JP4454319B2 - Polymer composition and production method thereof - Google Patents

Description

  INDUSTRIAL APPLICABILITY According to the present invention, in a thermoplastic polymer composition containing an organic polymer additive and / or a physiologically active substance, the allowable blending amount can be increased, and the bleed-out speed of the blend is adjusted. It is related with the polymer composition which can be manufactured, and its manufacturing method.

  When manufacturing molded products such as films, sheets, filaments, bottles, etc. using thermoplastic polymers as raw materials, organic polymers such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, etc. are added to the raw polymers. After blending the agent, products are produced using molding methods such as extrusion molding, blow molding, and injection molding.

  These organic additives, when the raw material resin is a vinyl chloride resin, have good compatibility with various compounding agents. Therefore, if necessary, the compounding amount is several percent or more, sometimes several tens percent or more. It is also easy to make. However, in polyolefin resins such as polyethylene and polypropylene, for example, the blending amount of ultraviolet absorbers and antistatic agents is usually less than 1%. The reason for this is that if a large amount of compounding agent is added to the polyolefin resin, the compounding agent gradually bleeds out on the surface during storage or use of the molded product, resulting in a feeling of stickiness, poor touch and reduced commercial value. Therefore, the blending amount is adjusted to be as small as possible.

  When considering the field of application of packaging film, an antistatic agent is generally added to the film-forming resin, but if the blending amount can be further increased, for example, 1% or more, the handling property as a film is further improved. The antistatic effect is expected to be improved. Even in the case of producing a molded product containing a chemical substance such as an insect control agent, if the blending amount is increased, it is possible to increase the efficacy and prolong the insecticidal and repellent effects. There are a wide variety of uses where it is considered that good effects can also be obtained for molded products containing other chemical substances. Therefore, if the compounding amount of the compounding agent can be increased without affecting the product touch and the like, it can contribute to the expansion of the range of use of the plastic molded product. Therefore, there is a need for technological development to increase the amount of many chemical substances such as polymer additives added to the thermoplastic polymer.

  A composition with a strong fragrance or deodorant power and excellent sustainability by blending a large amount of a fragrance or deodorant component and a sublimation substance into a thermoplastic polymer such as an ethylene / vinyl acetate copolymer. It is already known (see Patent Document 1). However, the composition is limited to the blending of fragrances or deodorant ingredients, and nothing is disclosed about application to chemicals such as common plastic additives such as antistatic agents and insect control agents. Not. Further, the thermoplastic polymer used in the publication is only used as a carrier for a fragrance or a deodorant component, and there is no mention of producing molded products of various shapes from the composition. .

JP 58-12654 A

  Therefore, the present invention is capable of blending a large amount of an organic polymer additive or a physiologically active substance with a thermoplastic polymer, and is capable of controlling the bleedout of these blends according to the function. The object is to provide a coalescence composition and a method for producing the same. In the present invention, the organic polymer additive and the physiologically active substance are organic antistatic agents, antifogging agents, or agricultural chemicals.

That is, the present invention relates to pyrethroid insecticide or poly (oxyethylene) alkylamine (B) 0.01 to 350 parts by mass and triisopropyl-S-trioxane, tri-t per 100 parts by mass of the olefin polymer (A). - concerning butyl -S- trioxane, p-dichlorobenzene, naphthalene, camphor, a polymer composition comprising a sublimable substance (C) 0.1 to 100 parts by weight selected from oxygen, sulfur and tricyclodecane.

The present invention also provides olefin polymer (A), pyrethroid insecticides or poly (oxyethylene) alkylamine (B) and the sublimable substance (C), preferably more inorganic filler (D), an olefin It is related with the manufacturing method of the polymer composition characterized by mixing under the melting condition of a system polymer (A).

  Since the polymer composition according to the present invention can contain a large amount of an organic polymer additive and / or a physiologically active substance in the polymer by containing a sublimable substance together, the obtained molded article From the above, the effect of the organic polymer additive and / or the physiologically active substance can be sufficiently obtained over a long period of time. Since it has become possible to add a large amount of these compounding agents, which has been considered difficult with conventional olefin polymers, the application range of olefin polymers can be expanded, and the present invention can also be applied to the production of masterbatches. can do.

