JPH0366738A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the title antifungal composition for safe, hygienic food packaging materials good in heat resistance and prevented from discoloration due to light by incorporating a silver zeolite-contg. vinyl chloride-based resin with a Mg-Al-based basic carbonate. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt., in terms of resin, of a resin composition prepared by adding antifungal silver zeolite to a vinyl chloride-based resin with (B) 0.01-10 (pref. 0.05-5.0) pts.wt. of a Mg-Al-based basic carbonate, Mg-Zn-Al-based basic carbonate or a blend thereof. The component A may contain a plasticizer and/or epoxy-based stabilizer.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an antibacterial and antifungal vinyl chloride resin composition with improved photochromic properties and a vinyl chloride resin composition for food packaging. .

<Conventional technology> Along with the cleanliness of the surrounding areas surrounding daily life.

The company is entering the market with products such as antibacterial wallpaper, antibacterial clothing, and antibacterial gloves. PVC resins are said to have high resistance to bacteria, mold, etc., but these resins are rarely used for resin cars, and depending on the purpose, they may be used as plasticizers, stabilizers, lubricants, etc. , and various other additives are usually added, and it is a well-known fact that these reduce the antibacterial and antifungal properties.

In order to solve this problem, methods of applying antibacterial and antifungal agents to the plastic surface or kneading them into the plastic are used. Organic compounds are often used as antibacterial and antifungal agents, such as the arsenic compound vinazine, the organic chlorine compound PCP, and the aniline derivative deapenzole. These are leaching from plastic, odor, and antibacterial.

It is said that there are problems in terms of stability, such as persistence of fatty mold properties, and safety and hygiene in terms of food packaging applications.

An inorganic antibacterial agent that has been developed in recent years is antibacterial silver zeolite, in which the metal ions in zeolite are replaced with silver ions. It is excellent and can be used in stable conditions.

It is well known that by kneading such materials into plastics, antibacterial and antifungal properties can be imparted, and products in which such materials are kneaded into polyolefin and polystyrene can also be seen.

<Challenges> However, silver compounds such as antibacterial silver zeolide are added to vinyl chloride-based PA resin to create a film.

When a sheet or the like is formed, the film, sheet, etc. is significantly discolored by light, reducing its commercial value.

Means for Solving the Problems> The present inventors have overcome the problems of the prior art described above, and have developed a vinyl chloride resin composition with improved photochromic properties, excellent antibacterial and antifungal properties, and a hygienic-free vinyl chloride resin composition. As a result of extensive research in order to develop food packaging films with excellent antibacterial properties, we found that magnesium-aluminum-based Adding 0.01 to 10 parts of a basic carbonate, a magnesium-zinc-aluminum basic carbonate, or a blend thereof, a vinyl chloride resin, a plasticizer, and an epoxy stabilizer.

A magnesium-aluminum basic carbonate, a magnesium-zinc-aluminum male carbonate, or a blend thereof is added to 100 ffl ffi parts of a vinyl chloride resin composition containing antibacterial silver zeolite. This means that 0.01 to 10.0 parts by weight was added.

Function> The present invention combines magnesium-aluminum basic P into a blended system in which antibacterial silver zeolite is added to vinyl chloride resin.
By adding Mjm or magnesium-zinc-aluminum basic carbonate or a blend thereof, more specifically, these resin compositions can be melted by calender rolling, extrusion, or inflation to form a film. The photochromic properties of films, sheets, etc. are improved.

<Example> The vinyl chloride resin according to the present invention includes polyvinyl chloride or polyvinyl chloride and other heptanomers, such as ethylene, propylene, alkyl vinyl ether, acrylic acid ester, and vinyl acetate.

Methacrylic ester, acrylic, acrylonitrile,
Examples include copolymers with urethane, nylidene, etc., or blends thereof.

Furthermore, the antibacterial silver zeolite used in the present invention refers to the zeolite (xMi) using natural or synthetic zeolite as a carrier.
o-#03 ysio-zlho) ion-exchangeable gold f! Silver, copper, zinc, mercury, and tin, in which part or substantially all of (M) has bactericidal properties.

Substituted with one or more metal ions selected from the group consisting of lead, bismuth, cadmium, and chromium,
Some contain silver ions. There is no limit to the amount of tll to be added, but from the viewpoint of antibacterial effects, it is preferably 0.01 parts by weight or more. If the amount is less than this, the resulting molded product will have antibacterial effects.
Although the antibacterial and antifungal effects are small and the antibacterial and antifungal effects can be improved by increasing the amount added, it is not necessary to add large amounts due to economic considerations.

