JPH0725929B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent properties such as heat resistance and weather resistance regardless of whether it is hard or soft.

[Prior art and its problems] In recent years, thermoplastic resin compositions are often used as raw materials for products used at high temperatures or outdoors, and these products are required to have particularly high heat resistance and weather resistance. Has been done. In order to satisfy such characteristics, it is the current situation that stabilizers and ester compounds are appropriately selected and used as auxiliary materials for resins according to the required characteristics.

However, conventional stabilizers have poor compatibility with polymers and cannot be used in large amounts, so there is a limit to product stabilization.

In addition, when applying ester-based auxiliary materials, it is required to have properties such as compatibility with resin, volatility resistance, transparency, bleeding property, migration resistance, etc., but all properties are well balanced. Nothing has been proposed yet.

Conventionally, epoxy-based ester compounds have been widely used as auxiliary materials with excellent heat resistance and weather resistance, but due to their characteristics,
There is room for improvement.

For example, epoxy hexahydrophthalic acid di (2-ethylhexyl) (hereinafter abbreviated as “E-PS”) is excellent in heat resistance, weather resistance, compatibility with resin, transparency, bleeding property, water resistance and the like. On the other hand, volatility and migration resistance are not satisfactory.

Epoxidized soybean oil (hereinafter abbreviated as "ESBO")
Is excellent in thermal stability, light stability, volatility resistance, migration resistance, etc., but it is difficult to bleed because it is incompatible with the resin,
Also, it tends to lack water resistance.

In order to develop a thermoplastic resin composition having excellent heat resistance, volatility resistance, and weather resistance, regardless of whether it is a soft or hard field, the present inventors have made various studies on epoxy-based ester compounds, particularly as auxiliary materials for resins. As a result, they have found that the desired object can be achieved by blending an ester compound having a specific structure, and have completed the present invention based on this finding.

That is, an object of the present invention is to provide a thermoplastic resin composition containing a novel epoxy ester compound as an auxiliary material.

[Means for Solving Problems] The thermoplastic resin composition according to the present invention is characterized by being blended with an ester represented by the following general formula (I).

(In the formula, R represents an alkyl group or an alkenyl group having 3 to 22 carbon atoms. X is an aliphatic or aromatic group having 2 to 13 carbon atoms, or an alicyclic carboxylic acid containing no epoxy ring. When X is an aliphatic or alicyclic carboxylic acid residue, n is an integer of 1 to 4. When X is an aromatic carboxylic acid residue, n is an integer of 2 to 3. .N
When R is 2 or more, each R may be the same or different, but at least one of them is 1 or 2
It must have at least one epoxy ring. ) Examples of the carboxylic acid component as a raw material of the ester according to the present invention include 2-ethylhexyl acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, oleic acid, linolenic acid and ricinoleic acid. Basic acids, aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanenic acid, citric acid, butanetetracarboxylic acid or their anhydrides, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid Alicyclic polybasic acids such as aromatic polybasic acids or their anhydrides, hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid or their anhydrides Can be illustrated.

On the other hand, as the alcohol component, for example, allyl alcohol, hexenyl alcohol, sorbyl alcohol, octenyl alcohol, undecenyl alcohol, dodecenyl alcohol, octadecenyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, Unsaturated alcohols such as ricinoleyl alcohol are mentioned.

Each of the carboxylic acid component and the alcohol component may be used alone or in combination of two or more.

The ester according to the present invention can be obtained by epoxidizing the ester having an unsaturated bond synthesized from the above-exemplified carboxylic acid component and unsaturated alcohol by a conventional method.

The ester compound is used alone or as a mixture of two or more kinds as an auxiliary material for the thermoplastic resin.

The amount of the ester compounded is appropriately selected depending on the type of resin to be applied and the properties required for the resin composition.

For example, when the thermoplastic resin is a chlorine-containing resin,
It is appropriately selected within the range of about 1 to 100 parts by weight, preferably about 3 to 50 parts by weight, based on 100 parts by weight of the resin.

Here, as the chlorine-containing resin, a resin produced from vinyl chloride or a comonomer copolymerizable with vinyl chloride by a method such as a suspension polymerization method, an emulsion polymerization method or a bulk polymerization method is used. The average degree of polymerization of such a resin is 400 to 10,000.
The degree is illustrated.

Examples of the comonomer copolymerizable with vinyl chloride include vinyl esters, methacrylic acid esters, maleic acid esters, vinyl ethers, α-olefins,
Examples thereof include vinyl halides other than vinylidene chloride and vinyl chloride.

Also, when the thermoplastic resin is a polyamide resin,
1 to 20 parts by weight, preferably 3 to 100 parts by weight of resin
It is appropriately selected within the range of up to 10 parts by weight.

Further, when the thermoplastic resin is a polyolefin resin, it is appropriately selected within the range of about 1 to 10 parts by weight with respect to 100 parts by weight of the resin.

