give various patterns. ing. A film that is soft and easy to stretch is likely to cause misalignment when performing multicolor printing, which lowers the commercial value.In the case of vinyl chloride resin film, use the plasticizer amount as a relatively hard film. Has been done. Such a vinyl chloride resin-based film is generally produced by a calender rolling method, but since it is a resin composition with a small amount of plasticizer, it has high viscosity when heated and melted, low fluidity, and As the heat stabilizer is large, frictional heat is large and it easily deteriorates due to heat. Therefore, a cadmium-based stabilizer is mainly used as a heat stabilizer.

[0003]

However, in recent years, a vinyl chloride resin film having a composition not containing cadmium, lead, chrome, etc. has been demanded as a market demand. The present invention provides a cosmetic vinyl chloride resin film that does not contain cadmium, lead or chrome in response to such market demands, and further, does not use such a stabilizer. A cosmetic having excellent thermal stability during processing of the composition, improving long-run property of processing so as not to cause inconvenience in actual production, and having a hiding power that is not affected by the color of a base material necessary for a cosmetic material. It is intended to provide a vinyl chloride resin film for a material.

[0004]

That is, the present invention is based on 100 parts by weight of a vinyl chloride resin, 5 to 25 parts by weight of a plasticizer, 1 to 5 parts by weight of an epoxidized compound, and 0.5 parts of titanium oxide.
-30 parts by weight, carbon black 0.2 parts by weight or less, iron oxide 0.1-10 parts by weight, hydrotalcite-based compound 0.5-5 parts by weight, and a stabilizer containing no cadmium or lead. And a vinyl chloride resin film.

Hereinafter, the present invention will be described in detail. As the vinyl chloride resin in the present invention, a homopolymer of vinyl chloride, a copolymer of vinyl chloride and another monomer copolymerizable with vinyl chloride, and a mixture of these resins can be used. Other monomers copolymerizable with vinyl chloride include, for example, ethylene, propylene, vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, fumaric acid, acrylonitrile and the like. . Preferred are vinyl chloride homopolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinyl acetate copolymers, and mixtures of two or more thereof. The degree of polymerization of these vinyl chloride resins is usually in the range of 600 to 1500, and among them, those having a degree of polymerization in the range of 700 to 1300 are suitable in view of the fluidity during melting.

Examples of the plasticizer include phthalate ester plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, diisononyl phthalate and diundecyl phthalate, and tri-2-.
Main component is one or more of trimellitic acid ester plasticizers such as ethylhexyl trimellitate, adipic acid as a dihydric alcohol and neopentyl glycol, propylene glycol, 1.4 butanediol as a polyhydric alcohol. The polyester-based plasticizer can be used as a main component in quantity. These plasticizers are used in an amount of 5 to 25 parts by weight, preferably 7 to 100 parts by weight of the vinyl chloride resin.
Used in the range of up to 20 parts by weight. If it is less than 5 parts by weight, the melt viscosity becomes high, which is unsuitable for production processing. If it exceeds 25 parts by weight, the film becomes soft and it becomes necessary to increase the film thickness, which is economically unsuitable. These plasticizers may be used alone or in combination of two or more. Further, there is no problem in using these plasticizers in combination with a commercially available plasticizer of a type other than the above.

As the epoxidized compound, epoxidized soybean oil, epoxidized linseed oil and the like can be used. These epoxidized compounds are 1 to 100 parts by weight of vinyl chloride resin.
It is used in an amount of 5 parts by weight, preferably 2 to 4 parts by weight.
If it is less than 1 part by weight, long-term stability during film processing is unsuitable, and if it is in the range of 5 parts by weight, long-run property at the time of processing is sufficient for actual production. Ink adhesion is impaired, and it is economically disadvantageous.

As the titanium oxide, rutile type and anatase type can be used. From the viewpoint of light resistance of the film, rutile type titanium oxide is preferable. The amount used is 0.5 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The amount used is 0.
When the amount is less than 5 parts by weight, the hiding property is low, which is not preferable.
If it is used in an amount of more than 0 parts by weight, the workability will be deteriorated and the physical properties required as product characteristics will be affected. The amount of carbon black used was 0.
It is not more than 2 parts by weight, and if it is used in excess of 0.2 parts by weight, the black color is too strong and is unsuitable. The amount of iron oxide used is 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount used is less than 0.1, the hiding property is low and unsuitable, and if it exceeds 10 parts by weight, the processability of the film is also deteriorated and the physical properties required as product properties are also affected. Since the amounts of titanium oxide, carbon black and iron oxide used are related to the degree of hiding of the film, the respective additives are appropriately selected and used within the above range depending on the film thickness. Iron oxide is the first iron oxide compound FeOO
H, Fe ₂ O ₃ which is a ferric oxide compound. This iron oxide may be used alone or in combination.

