JPH10265634A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin compsn. which is excellent not only in antibacterial properties and thermal stability by also in processibility such as during roll processing and in printability after being processed. SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. vinyl chloride resin with 0.01-10 pts.wt. inorg silver-based antibacterial agent (A), 0.01-5 pts.wt. at least one metal carboxylate (B) selected from among calcium, barium, magnesium, and zinc carboxylates, and 0.01-3 pts.wt. 8-22C satd. or unsatd. fatty acid (C) and/or 0.01-5 pts.wt. at least one phosphite compd. (D) selected from among a trialkyl phosphite, a dialkylpentaerythritol diphosphite, a di(alkylphenyl) pentaerythritol diphosphite, and a tetraalkyl-4,4'-isopropylidenediphenyl diphosphite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition having excellent antibacterial properties and heat stability.

[0002]

2. Description of the Related Art Vinyl chloride resins are widely used because of their excellent mechanical properties, ease of molding and economic advantages. In particular, the flexibility can be freely adjusted by compounding a plasticizer. Floor materials, wallpaper, table cloth, agricultural vinyl, accordion curtain, waterproof sheet
It is widely used for products, hoses, tubes and food packaging. However, since these vinyl chloride resins are often used in a humid environment, it has been pointed out that various fungi and molds are generated on the surface or inside of the resin, which is harmful to hygiene and impairs the appearance. ing.

[0003] Various antibacterial agents have been developed to solve this problem. Specifically, JP-A-62-241932, JP-A-63-270756, JP-A-1-31
No. 1008 reports that zeolites, particularly silver-based zeolites, exhibit excellent antibacterial properties. In addition to zeolite, Japanese Patent Application Laid-Open No. 5-156103 discloses a polymer containing at least a vinylbenzylphosphonium salt as a monomer component.
A metal soap of a polycyclic compound carboxylic acid having at least one carboxyl group is a metal soap of a carboxylic acid, an organopolysiloxane compound having a biguanidyl group is disclosed in JP-A-6-192428, and a softening point of 30 to 120 is disclosed in JP-A-8-53538. ℃,
A salicylic acid ester resin having a molecular weight of 500 to 10,000 is reported in JP-A-8-113729 as silica particles having zinc sulfate adsorbed and held as an antibacterial agent having excellent antibacterial action. Further, JP-A-8-83320 reports that a strong acid-resistant and strong alkali-resistant antibacterial agent can be obtained by using amorphous titanium oxide fine particles containing silver.

[0004] Among these antibacterial agents, silver zeolite has the best antibacterial property against vinyl chloride resin. However, when an antibacterial agent including this silver zeolite is added to a vinyl chloride resin, there is a problem that thermal stability is greatly reduced. To solve this problem, Japanese Patent Application Laid-Open
Japanese Patent No. 17617 discloses that a silver compound having a thermal deterioration temperature of 300 ° C. or more, such as silver oxide or silver phosphate, is used to improve thermal stability, and Japanese Patent Application Laid-Open No. 8-59935 discloses a bamboo extract. To obtain a vinyl chloride resin composition having both heat stability and antimicrobial properties by adding the compound to a vinyl chloride resin. However, these measures have insufficient antibacterial properties.

[0005] Incidentally, since the molding temperature of the vinyl chloride resin is close to the decomposition temperature, it inherently has a problem that it is decomposed during molding and the thermal stability is reduced. Therefore, a stabilizer is usually added. This type of stabilizer improves thermal stability by capturing hydrogen chloride gas generated from a vinyl chloride resin or by directly reacting with the vinyl chloride resin.