  Moreover, the phenomenon in which a compounding agent bleeds out on the surface of a molded article can be suppressed with the sublimation substance added together with the polymer composition. Therefore, the molded product obtained from the polymer composition has a good texture without sticking to the surface and can maintain an excellent product form.

  On the other hand, the effect of the compounding agent can be controlled by adjusting the compounding amount of the compounding agent and the sublimable substance. For example, in the case of a polymer composition containing an insect control agent, the amount of time until the molded product is used after it is manufactured is not constant, so the amount of the insect control agent and sublimation substance should be adjusted. By this, it becomes possible to control the expression time or expression period of the insect control agent.

Next, each structural component which concerns on the polymer composition of this invention is demonstrated concretely.
The olefin polymer (A) may be resinous or elastomeric as long as it has a molecular weight that can be formed into a film, sheet, fiber, or the like. More specifically, a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, such as high pressure polyethylene, medium / high density polyethylene, linear low density polyethylene, and ultra low density polyethylene. Polyethylene resins such as polypropylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc., copolymers of ethylene and polar monomers, such as ethylene / vinyl acetate copolymers, ethylene and unsaturated Copolymers with carboxylic acids such as acrylic acid, methacrylic acid, monoethyl maleate, maleic anhydride, ethylene and one or more unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, acrylic acid Isobutyl, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylate Methyl, copolymers of dimethyl maleate, a copolymer of ethylene and an unsaturated carboxylic acid and an unsaturated carboxylic acid ester as described above, such as olefin polymer of the polyolefin elastomer Karadaa Rui These two or more The mixture of these can be illustrated. Among these, the most preferred mass formulation of Riwake various organic additives is applied to a hard polyolefin resin.

In the present invention as a component (B), organic antistatic agents, can be exemplified antifogging agents and pesticides. These may be solid or liquid at room temperature, and may be easily volatile or hardly volatile, but particularly effective ones are volatile and have a boiling point of, for example, 100 ° C. or higher. It is a liquid material. As the component (B), a pyrethroid insecticide or a poly (oxyethylene) alkylamine antistatic agent or an antifogging agent is preferable.

  Examples of the antistatic agent or antifogging agent include polyoxyalkylene ether, partial ester of polyhydric alcohol, partial ester of polyhydric alcohol alkylene oxide adduct, poly (oxyethylene) alkylamine, and poly (oxyethylene) alkyl. Examples include amides, higher alcohol sulfates, alkali metal salts, alkylaryl sulfonates, and quaternary ammonium salts. More specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Palmitate, glycerol monolaurate, glycerol monopalmitate, glycerol monostearate, glycerol monooleate, pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monostearate, sorbitan distearate, diglycerol Monooleate, triglycerindiolate, lauryldiethanolamine, N, N-bis (2-hydroxyethyl) Stearylamine, polyoxyethylene laurylamine capryl ester, stearyl diethanolamine monostearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride, trimethylbenzylammonium chloride, triethylcetylammonium iodide, Examples thereof include dodecylamine hydrochloride, lauric acid laurylamide ethyl phosphate, oleylaminodiethylamine hydrochloride, dodecylpyridinium sulfate, and the like.

  As an agrochemical, an insecticide (insect control agent) etc. can be illustrated. Specific examples of insecticides (insect control agents) are allethrin, dl · d-T80-alleslin, dl · d-T-alleslin, d · d-T-alleslin, d · d-T80-alleslin, resmethrin, d -80-resmethrin, empentrin, teraleslin, transfluthrin, methoflutrin, etofenprox, tefluthrin, fenpropatorin, fenfluthrin, framethrin, phthalthrin, d-T80-phthalthrin, permethrin, phenothrin, imiprotolin, fenvalerate, cypermethrin And pyrethroid insecticides such as cyphenothrin.

  The sublimable substance (C) used in the present invention is a substance having a property of changing directly from a solid to a vapor, and specifically includes triisopropyl-S-trioxane, tri-t-butyl-S-trioxane, paradioxide. Examples include chlorobenzene, naphthalene, camphor, sulfur, tricyclodecane and the like. Of these, the use of triisopropyl-S-trioxane or tri-t-butyl-S-trioxane is particularly preferable.