Also, what is magnesium-aluminum basic carbonate?
kz,t /V2 (ON) 124 Co3
, or (yoF%1trA72(ON)+3Co33.
51-120. Furthermore, it refers to an inorganic substance represented by the linear formula (a). Moreover, the magnesium-zinc-aluminum basic carbonate refers to an inorganic substance represented by the following formula (b)'Z-.

(a) t%n-x^N%(Oll) 2
(CO3) im mouth 2.

However, O<X<1 ' O≦m≦5(b)3i
0-ZnO-#zO3Co2nHz.

However, O≦n≦9, the appropriate amount to add is 0.01 to 10 parts,
If it is less than 0.01, no improvement in photochromic property is observed, and 10
If the weight part is exceeded, the coloring of the processed samurai will become severe. Preferably it is 0.05 to 5.0 parts by weight.

The present invention uses the antibacterial silver 1ffi, 1 as the first component.
Light is combined with a vinyl chloride-based 84 fat and a magnesium-aluminum basic carbonate, a magnesium-zinc-aluminum basic carbonate, or a blend thereof as a second component.

In the present invention, such a vinyl chloride resin composition is formulated with a plasticizer suitable for the purpose of use.

Stabilizer, anti-fog agent, metal stabilizer 1 anti-coloring agent, antioxidant,
Antistatic agents, ultraviolet absorbers, lubricants, etc. are optionally added. In addition, other ingredients such as metal soap and h-bosphite compound can be used in combination within the usual range depending on the quality required.

As a plasticizer, di-n-octyl phthalate.

Di-2-ethylhexyl phthalate, dibutyl phthalate, diisononyl phthalo-1-, butylbenzyl phthalate, dilauryl phthalate, diheptyl phthalate,
Dimedyl butarate, diisodecyl phthalate, geo”
Phthalic acids such as ctyl phthalate and dicyclohexyl phthalate, dioctyl adipate, diisodecyl adipate, diisononyl adipate, carbon number is 6.8.1
Di(n-hexyl, n-ocdyl, n-decyl) adipate having 0 linear alkyl groups, carbon number is 7 or 9
Adipic acids such as di(i-heptyl, i-nonyl) adipate having a linear and/or side chain alkyl group, di-1-butyl azelate, di-n-hexyl azelate, di-octyl azelate 7-pyraic acids such as 7-pyraic acids, benzoic acids such as jepurene glycol dibenzoate, 7-malic acids such as dibutyl fumarate, dioctyl fumarate, diphenoxyethyl fumarate, butyl laurate, ethylene glycol monoethyl ether laure. lauric acid series such as i, pentaerythritol series such as pentaerythrithortetraacetate, silinol series such as medyl aldersilinolate, sepacic acid series such as dimethyl sebacate, citric acid series such as acetyltributyl citrate, glyceryl monomers. Glychline esters such as lauryl diacetate,
Other examples include polyester.

The plasticizer used in the present invention is used to impart flexibility to the molded product, and there is no limit to the amount added (6), but it is preferably 20 parts or more.

Examples of epoxy stabilizers include (2) epoxidized vegetable oils such as epoxidized human bean oil and epoxidized linseed oil, and epoxy resins. The addition 61 can be added as necessary depending on the film forming method.

In addition, examples of the stabilizer include 1M7 metal salts of galenic acid, such as zinc stearate, barium stearate, and calcium stearate. (Fatty acid carbonate number: 07 to C22) The amount added is 0.01 per 100 suspended parts of the resin.
~10 weight 61 parts, preferably HaO,O5=5 i[i
Q% part is appropriate.

Further, as organic phosphite compounds, trisnonylphenyl phosphite, triphenylbosphite, diphenyldecyl phosphite, tridecyl phosphite, tris(2-ethylhexyl>phosphite, i~listearyl phosphite, octyldiphenyl phosphite) The amount added is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In addition, as lubricants, isosudearic acid, stearic acid,
Aliphatic acid lubricants such as valmibonic acid 2, fatty acid amide lubricants such as stearic acid 7mide and medilene bisstearomide, ester lubricants such as butyl stearate, and polyethylene wax.

Examples include liquid paraffin and higher alcohols.

Examples of the antioxidant include phenolic antioxidants, aliphatic sulfides, silylphide antioxidants, thiodib a pionate, and the like.