Heretofore, in systems containing no plasticizer, lead-based stabilizers such as lead stearate and tribasic lead sulfate have been used because of their excellent thermal stability and processability. Thus, tin-based stabilizers such as dibutyltin maleate and dibutyltin laurate have been used. In systems containing plasticizers, metal soap-based stabilizers, mainly cadmium soap, barium soap, calcium soap, magnesium soap, and zinc soap, have been used ["Elucidation and stabilization of polyvinyl chloride stabilization". Actual Mixing and Effect of Auxiliary Agents ”(issued by Soft Giken Publishing Department on March 15, 1984). However, in any system, when a silver zeolite is added in order to obtain a molded article of a vinyl chloride resin having antibacterial properties, the thermal stability is greatly reduced.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional circumstances, and has excellent antibacterial properties and heat stability.
In addition, it is an object of the present invention to provide a vinyl chloride resin composition which is excellent in workability at the time of roll processing and the printability after processing.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, blended an inorganic silver-based antibacterial agent and a metal carboxylate with a vinyl chloride-based resin, When a specific fatty acid and / or a specific phosphite compound are further added to the mixture, good processability is obtained in which both antibacterial properties and thermal stability are excellent and roll-out does not cause problems such as plate-out. It was also found that a vinyl chloride resin composition having excellent printability after processing was obtained, and the present invention was completed.

That is, the present invention relates to a vinyl chloride resin 1
A) 0.01 to 1 part by weight of inorganic silver-based antibacterial agent
0 parts by weight, b) 0.01 to 5 parts by weight of at least one metal salt of carboxylic acid selected from calcium, barium, magnesium and zinc salts of carboxylic acid;
c) 0.01 saturated or unsaturated fatty acid having 8 to 22 carbon atoms
The present invention relates to a vinyl chloride resin composition (Claim 1) characterized in that the composition contains up to 3 parts by weight.

Further, the present invention relates to a vinyl chloride resin
A) 0.01 to 10 parts by weight of an inorganic silver-based antibacterial agent, and b) at least one metal carboxylate selected from calcium salts, barium salts, magnesium salts and zinc salts, based on parts by weight. 0.01 to 5 parts by weight of salt, d) trialkyl phosphite, dialkyl pentaerythritol
Rudiphosphite, di (alkylphenyl) pentaerythritol-diphosphite, tetra (alkyl) -4,
At least one phosphite compound selected from 4'-isopropylidene diphenyl diphosphate;
The present invention relates to a vinyl chloride resin composition (Claim 2), which contains from 0.01 to 5 parts by weight.

Further, the present invention relates to a vinyl chloride resin
A) 0.01 to 10 parts by weight of inorganic silver-based antibacterial agent
Parts by weight, b) calcium salt, barium salt of carboxylic acid,
0.01 to 5 parts by weight of at least one metal carboxylate selected from a magnesium salt and a zinc salt; c) 0.01 to 3 parts by weight of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms; d) At least one selected from trialkylphosphites, dialkylpentaerythritol diphosphites, di (alkylphenyl) pentaerythritol diphosphites, and tetra (alkyl) -4,4'-isopropylidenediphenyldiphosphates (Claim 3), characterized in that the composition contains 0.01 to 5 parts by weight of a phosphite compound of the formula (1).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin used in the present invention is not only a homopolymer of vinyl chloride but also a copolymer of vinyl chloride with other monomers such as vinyl acetate and vinyl alcohol. Especially when the degree of polymerization is 500 to 4.0
00 is preferred.

The inorganic silver antibacterial agent of the component a in the present invention includes silver zeolite, silver ceramics, silver calcium phosphate, silver silica gel, silver titania, silver / glass / silver silicate, silver titanium phosphate / zinc oxide and the like. be able to. Among these, silver zeolite and silver silica gel are particularly preferred. The amount of these inorganic silver-based antibacterial agents used is 0.0 to 100 parts by weight of the vinyl chloride-based resin.
It is 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
When the amount is less than 0.01 part by weight, it is difficult to obtain the antibacterial effect, and when it exceeds 10 parts by weight, the thermal stability is reduced.

In the carboxylate metal salt of the component b in the present invention, a saturated or unsaturated carboxylic acid having 4 to 24 carbon atoms or a carbocyclic carboxylic acid having 7 to 16 carbon atoms is used as the carboxylic acid. These carboxylic acids include hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid, oleic acid, linoleic acid , Linolenic acid, palmito oleic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid, adipic acid, pimelic acid,
Glutaric acid, azelaic acid, sebacic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthenic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, anisic acid, salicylic acid And the like.