In the preparation of the polymer composition of the present invention, the blending ratio of the compounding agent (B) selected from the pyrethroid insecticide and the poly (oxyethylene) alkylamine varies depending on the compounding purpose, but the olefin polymer (A ) Preferably, it is in the range of 0.01 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, and still more preferably 0.5 to 30 parts by mass per 100 parts by mass. The mixing ratio of the sublimable substance (C) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 5 to 30 parts by mass per 100 parts by mass of the olefin polymer (A). Part range. Moreover, it is preferable to adjust a compounding agent (B) and a sublimable substance (C) to the range of 1 / 15-15 / 1 by mass ratio.

In the preparation of the polymer composition of the present invention, when the compounding agent (B) and the sublimable substance (C) are used within the above range with respect to the olefin polymer (A), the resin has a machine. Properties that the compounding agent (B) has, for example, antistatic effect, insect control effect, etc., appear strongly from the molded product without damaging the physical properties of the molded product such as mechanical strength, and a composition that lasts for a long time is obtained. be able to. Moreover, the expression level of the property which a compounding agent (B) has can be controlled by changing the compounding ratio of a compounding agent (B) and a sublimable substance (C) into the said range.

  In particular, the compounding agent (B) in the polymer composition is preferably 1 to 350 parts by mass and the sublimable substance (C) is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic polymer. When contained, the composition can be used as a masterbatch of both additives used in producing a molded article. The polymer used when producing the masterbatch is not necessarily the same as the polymer constituting the molded product. For example, a low-density resin as a masterbatch resin for an antistatic agent used for molding a polypropylene film. Polyethylene can be used.

The polymer composition is prepared by uniformly mixing the olefin polymer (A), the compounding agent (B) and the sublimable substance (C) in the above-described ratio. The mixing is preferably performed under the melting conditions of the olefin polymer (A). The order of mixing is not particularly limited, and each of the compounding agent (B) and the sublimable substance (C) may be added to the thermoplastic polymer (A) either sequentially or at once and mixed. The agent (B) and the sublimable substance (C) may be mixed in advance and then added to and mixed with the thermoplastic polymer (A), or may be further mixed using the master batch described above. . For the mixing, dry blending of (A), (B), (C) is usually performed using a mixer such as a super mixer or a Henschel mixer, and then a single screw extruder, twin screw extruder, roll, etc. are used as necessary. It is preferable to add melt blending and mix even more uniformly. In the case of melt blending, although it depends on the melting point and softening point of the resin, it is desirable to carry out at as low a temperature as possible, thereby avoiding loss of sublimable substances.

  In the polymer composition prepared as described above, depending on the mixing apparatus and mixing temperature, a part of the sublimable substance (C) may dissipate and may not be taken into the composition. The bleed-out tendency is suppressed from the similar polymer composition prepared without blending (C). Depending on the combination of (A), (B), and (C), the sublimable substance (C) may bleed out to the surface of the polymer composition over time, but this may be wiped off with a cloth. Even when the above operation is performed, the bleed-out tendency of the compounding agent (B) is suppressed from the similar polymer composition prepared without compounding the sublimable substance (C).

  Other additives can be blended with the polymer composition of the present invention within a range not departing from the object of the present invention. Examples of such additives include inorganic fillers, pigments, lubricants and the like. Examples of the inorganic filler include silica, talc, clay, zeolite, alumina, titanium oxide, magnesium oxide, calcium carbonate, sodium sulfate, barium sulfate, magnesium hydroxide, and aluminum hydroxide. In particular, it is preferable to add an inorganic filler having a large surface area, such as silica or zeolite, because a large amount of an organic polymer additive and / or a physiologically active substance can be added, and handling at the time of preparing the composition can be improved. . A suitable compounding amount of silica or zeolite is 100 parts by mass or less, particularly 0.1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic polymer (A).

