JPS5823843A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved transparency and resistance to color change by heating free from smell of its own, obtained by adding a 2- alkyl-3-hydroxy-4-pyrrone to a vinyl chloride resin composition. CONSTITUTION:A 2-alkyl-3-hydroxy-4-pyrrone shown by the formula (R is 1-5C alkyl) is added to a vinyl chloride resin composition. In order to eliminate smell and to improve transparency, 100pts.wt. resin is blended with 0.0001-3pts.wt. of the compound, and to increase heat stability, it is blended with 0.0005- 0.5pts.wt., preferably 0.0001-1pts.wt. of the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition that eliminates the odor peculiar to vinyl chloride resin compositions and has improved transparency and thermal stability.

Vinyl chloride resin compositions have a unique odor due to the plasticizers and various stabilizers blended therein, giving the illusion that the odor is unique to vinyl chloride resins.

Increasing the amount of stabilizer is most effective for improving the thermal stability of vinyl chloride resin compositions, but this also increases odor. On the other hand, in vinyl chloride resin compositions, transparency is generally better when there is less stabilizer, and heat resistance and transparency are contradictory, and it is difficult to obtain the effect of having both properties.

Conventionally, resin compositions, for example, compositions used in toy article molding, have been used for the purpose of forcibly imparting a fruit aroma to the resin composition, rather than for the purpose of counteracting the odor of the i-nyl chloride-based resin composition. Attempts have been made to add various flavoring agents to give various fruit aromas. However, even if a molded article is manufactured by adding a fragrance to a resin composition, the fragrance escapes or disappears due to heating during the molding process.
Even if the odor remained, it would disappear within a short period of time, and in the worst case scenario, it would even begin to emit a foul odor.

The present inventors have attempted to add various chemicals for the purpose of counteracting the odor peculiar to vinyl chloride resin compositions. Adding just a small amount eliminates the characteristic odor of vinyl chloride resin compositions, and even when heated and molded, the odor is the same as before heating, and even if left for a long time, the characteristic odor of vinyl chloride resin compositions disappears. It turned out that the smell never returned. Furthermore, the transparency of the molded product is better than when λ-alkyl-3-hydroxy-pyrone is not added, and the thermal stability is better when it is added within a certain range than when it is not added. In other words, in order to obtain the same level of transparency in all ranges, it was possible to add a large amount of stabilizer, and by extension, it was found that the coloring property due to heat could be improved, and the present invention was achieved. .

That is, an object of the present invention is to provide a vinyl chloride resin composition that does not have the dullness characteristic of conventional vinyl chloride resin compositions, has improved transparency, and has improved coloring property by heating.

Therefore, the gist of the present invention is to provide an alkyl group of the general formula [wherein the hill represents an alkyl group having a carbon atom number/~j]. ] A vinyl chloride resin composition containing λ-alkyl-3-hydroxyliviron represented by the following.

The present invention will be described in detail.

The vinyl chloride resin composition of the present invention usually contains a vinyl chloride resin, a plasticizer or a stabilizer, and 2-alkyl-3-hydroxy-gupilone as constituent components. Of course, a plasticizer and a stabilizer may be present together.

Vinyl chloride-based resins include, but are not particularly limited to, homopolymers such as vinyl chloride or vinylidene chloride, or monomers copolymerizable with these monomers, such as ethylene, propylene, vinyl acetate, and acrylic acid. , methyl acrylate, methacrylic acid, methyl methacrylate, copolymers with styrene, etc. Among these, vinyl chloride resin or chloride obtained by polymerizing or copolymerizing vinyl chloride alone or with vinyl acetate Preferably, it is a vinyl/vinyl acetate copolymer. The vinyl chloride resin may be a post-chlorinated polyvinyl chloride resin.