As the carboxylate metal salt of the component (b), use may be made of one or a mixture of two or more of the above carboxylic acids, or a mixture of two or more of the one carboxylic acid metal salts. To use. Metal salts include calcium, barium, magnesium or zinc salts. The amount of the metal carboxylate of the component b is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.01 part by weight, it is difficult to obtain the effect of thermal stability (initial coloring, long-term thermal stability). On the other hand, if the amount exceeds 5 parts by weight, problems such as occurrence of plate-out during roll processing and deterioration of workability such as molding failure due to excessive lubricity are liable to occur, and deterioration of printability after processing. Is also likely to occur.

The fatty acid of the component c in the present invention is a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, specifically, 2-ethylhexylic acid, n-octylic acid, decanoic acid, isodecanoic acid, lauric acid. , Myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, palmitooleic acid, isostearic acid, etc., and one or more of these are used. . Fatty acids having less than 8 carbon atoms have a problem of initial coloring, and fatty acids having more than 22 carbon atoms have a problem of reduced printability. The amount of the fatty acid used as the component c is 0.01 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.01 part by weight, the problem of initial coloring tends to occur. On the other hand, if the amount exceeds 3 parts by weight, problems such as occurrence of plate-out during roll processing and deterioration of printability after processing are likely to occur.

The phosphite compound of the component d in the present invention includes trialkyl phosphite, dialkylpentaerythritol diphosphite, di (alkylphenyl) pentaerythritol diphosphite, tetra (alkyl) -4,4'-isopropylidene At least one selected from diphenyl diphosphite is used. If other phosphite compounds such as diphenylmonodecyl phosphite and tris (nonylphenyl) phosphite are blended, the problem of initial coloring is likely to occur and cannot be used in the present invention.

The above trialkyl phosphite has an alkyl group having 8 to 22 carbon atoms, for example, tributyl phosphite, triisooctyl phosphite,
There are tridecyl phosphite, tris (tridecyl) phosphite, tris (octadecyl) phosphite and the like. The dialkylpentaerythritol diphosphite has an alkyl group having 4 to 22 carbon atoms, for example, diisodecylpentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, dioctadecylpentaerythrite. And rudiphosphite.

The di (alkylphenyl) pentaerythritol diphosphite has 4 to 22 carbon atoms.
For example, bis (nonylphenyl) pentaerythritol diphosphite. Further, the tetra (alkyl) -4,4'-isopropylidenediphenyldiphosphate has an alkyl group having 4 to 22 carbon atoms, for example, tetra (tridecyl) -4,4'-isopropylidene. And diphenyldiphosphite.

Among these phosphite compounds, particularly preferred are dialkylpentaerythritol diphosphite and di (alkylphenyl) pentaerythritol diphosphite having an alkyl group having 4 to 20 carbon atoms, and most preferred are dialkylpentaalkyl phosphite compounds. Erythrit
It is rudiphosphite. The amount of the component d is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.01 part by weight, it is difficult to obtain the effect of thermal stability (initial coloring, long-term thermal stability). On the other hand, if the amount exceeds 5 parts by weight, problems such as occurrence of plate-out during roll processing and deterioration of workability such as molding failure due to excessive lubricity are liable to occur, and deterioration of printability after processing. Is also likely to occur.

The vinyl chloride resin composition of the present invention contains stearyl alcohol as long as the characteristics of the present invention are not impaired.
Lubricants such as high-grade alcohols such as alcohol, paraffin wax, polyethylene wax, polypropylene wax, montanic acid wax, etc., lubricants such as amides such as stearic acid amide and methylenebisstearic acid amide, calcium silicate, carbonic acid Fillers such as calcium, talc, hydrotalcite, and titanium oxide, polyols such as pentaerythritol and dipentaerythritol, β-diketones, epoxidized soybean oil, epoxidized linseed oil, glycidyl ( Epoxy compounds such as (meth) acrylate-containing polymers, plasticizers such as dioctyl phthalate and dioctyl adipate, and pigments, flame retardants, antistatic agents, ultraviolet absorbers, and the like can be added.

[0022]

The present invention will now be described more specifically with reference to examples.

Examples 1 to 12 As a vinyl chloride resin, a vinyl chloride resin (degree of polymerization: 1,050) manufactured by ZEON CORPORATION was used. The mixture was kneaded at 190 ° C. for 3 minutes to form a sheet having a thickness of 0.5 mm.