  From the polymer composition according to the present invention, it is formed into a shape such as a film, a sheet, a filament, and a container by using a molding method such as extrusion molding, blow molding, injection molding, vacuum molding, foam molding, etc. It can be used as supplies or industrial materials. Above all, films containing a lot of antistatic agents (antifogging agents) are effective as agricultural and horticultural films, and sheets containing lots of insect control agents are hygienic pests such as mosquitoes, flies, cockroaches, fleas, ticks, etc. It is useful as an insecticide and repellent sheet for unpleasant pests such as peanuts, centipedes and ants

  EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited at all by those Examples.

[Examples 1-2]
Ethylene / vinyl acetate copolymer (Evaflex P1405, manufactured by Mitsui DuPont Polychemical Co., Ltd .: abbreviated as EVA) as olefin polymer (A), and phenothrin (insecticide: Sumitomo Chemical) as compounding agent (B) Kogyo Co., Ltd., trade name Smithlin), triisopropyl-S-trioxane as the sublimable substance (C), and silica (AZ-200, manufactured by Nippon Silica Kogyo Co., Ltd.) as the inorganic filler (D) were used. . The above substances were mixed in the proportions shown in Table 1 first using ethylene / vinyl acetate copolymer, silica and sublimation substance using a super mixer, then phenothrin was added and stirring was continued.

  The mixture was supplied to a twin-screw extruder, further kneaded at a resin temperature of 120 ° C., extruded into a strand, cooled in a water bath, and further pelletized. Thereafter, the pellets were supplied to an injection molding machine and injection molded at a resin temperature of 120 ° C. to form a plate.

  Using the molded plate, the amount of blenotrin bleed out was measured, and the results are also shown in Table 1. The bleed-out amount was measured by the following test method. That is, a hole is made at the tip of the plate sample and a hanging hook is attached. First, the initial mass at that time is measured. Next, the sample is placed in a constant temperature air oven at 37 ° C., taken out every predetermined number of days, the surface is wiped with paper, and the mass of the sample is measured. The difference in mass before and after the test was determined, and the value was converted into a numerical value per unit area and displayed as a bleed-out amount.

[Comparative Examples 1-2]
In Examples 1 and 2, the same procedure as in Examples 1 and 2 was performed, except that no sublimable substance was blended in the polymer composition. The measurement results of the resin composition and bleed-out amount are also shown in Table 1.

  As is clear from the test results of Examples 1 and 2 shown in Table 1, as much as 14% by mass of phenothrin as a whole can be added to EVA, and at the same time, by adding triisopropyl-S-trioxane. The blenotrin bleed-out amount could be suppressed over a long period of about 5 months. However, as is clear from Comparative Examples 1 and 2, it was observed that phenothrin bleeds out early when triisopropyl-S-trioxane was not added.

[Examples 3 to 8]
The same ethylene / vinyl acetate copolymer (abbreviated as EVA) used in Example 1 as the olefin polymer (A), polyvinyl chloride (abbreviated as “PVC” manufactured by Sun Arrow Chemical Co., Ltd.) (reference example) Linear low density polyethylene (Ultzex 20100J, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., abbreviated as LLDPE), propylene homopolymer (J105W, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., abbreviated as PP), propylene random copolymer (J704WA) Sumitomo Mitsui Polyolefin Co., Ltd., abbreviated as r-PP) and propylene block copolymer (J226EA, Mitsui Sumitomo Polyolefin Co., Ltd., abbreviated as b-PP) were used. Moreover, the antistatic agent [ Electro stripper EA (lauryl diethanolamine), the Kao Co., Ltd. product ] was used as a compounding agent (B). The same sublimable substance and silica as those used in Example 1 were used.

First, an olefin polymer (A), an antistatic agent, a sublimation substance and silica are mixed in the following proportions, and the same procedure as in Example 1 is performed except that the resin temperature in the extruder is changed. Got.
Thermoplastic polymer (A): 66% by mass
Antistatic agent: 14% by mass
Sublimable substance: 10% by mass
Silica: 10% by mass

Using this pellet, a plate was formed by injection molding, and using this as a sample, a test for measuring the bleed-out amount was conducted in the same manner as in Example 1. The measurement results are shown in Table 2, but here the bleed is shown. The amount of out was evaluated in four stages and indicated by the following criteria.
4: No bleed out was observed.
3: A slight bleed-out was observed on the surface.
2: Slight bleed out was observed.
1: A very large bleed out was observed.