Although it is not clear how the resin composition of the present invention improves photochromic properties, basic carbonates capture the de-11C1 that is released from the vinyl chloride resin, neutralize 11C1, and
This is thought to be because the 01'' ion is ion-exchanged and incorporated into the structure to inactivate it, which effectively works to prevent the formation of silver compounds such as the formation of Al;l Cj 2.

Next, examples of specific aspects of the present invention and comparative examples will be explained in detail.

(Examples 1-7. Comparative Examples 1-5) Antibacterial silver violite and magnesium-aluminum basic carbonate shown in Group 1 in the following formulations.

Magnesium-zinc-aluminum basic carbonate,
Alternatively, blends thereof are added in various proportions, kneaded with rolls with a surface temperature of 150°C, a sheet of 0.17 FL/m is prepared, and the discoloration under natural light and heat discoloration resistance (oven 200°C) are examined. . Also conduct an antibacterial test.

~Composition~ Vinyl chloride resin 100 DOP, 46 eboxidized linseed oil 4 Zinc stearate 0.1 Calcium stearate 0.1 Polyethylene wax
The 0.1 evaluation was as shown in Table-1.

(Examples 8 to 14. Comparative Examples 6 to 12) Examples 1 to 7. In the formulation of Comparative Examples 1 to 5, DINA was used instead of DOP as a plasticizer, and epoxidized Soyura was used instead of epoxidized Flax porcelain. The other conditions were the same.The evaluation was no different from Examples 1 to 7 and Comparative Examples 1 to 5 shown in Group 1.

<Effects of the Invention> The present invention provides a resin composition prepared by adding antibacterial silver zeolite to a vinyl chloride resin, or a vinyl chloride resin, a plasticizer,
A vinyl chloride resin composition prepared by adding an epoxy stabilizer and an antibacterial silver zeolite is chopped into 100 ffiffi parts of a resin, and then processed into a magnesium-aluminum salt carbonate, or a magnesium-zinc-aluminum basic carbonate, or Since these blends are added in an amount of 0.01 to 10 parts, it can be processed by any suitable processing method, such as a calender rolling method, an extrusion method, or an inflation method.

Hollow molding! ) Films and sheets formed after melting by one-shot molding, slush molding, dip molding, etc.

Tubes, etc. or molded products not only have excellent antibacterial and antifungal properties, but also have good photochromic properties and heat resistance, making them safe and sanitary for food packaging. It is possible.

Procedural amendment 1, Indication of the case 1999 Patent application No. 202619 2, Name of the invention 1998 Amended specification (1 Name of the invention Vinyl chloride resin composition 2, Claims (1) Vinyl chloride Magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or a blend thereof is added to 100 parts by weight of a resin composition obtained by adding antibacterial silver zeolite to a system resin. A vinyl chloride resin composition, characterized in that it contains 0.01 to IO parts by weight.

(2) Vinyl chloride resin, plasticizer, epoxy stabilizer,
Magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or a blend thereof is added to 100 parts by weight of the vinyl chloride resin composition containing antibacterial silver zeolite. A vinyl chloride resin composition for food packaging, which contains 0.01 to 1010 parts by weight.

3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an antibacterial and antifungal vinyl chloride resin composition with improved photochromic properties and a vinyl chloride resin composition for food packaging. .

<Conventional technology> As the surroundings surrounding our living environment become cleaner.

Products such as antibacterial wallpaper, antibacterial clothing, and antibacterial gloves are entering the market. PVC resins are said to be highly resistant to bacteria, mold, etc., but these resins are rarely used as resins alone, and depending on the purpose, they can be used as plasticizers, stabilizers, lubricants, etc. It is common to add various other additives, and it is a well-known fact that these reduce the antibacterial and antifungal properties.

In order to solve this problem, methods of applying antibacterial and antifungal agents to the plastic surface or kneading them into the plastic are used. Organic compounds are often used as antibacterial and antifungal agents, such as the organic arsenic compound vinazine, the organic chlorine compound PCP, and the aniline derivative thiapenzole. These are leaching from plastic, odor, and antibacterial.

It is said that there are problems in terms of safety and hygiene in terms of stability, such as the persistence of mold resistance, and in food packaging applications.

As an inorganic antibacterial agent developed in recent years, there is antibacterial silver zeolite, which replaces the metal ions in zeolite with silver ions, but because it is inorganic, it has excellent sustainability, dissolution, odor, and heat resistance. Therefore, it can be used in a stable state.

It is well known that by kneading such materials into plastics, antibacterial and antifungal properties can be imparted, and products in which such materials are kneaded into polyolefins, polystyrene, etc. can also be seen.