Comparative Examples 1 to 18 Sheets having a thickness of 0.5 mm were prepared in the same manner as in Examples 1 to 12, except that the composition was changed as shown in Tables 5 to 10.

In Tables 1 to 10 below, the silver zeolite as the component a is "Zeomics" of Shinagawa Fuel Co., Ltd., and the silver silica gel is "pentanone" of Paint House Co., Ltd. In Tables 9 and 10,
The bamboo extract, which is another component, is a brown extract obtained by pulverizing Moso bamboo stems with a ball mill, extracting with ether, and evaporating the extract to dryness under reduced pressure.

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

The above Examples 1 to 12 and Comparative Examples 1 to 1
Each sheet prepared in 8 was cut to obtain a test piece of 5 cm × 5 cm, and using this test piece, the thermal stability, antibacterial property and printability were evaluated by the following methods. Further, the plate-out and lubricity when each sheet was manufactured by rolling were evaluated by the following methods. The results were as shown in Tables 11 and 12 below.

<Thermal Stability> The test piece was placed in an oven at 190 ° C., and the color tone after 15 minutes and the time until it became black, dark red or dark red-brown were examined. The color tone after 15 minutes was evaluated as initial coloring, and the time until black, dark red or dark reddish brown was evaluated as long-term thermal stability.

<Antibacterial Property> The test strain was Escherichia coli (Esch
erichia coli IFO3301) and Staphylococcus au
reus IFO14462). Bacterial liquid was prepared by transforming these strains on SCD agar [Nippon Pharmaceutical Co., Ltd.] slant medium.
The culture obtained by culturing at 7 ° C. for 24 hours is sterilized with PBS.
It was adjusted by suspending in [Nippon Pharmaceutical Co., Ltd.].
The bacterial concentration was adjusted to a level of 5 × 10 ⁷ cells / ml of the bacterial solution by measurement using a calculator.

A 75% by volume aqueous ethanol solution was sprayed on the surface of the test piece, and then dried and subjected to the test. The antibacterial activity was measured by a contact method. That is, a test piece was placed on a sterile dish, and 200 μl of the above bacterial solution was placed on the surface of the test piece.
Further, a sterilized polybag for S. matsuka cut into 7 cm squares (Eiken Kiki Co., Ltd.) was placed on the test piece, and the solution was spread over the entire surface of the test piece. The surface of the wrap was rinsed with a total of 10 ml of SCD liquid [Nippon Pharmaceutical Co., Ltd.] medium, 1 ml of the washing liquid was placed in a shear, about 20 ml of SCD agar medium was poured, stirred, coagulated, and coagulated. After culturing for 24 hours, the number of colonies formed was counted. As evaluation criteria, “「 ”: no colonies were observed on the medium,“ △ ”: number of colonies on the medium was 1 to 10
Less than 0, "x": The number of colonies on the medium was 100 or more.

<Printability> A test piece was placed in a constant temperature bath at 80 ° C. and 90% RH for one week, and then a PVC ink (“VCH 3 red” manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied with a bar coater. After being applied and dried, a cellophane tape was stuck thereon, and the state of peeling of the ink when vigorously peeled off was visually observed. As evaluation criteria, “◎”: almost no ink peeling, “、”: less than 20% of ink peeling,
“△”: Peeling of ink is 20% or more but less than 50%, “×”:
It was determined that the peeling of the ink was 50% or more.

<Plate-out> Roll during roll kneading
The presence or absence of deposits on the shell was examined.

<Lubricity> The lubrication during roll kneading was examined.
The evaluation criterion is “excess”: the sheet is too slippery to form a sheet, or becomes a mesh sheet.
“Normal”: Moderate peelability from the roll and a glossy sheet were obtained. “Insufficient”: Insufficient lubricity and poor peelability from the roll.

[0043]

[0044]

As is clear from the results in Table 11 above,
Each of the sheets of Examples 1 to 12 of the present invention has no initial coloring and has a long-term thermal stability of at least 55 minutes using a fatty acid of the component c, and a phosphite compound of the component d is used for 55 minutes or more. It has excellent heat stability and excellent antibacterial properties for more than 80 minutes, and has no slip-out during hot roll kneading, showing moderate lubricity. It can be seen that it has good workability and also has good printability after processing.