  Further, after applying a charge of 7000 V to the surface of the press sheet prepared in the same manner using SJ-S020 manufactured by Keyence Corporation, it was charged using a high-precision electrostatic sensor (SK-030 / 200 manufactured by Keyence Corporation). The time for the amount to halve was measured. Those with a half-life of 5 seconds or less were evaluated as good, and those with a half-life exceeding 30 seconds were evaluated as poor. The results are also shown in Table 2.

[Comparative Examples 3 to 8]
In Example 3-8, it carried out like Example 3-8 except not having mix | blended the sublimable substance. That is, the mixing ratio of each component was as described below.
Thermoplastic polymer (A): 76% by mass
Antistatic agent: 14% by mass
Sublimable substance: 0% by mass
Silica: 10% by mass

  Using the resulting composition pellets, a plate was formed by injection molding, and the bleed-out amount was measured in the same manner as in Example 1 using the plate as a sample. The measurement results are shown in Table 3.

From the results of Examples 3 to 8 and Comparative Examples 3 to 8 shown in Tables 2 and 3, an antistatic agent as much as 14% by mass can be blended regardless of the type of the olefin polymer (A). It has been found that the use of a sublimable substance brings about the effect of suppressing the bleeding out of the antistatic agent.

[Examples 9 to 11, Comparative Examples 9 to 13]
In Example 5 or Comparative Example 5, the same evaluation was performed except that the blending amounts of the antistatic agent, the sublimable substance (C) and the silica (D) were changed as shown in Table 4. The results of Example 5 and Comparative Example 5 are shown together in Table 4.

[Examples 12 to 13]
In Example 8, the same evaluation was performed except that the blending amounts of the antistatic agent, the sublimable substance (C) and the silica (D) were changed as shown in Table 5. The results of Example 8 and Comparative Example 8 are shown together in Table 5.

Claims (10)

Olefin polymer (A), pyrethroid insecticide or poly (oxyethylene) alkylamine (B) 0.01 to 350 parts by mass and triisopropyl-S-trioxane, tri-t-butyl-S per 100 parts by mass -A polymer composition comprising 0.1 to 100 parts by mass of a sublimable substance (C) selected from trioxane, paradichlorobenzene, naphthalene, camphor, sulfur and tricyclodecane . The polymer composition according to claim 1, wherein the olefin polymer (A) is a polyolefin resin.   The polymer composition according to claim 1 or 2, wherein the pyrethroid insecticide or poly (oxyethylene) alkylamine (B) is lauryldiethanolamine.   The polymer composition according to claim 1 or 2, wherein the pyrethroid insecticide or the poly (oxyethylene) alkylamine (B) is phenothrin. The polymer composition according to any one of claims 1 to 4, wherein the sublimable substance (C) is triisopropyl-S-trioxane. The olefin polymer (A), the pyrethroid insecticide or poly (oxyethylene) alkylamine (B) and a sublimable substance (C) are mixed under the melting conditions of the olefin polymer (A). The polymer composition according to any one of claims 1 to 5 . Furthermore, 0.1-100 mass parts of inorganic fillers (D) are mix | blended per 100 mass parts of olefin type polymers (A), The polymer composition in any one of Claims 1-6 . The polymer composition according to claim 7 , wherein the inorganic filler (D) is silica. 0.01-350 parts by mass of pyrethroid insecticide or poly (oxyethylene) alkylamine (B) and triisopropyl-S-trioxane, tri-t-butyl-S per 100 parts by mass of olefin polymer (A) -Mixing 0.1 to 100 parts by mass of a sublimable substance (C) selected from trioxane, paradichlorobenzene, naphthalene, camphor, sulfur and tricyclodecane under the melting conditions of the olefin polymer (A). A method for producing a polymer composition. It melt-mixes in presence of an inorganic filler (D), The manufacturing method of the polymer composition of Claim 9 characterized by the above-mentioned.