A typical example of the hydrotalcite compound is Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .mH ₂ O Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .mH ₂ O Mg _4.5 Al ₂ (OH) CO It is a compound represented by ₃ · mH ₂ O (provided that m ≧ 0). It should be noted that any other hydrotalcite compound may be used alone or in combination. The amount used is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If it is less than 0.5 parts by weight, the effect of improving long-term stability during film processing cannot be obtained, and it is unsuitable. If it is used in an amount of more than 5 parts by weight, it is unsuitable because it accelerates the yellow color change of the vinyl chloride resin film. Is.

Examples of stabilizers containing no cadmium or lead include barium / zinc stabilizers, calcium / zinc stabilizers, magnesium / zinc stabilizers and the like. These stabilizers may be in the form of powder or liquid, and those generally available as composite stabilizers can be used. The complex stabilizer includes two or more kinds such as a fatty acid salt, an aromatic carboxylic acid salt, a basic salt, a phosphoric acid ester salt and a phosphorous acid ester compound, and a β-diketone compound such as dibenzoylmethane and stearylbenzoylmethane. It contains at least one kind.

In addition to the above additives, UV absorbers, hindered amine light stabilizers, antioxidants, lubricants, pigments, and other additives commonly used for vinyl chloride resins, as well as ABS, MBS, EVA. , MAS, acrylic-based grafters, and other modified resins and processability-improving resins can be added as necessary.

The vinyl chloride resin film has a thickness of 0.0
It is 5 to 0.1 mm. If the thickness is less than 0.05 mm, the strength becomes low, which is not preferable, and if the thickness exceeds 0.1 mm, the finish of sharp-angled corners is unfavorable at the time of bending a product processed into a decorative material, which is not suitable. The degree of hiding is a property related not only to the amount of additive added and the material, but also to the thickness of the processed film. Concealment is log1 /
T (where T = I / I _O , I _O is incident light, I is transmitted light, and T is transmittance). The degree of hiding as a cosmetic material is preferably in the range of 0.5 to 3 in practical use. If the hiding degree is less than 0.5, the influence of the hue of the undercoating material is likely to appear on the surface when it is attached to the undercoating material, and it is necessary to additionally use a layer having a function of enhancing the hiding property on the undercoating surface in advance. And so on, which is not preferable. When the hiding power exceeds 3, the long-term stability during processing is insufficient and unsuitable. The long-term stable continuous performance will be described with reference to the measuring method in the examples described later. According to the measuring method, if it is 30 minutes or more, there is no problem in actual production processing.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded. Examples 1 to 6 and Comparative Examples 1 to 4 The compositions shown in Table 1 were uniformly mixed with a 10 l Henschel mixer to prepare compounds. The following evaluation tests were carried out on each compound, and the results are shown in the lower part of Table 1. The numbers in the composition formulation table in Table 1 indicate parts by weight.

(1) Long-term stable continuity during processing Each compound is a plastic coder P manufactured by Brabender
Using an LV15 type kneader type kneader, 60 g of the compound was filled, and the kneader jacket was kneaded under heating with heating oil of 180 ° C., so that discoloration-deteriorated foreign matter was generated in the compound in contact with the rotor shaft surface. The time (minutes) required was evaluated. (2) Concealment Degree Each compound was heated and rolled with a 14-inch two-roll at 180 ° C. to produce a film having a thickness of 0.1 mm. The hiding degree of the film was evaluated using a 2112 type digital color densitometer manufactured by Dainichiseika Kogyo KK.

[0015]

[Table 1]

[0016]

EFFECTS OF THE INVENTION According to the present invention, it is possible to improve long-term stability in film production processing without using a stabilizer containing cadmium, lead or chromium as a stabilizer for a vinyl chloride resin film. Therefore, it is possible to efficiently provide a vinyl chloride-based film for a cosmetic material that does not contain cadmium, lead, or chromium, and it is possible to provide a vinyl chloride-based resin film having a degree of hiding that is suitable as a cosmetic material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08K 5/10 KGY C08K 5/10 KGY 5/15 5/15

Claims (3)

[Claims] 1. A 100 parts by weight of vinyl chloride resin,
Plasticizer 5 to 25 parts by weight, epoxidized compound 1 to 5 parts by weight, titanium oxide 0.5 to 30 parts by weight, carbon black 0.2 parts by weight or less, iron oxide 0.1 to 10 parts by weight, hydrotalcite-based. A vinyl chloride resin film comprising 0.5 to 5 parts by weight of a compound and a stabilizer containing neither cadmium nor lead. 2. Iron oxide is FeOOH and / or Fe ₂ 0
_{3. The} vinyl chloride resin film according to claim 1, which is ₃ . 3. The vinyl chloride resin film has a thickness of 0.0.
The vinyl chloride resin film according to claim 1 or 2, which has a degree of hiding of 5 to 0.1 mm and a hiding degree of 0.5 to 3.