On the other hand, as is apparent from Table 12, Comparative Example 1 using only the component a had poor thermal stability (initial coloring and long-term thermal stability) and lacked lubricity. Yes,
Comparative Example 2 using only the component b has a problem in initial coloring and is inferior in antibacterial properties. Comparative Example 3 using only component c and Comparative Example 4 using only component d both have poor thermal stability (initial coloring, long-term thermal stability) and poor antibacterial properties. The nature is also lacking.
Comparative Example 5 using only the two components a and b has a problem of initial coloring and lacks lubricity. Further, a,
Comparative Example 6 using the c-component and Comparative Example 7 using the a and d-components both have poor thermal stability (initial coloring and long-term thermal stability) and lack lubricity. Comparative Example 8 using two components b and c has a problem in initial coloring and is inferior in antibacterial properties.

Comparative Example 9 in which the amount of the component a exceeds 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin is as follows:
Thermal stability (initial coloring, long-term thermal stability) is poor, and printability is also reduced. Comparative Example 1 in which the amount of the component b exceeds 5 parts by weight based on 100 parts by weight of the vinyl chloride resin
Comparative Example 11, in which the amount of the 0 and c components exceeds 3 parts by weight, d
In Comparative Example 12 in which the amount of the component exceeds 5 parts by weight, processing was difficult due to excessive lubricity, plate-out occurred, and printability after processing was poor.

Further, Comparative Example 13 using butyric acid instead of the component c has a problem in initial coloring, and Comparative Example 14 using montanic acid is inferior in printability after processing. further,
Comparative Example 15 using diphenylmonodecyl phosphite and Comparative Example 16 using tris (nonylphenyl) phosphite as the phosphite compounds other than the component d both have problems in initial coloring. Further, instead of the component a,
Comparative Example 17 using a bamboo extract had reduced antibacterial properties,
In Comparative Example 18 using zinc zeolite and no c and d components, the antibacterial properties and the long-term heat stability were reduced.

[0049]

As described above, according to the present invention, a specific fatty acid and / or a specific phosphite compound is blended with a vinyl chloride resin together with an inorganic silver-based antibacterial agent and a metal carboxylate. As a result, excellent antibacterial properties and thermal stability are obtained, and in addition, good workability with moderate lubricity and no hindrance such as plate-out during roll processing is obtained. It is possible to provide a vinyl chloride resin composition which is excellent in later printability.

Claims (3)

[Claims] 1. A method comprising: a) 0.01 to 10 parts by weight of an inorganic silver-based antibacterial agent, and b) calcium, barium, magnesium and zinc salts of a carboxylic acid, based on 100 parts by weight of a vinyl chloride resin. A vinyl chloride-based material containing 0.01 to 5 parts by weight of at least one selected metal carboxylate; and c) 0.01 to 3 parts by weight of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms. Resin composition. 2. Among 100 parts by weight of a vinyl chloride resin, a) 0.01 to 10 parts by weight of an inorganic silver-based antibacterial agent, and b) calcium, barium, magnesium and zinc salts of carboxylic acid. 0.01 to 5 parts by weight of at least one selected metal carboxylate, d) trialkyl phosphite, dialkyl pentaerythritol diphosphite, di (alkylphenyl) pentaerythritol diphosphite, tetra (alkyl)- A vinyl chloride resin composition comprising 0.01 to 5 parts by weight of at least one phosphite compound selected from 4,4'-isopropylidene diphenyl diphosphite. 3. A method comprising: a) 0.01 to 10 parts by weight of an inorganic silver-based antibacterial agent; and b) calcium, barium, magnesium and zinc salts of a carboxylic acid, based on 100 parts by weight of a vinyl chloride resin. 0.01 to 5 parts by weight of at least one selected metal carboxylate, c) 0.01 to 3 parts by weight of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, d) trialkyl phosphite, dialkyl pentaerythris Reto
Rudiphosphite, di (alkylphenyl) pentaerythritol-diphosphite, tetra (alkyl) -4,
At least one phosphite compound selected from 4'-isopropylidene diphenyl diphosphate;
A vinyl chloride resin composition comprising from 0.01 to 5 parts by weight.