However, silver compounds such as antibacterial silver zeolite are added to vinyl chloride resin to create a film.

When a sheet or the like is formed, the film, sheet, or the like is significantly discolored by light, reducing the commercial value.

Means for Solving the Problems> The present inventors have overcome the problems of the prior art described above, and have developed a vinyl chloride resin composition with improved photochromic properties, excellent antibacterial and antifungal properties, and a hygienic-free vinyl chloride resin composition. As a result of extensive research in order to develop food packaging films with excellent antibacterial properties, we found that magnesium-aluminum-based Adding 0.01 to 10 parts by weight of a basic carbonate, a magnesium-zinc-aluminum basic carbonate, or a blend thereof, a vinyl chloride resin, a plasticizer, and an epoxy stabilizer.

Magnesium-aluminum-based basic carbonate, magnesium-zinc-aluminum-based basic acid salt, or a blend thereof is added to 100 parts by weight of the vinyl chloride resin composition prepared by adding antibacterial silver zeolite. 0.01 to 10.0 parts by weight of the compound was added.

Effects> The present invention is characterized by adding magnesium-aluminum basic carbonate, magnesium-zinc aluminum basic carbonate, or a blend thereof to a blended system in which antibacterial silver zeolite is added to vinyl chloride resin. More specifically, after these resin compositions are melted by a calender rolling method, an extrusion method, an inflation method, or the like, the photochromic properties of the formed film, sheet, etc. are improved.

<Example> The vinyl chloride resin in the present invention includes polyvinyl chloride or polyvinyl chloride and other monomers such as ethylene, propylene, alkyl vinyl ether, acrylic acid ester, and vinyl acetate.

methacrylic acid ester, acrylic, acrylonitrile,
Examples include copolymers with urethane, vinylidene, etc., and blends thereof.

Furthermore, the antibacterial silver zeolite used in the present invention refers to the zeolite (xMi) using natural or synthetic zeolite as a carrier.
O@A1203 7sio.

! Some or substantially all of the ion-exchangeable metals (M) in H20) have bactericidal properties, such as silver, copper, and zinc.

It is a substance substituted with one or more metal ions selected from the group consisting of mercury, tin, lead, bismuth, cadmium, and chromium, and contains silver ions. There is no limit to the amount added, but from the viewpoint of antibacterial effects, it is preferably 0.01 parts by weight or more. If the amount is less than this, the antibacterial and antifungal effects of the resulting molded product will be low, and the antibacterial and antifungal effects will be improved by increasing the amount added, but it is not necessary to add a large amount from economical considerations.

Also, magnesium-aluminum basic carbonate is M
g4.2 AA' 2 (OH) 1□, 4CO,
, or seasonal 4.5 A12 (OH) + 1COs
3.5Hz O.

Furthermore, it refers to an inorganic substance represented by the following formula (a).

Moreover, the magnesium-zinc-aluminum basic carbonate refers to an inorganic substance represented by the following formula (b).

(a) Mg+-* A1. (OH)2 (c
o3) 4H20 However, 0<X<1 0≦m≦5(b) 3M
g0-210- AI 201 CO2+182
0 However, 0≦n≦9 The appropriate amount to add is 0.01 to 10 parts by weight,
If the amount is less than 0.401 parts by weight, no improvement in photochromic properties will be observed, and if it exceeds 10 parts by weight, coloration during processing will become severe. Preferably it is 0.05 to 5.0 parts by weight.

The present invention uses the above-mentioned antibacterial silver zeolite as the first component, magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or a blend thereof as the second component, and vinyl chloride. It is used in combination with the system resin.

In the present invention, such a vinyl chloride resin composition is formulated with an amount of plasticizer depending on the intended use.

Stabilizer, anti-fog agent, metal stabilizer 1 anti-coloring agent, antioxidant,
Antistatic agents, ultraviolet absorbers, lubricants, etc. are optionally added. Further, other components such as metal soaps and organic phosphite compounds can be used in combination within the usual range depending on the quality required.

As a plasticizer, di-n-octyl phthalate.