The plasticizer used in the composition of the present invention is not particularly limited, and may be any of a variety of plasticizers that can be used as plasticizers for vinyl chloride resins. For example, heptalic acid esters such as diptyl phthalate (DBP), diheptyl phthalate, dioctyl phthalate (DOP), diindecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate. Plasticizers, phosphate ester plasticizers such as tricresyl phosphate and trioctyl phosphate, tri-n- citrate
Examples include fatty acid ester plasticizers such as butyl, dioctyl adipate, dioctyl azelaate, dioctyl sebacate, and methyl acetyl ricinoleate, and epoxy plasticizers such as alkyl epoxy stearate and epoxidized soybean oil. One type of plasticizer or a mixture of two or more types can be used. Therefore, the amount of plasticizer contained in the vinyl chloride resin composition is
The range is from 30 to 200 parts by weight, preferably from 30 to 200 parts by weight.

Furthermore, the type of stabilizer contained in the composition of the present invention is not particularly limited, and includes heat stabilizers, light resistance imparting agents, ultraviolet stabilizers, antioxidants, etc. The main one is a heat stabilizer for vinyl chloride resin. Specifically, lead white, basic lead silicate, tribasic lead sulfate, tribasic lead phosphite, dibasic lead phthalate, tribasic lead maleate, silica gel co-precipitated lead silicate, normal salicylic acid. Inorganic lead salt stabilizers such as lead, cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexoate, barium stearate, barium laurate, barium ricinoleate, barium naphthenate, λ - Barium ethylhexinate, calcium stearate, calcium laurate, calcium ricinoleate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexinate, lead stearate, dibasic lead stearate, naphthenic acid Metal soaps such as lead, tin stearate, magnesium stearate, cadmium-barium type,
Cadmium-barium-zinc system.

Examples include composite stabilizers such as barium-zinc type, organotin stabilizers such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin dodecyl mercaptide (dibutyltin mercaptides), other epoxy stabilizers, and organic phosphorous acid compounds. It is desirable that at least one kind is contained. Therefore, the content of the stabilizer is θ, 0/−j parts by weight, preferably in the range of 0.1 to 3 parts by weight, based on ioo parts by weight of the vinyl chloride resin.

Specifically, the compound represented by the general formula [I], which is an essential component of the composition of the present invention, is -methyl-3-hydroxy-Hiro-pyrone, λ-ethyl-3-hydroxy-≠-pyrone, 2- Propyl-3-hydroxy≠-pyrone, -
-isoprobyl-3-hydroxy-ti--pyrone,!
-Butyl-3-hydroxy-t-pyrone, nopentyl-3-hydroxy-μm-pyrone, etc. are hb, and considering that they are easily available, it is desirable to use the 2-methyl form or the λ-ethyl form. -The longer the chain length of the alkyl group at the 1-position, the greater the deodorizing effect tends to be. However, 2-
The amount of the alkyl-3-hydroxy-t-pyrone compound added is 0.0001 to 3 parts by weight per 100 parts by weight of the vinyl chloride resin when the purpose is odor elimination and transparency.
0.00 for odor, transparency, and thermal stability purposes
0/-0.6 parts by weight, especially o, o o o s to 09.
It is preferable to add in a range of 2 parts by weight. Addition amount is 0.0
If the amount is less than 0.007 parts by weight, the deodorizing effect will be negligible, and if it is more than 7 parts by weight, the thermal stability will tend to deteriorate.
It would be best to contain it in the range of / to / parts by weight.

In addition to the above-mentioned components, the composition of the present invention includes a lubricant, a flame retardant, a coloring agent, a blowing agent, an inorganic or organic filler,
Resins other than vinyl chloride resins, such as polyurethane and Bakelite powder, may be added in desired amounts as long as they do not impair the physical properties of the intended use of the composition.

To produce the compositions of the invention, the above-mentioned components can be mixed at once or sequentially in a dice mixer, a V-mixer, a Henschel mixer, a Spar mixer, a Banbury mixer.
It is produced by uniformly stirring and mixing with a mixer such as a kneader or the like. The composition may be mixed uniformly and then kneaded with a calendar roll to form a sheet, or processed into a sheet with an extruder, if desired.
It may also be used after being melted into a gel and made into pellets. The composition is formed into a molded product in powder or pellet form using an extruder, injection molding machine, press molding machine, rotary molding product, inflation molding machine, etc., and is particularly suitable for use in hoses, flooring materials, wall materials, etc. Suitable for use in molding household products that are undesirable due to their odor.