Phthalic acids such as di-2-ethylhexyl phthalate, dibutyl phthalate, diisononyl phthalate, butylbenzyl phthalate, dilauryl phthalate, diheptyl phthalate, dimethyl phthalate, diisodecyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dioctyl adipate, diisodecyl adipate , diisononyl adipate, carbon number is 6. 8. Di(n-hexyl, n-octyl, n-decyl) adipate having 10 linear alkyl groups, di(i- Adipic acids such as heptyl, i-nonyl) adipate, di-i-butyl azelaate, di-n-hexyl azelaate,
Azelaic acids such as di-octyl azelate, benzoic acids such as diethylene glycol dibenzoate, fumaric acids such as dibutyl fumarate, dioctyl fumarate, diphenoxyethyl fumarate, butyl laurate, ethylene glycol monoethyl ether laurate, etc. lauric acid-based compounds such as esters, pentaerythritol-based compounds such as pentaerythritol tetraacetate, silinol-based compounds such as methyl alkylsilinolate, sebacic acid-based compounds such as dimethyl sebacate, citric acid-based compounds such as acetyltributyl citrate, and glyceryl monomers. Examples include glycerin esters such as lauryl diacetate, and other polyesters.

The plasticizer used in the present invention is used to impart flexibility to the molded article, and there is no limit to the amount added, but it is preferably 20 parts by weight or more.

Epoxy stabilizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxy resins. The required amount can be added depending on the film forming method.

Further, examples of the stabilizer include fatty acid metal salts such as zinc stearate, barium stearate, and calcium stearate. (Carbonic acid number C7 to C22 of fatty acid) The amount added is 0.01 per 100 parts by weight of resin.
~10 parts by weight, preferably 0.05 to 5 parts by weight are suitable.

Further, as organic phosphite compounds, trisnonylphenyl phosphite, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tristearyl phosphite, octyldiphenyl phosphite, etc. can be given. The amount added is 0.1 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In addition, as lubricants, isostearic acid, stearic acid,
Aliphatic acid lubricants such as palmitic acid 1, fatty acid amide lubricants such as stearamide and methylene bisstearomite, ester lubricants such as butyl stearate, and polyethylene wax.

Examples include liquid paraffin and higher alcohols.

Examples of the antioxidant include phenolic antioxidants, aliphatic sulfides, disulfides, thiodipropionic acid esters, and the like.

The reason why the resin composition of the present invention improves photochromic properties is not clear, but basic carbonates supplement deHC1, which is released from vinyl chloride resin, neutralize HC1, and improve CI
This is thought to be because the -ions are incorporated into the structure through ion exchange and inactivated, which works effectively to prevent the formation of silver compounds such as the formation of Heg C12.

Next, Examples and Comparative Examples of specific embodiments of the present invention will be described in more detail.

(Examples 1 to 7. Comparative Examples 1 to 5) Antibacterial silver zeolite and magnesium-aluminum basic carbonate shown in Table 1 were added to the following formulations.

Magnesium-zinc-aluminum basic carbonate,
Or, add a blend of these in various proportions, knead with a roll with a surface temperature of 150°C, create a sheet of 0.1 m/m, and check for discoloration under natural light and heat discoloration resistance (open 20Q°C). . Also conduct an antibacterial test.

~ Distribution ~ vinyl chloride resin DOP Epoxidized linseed oil zinc stearate Calcium stearate polyethylene wax The evaluation was as shown in Table-1.

(Examples 8-14. Comparative Examples 6-12) Examples 1-7. In the formulations of Comparative Examples 1 to 5, DINA was used instead of DOP as a plasticizer, and epoxidized soybean oil was used instead of epoxidized linseed oil, and the other conditions were the same. The evaluation was completely unchanged from Examples 1 to 7 and Comparative Examples 1 to 5 shown in Table 1.

100 parts by weight 46 parts by weight 4 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight <Effects of the Invention> The present invention provides a resin composition formed by adding antibacterial silver zeolite to a vinyl chloride resin. Or vinyl chloride resin, plasticizer,
Magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or Since 0.0 to 10 parts by weight of these blends are added, it can be processed by any processing method such as calendar rolling, extrusion, inflation, blow molding, injection molding, slush molding, dip molding, etc. After melting, the formed film, sheet, tube, etc. or molded product has excellent antibacterial and antifungal properties, as well as good photochromic properties and heat resistance, making it suitable for food packaging. It is also possible to provide safe and sanitary products.

Claims (2)

[Claims] (1) Magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or A vinyl chloride resin composition comprising 0.01 to 10 parts by weight of a blend of these. (2) Vinyl chloride resin, plasticizer, epoxy stabilizer,
Magnesium-aluminum basic carbonate, magnesium-zinc-aluminum basic carbonate, or a blend thereof is added to 100 parts by weight of the vinyl chloride resin composition containing antibacterial silver zeolite. A vinyl chloride resin composition for food packaging, which contains 0.01 to 10.0 parts by weight.