The composition of the present invention comprises λ-alkyl-3-hydroxy-t
- The odor peculiar to vinyl chloride resin compositions can be canceled by just containing a small amount of pyrone, and the molded articles obtained from the compositions are 2-alkyl-3-hydroxy-
The transparency is superior to molded articles obtained from compositions that do not contain t-pyrone. Therefore, to achieve the same degree of transparency for both, 2-alkyl-3-hydroxy-≠
- A large amount of heat stabilizer can be added to a composition containing pyrone, making it possible to produce a composition with excellent heat stability.

The effect of eliminating odor is that when λ-alkyl-3-hydroxy-goupirone is added to each of the plasticizer and stabilizer,
In each case, it is not possible to deodorize, and deodorization occurs only when it is included in a vinyl chloride resin composition.

This is probably due to a synergistic effect.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Example 1 Vinyl chloride resin (average degree of polymerization F s, 3oo ) 10° parts by weight, DOP 6j parts by weight, DBP/j parts by weight, epoxidized soybean oil 2 parts by weight, cadmium stearate 0.1 parts by weight, barium stearate O, aZ amount part, lead stearate 0. / parts by weight and λ-methyl-3-hydroxyderpyrone were mixed in a beaker to obtain a vinyl chloride resin composition. The composition is heated and kneaded using two rolls at a temperature of 760°C to form a rough sheet. The following test was conducted using the rough sheet to evaluate the composition.
It is listed in the table.

[Presence or absence of odor of vinyl chloride resin composition] The odor of the composition after mixing in a beaker, the coloring test described below, and the 20 min thick sheet were evaluated.

〔transparency〕

The rough sheet was pressed at 1♂O℃ for 5 minutes to produce a sheet with a thickness of J. It was visually compared and evaluated, and it was evaluated as J grade (J grade (good) -
Grade 7 (poor)).

[Colorability (press heat resistance)]

The pressing time of the transparency test was increased and the degree of coloring was visually evaluated and expressed as a J grade (J grade (good)←→1 grade (poor)). .

[Thermal stability (gear open heat resistance)] A rough sheet of o, p, thickness was heated in a gas ozone having an atmosphere of lrO ℃, and the time until the rough sheet turned black and deteriorated was measured. The degree of coloring between them was also visually compared and evaluated.
Displayed as ○×.

Table 1 Qin Discoloration from pale yellow to brownish Example 2=ethyl-3-hydroxy-
The same test as in Example 1 was conducted, except that a predetermined amount of l-pyro/ was contained, and the results are shown in Table 2.

2nd table vase Pale yellow to brownish color Example 3 In Example 1, Experiment A4Z and j, cadmium stearate f, /, - parts by weight, barium stearate fO
A vinyl chloride resin composition was obtained in the same manner as in Example 1, except that the amounts were increased to 3 parts by weight.

The transparency of the pressed sheet obtained by using the same core composition as in Example 1 was comparable to that in Experiment A/ of Example 1. The results of the colorability test are shown in Table 3.

As is clear from the Examples in Table 3, when λ-alkyl-3-hydroxy-≠-pyrone f 0.0002 or more is added, the characteristic odor of the vinyl chloride resin composition is eliminated and the thermal stability is slightly improved.

Further, when 0.00/- or more is added, the transparency is good, and especially in the range of 0.0.0/-0.1 parts by weight, the thermal stability is significantly improved. In Example 3, in which a heat stabilizer was added to the same level as without addition of λ-alkyl-3-hydroxy-q-pyrone, the coloring property test was improved by 7 ranks compared to the case without addition. That is clear.

Claims (1)

[Claims] (1) A vinyl chloride resin composition containing λ-alkyl-3-hydroxy≠-pyrone represented by the general formula [wherein R represents an alkyl group having a carbon number/-j]