Here, as the polyolefin-based resin, high-density polyethylene, medium-density polyethylene, low-density polyethylene that also includes linear polyethylene, ethylene-based polymers such as copolymers having a polyethylene content of 50% or more, homopolypropylene, and propylene. Ethylene as main component and / or α-
Examples include polypropylene-based polymers such as random copolymers and block copolymers with olefins. The α
-Representative examples of olefins include butene-1, hexene-1, octene-1 and the like.

As the thermoplastic resin to which the epoxy ester compound according to the present invention can be applied, in addition thereto, cellulose acetate, ethyl cellulose, cellulose acetate butyrate, cellulosic resin such as celluloid, vinyl acetate resin, ABS resin, polycarbonate resin, polyvinyl butyral. Butyral resin such as urethane resin, polyester resin, polystyrene resin, polyacetal, polyphenylene oxide, polysulfone, fluororesin, polyimide, natural rubber or styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene Various synthetic rubbers such as rubber and ethylene-propylene rubber are exemplified.

The thermoplastic resin composition according to the present invention includes diheptyl phthalate and di (2-ethylhexyl phthalate) (hereinafter referred to as “DO
It is abbreviated as "P". ), Diisononyl phthalate, diisodecyl phthalate, di (2-ethylhexyl) adipate,
A general-purpose or secondary plasticizer typified by tri (2-ethylhexyl) trimellitate, epoxidized soybean oil, tricresyl phosphate, or another ester used as a processing aid can be appropriately used in combination.

In this case, the amount thereof is appropriately selected as long as a predetermined effect is exhibited, but the resin 100 is used as the total amount of the ester compound.
It is up to about 100 parts by weight with respect to parts by weight. If the content is more than the above range, bleeding or whitening phenomenon occurs, which is not preferable.

Furthermore, stabilizers, lubricants, flame retardants, antioxidants, ultraviolet absorbers, fillers, colorants, mold release agents, antifogging agents, antistatic agents, crosslinkers, which are usually used as auxiliary materials for resins. , Antibacterial agents, antifungal agents, antialgal agents, foaming agents and the like can be appropriately added.

The method of blending the resin composition components according to the present invention is not particularly limited to the order of addition and the equipment, but is generally used extruder, heating roll, Henschel mixer, V blender, ribbon blender, Banbury mixer, kneader blender. It is made by mixing for a predetermined time using a kneader such as.

The thermoplastic resin composition thus obtained is a window frame, a signboard,
Hard products such as telephones, tubs, plates, pipes, floor materials,
Roofing materials, packaging materials, leather, vinyl films for agriculture, general-purpose films, wallpapers, hoses, electric wires, paste sol molded products,
It is useful in various fields of soft products such as tents, sheets, curtains, and sealing materials.

In particular, the resin composition for the marking film is required to have excellent properties such as volatility resistance, weather resistance, heat resistance, migration resistance, water resistance, and adhesiveness, and to be free from bleeding. The thermoplastic resin composition according to (1) exhibits excellent performance in the field and is used as a prize.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples.

Examples 1 to 4 A vinyl chloride resin composition having the following composition was roll-kneaded (conditions: 163 to 165 ° C x 4 minutes, thickness 0.8 mm) and then press-molded (conditions: 165 ° C x 10 minutes, 100 Kg / cm ² and thickness 1 mm) to prepare a test sheet, which was evaluated for heat resistance, volatility resistance, weather resistance and water resistance. The results obtained are shown in Table 1.

Composition of resin composition (parts by weight) -Vinyl chloride resin 100 [Geon101EP (degree of polymerization = 1450); manufactured by Nippon Zeon Co., Ltd.]-Ester 50-Calcium stearate 0.3-Zinc stearate 0.2 Evaluation of physical properties of resin composition , By the following method.

(1) Heat coloring test (evaluation of heat resistance) The molded sheet is heated in a gear oven at 170 ° C, and the discoloration of the test piece is visually observed at regular intervals, and the heat resistance is evaluated from the degree of coloring of the sheet. did. It should be noted that the case of no discoloration is represented by ⊚, the case of light yellow color is represented by ◯, and the case of discoloration to black brown is represented by x.

(2) Volatility resistance During the heat coloring test, the weight loss (volatilization loss: weight%) of the plasticized resin composition was measured to evaluate the degree of volatility.

(3) Weather resistance An accelerated weather resistance test using a closed UV carbon arc type weatherometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to visually observe the degree of discoloration of the resin composition to judge the weather resistance. Specifically, the temperature of the black panel was set to 60 to 70 ° C, and the water spray cycle was adopted as the water spraying condition after the light irradiation for 102 minutes and then for 18 minutes.

(4) Water resistance The molded sheet was immersed in water at room temperature for 1 week, then naturally dried, and the transparency of the sheet was evaluated by visually observing the presence or absence of cloudiness.

The esters used in each example are as follows.

Ester I: 9,10-epoxyoctadecylcarboxylic acid-9,10-epoxyoctadecyl ester II: Adipic acid di (9,10-epoxyoctadecyl) ester III: Butanetetracarboxylic acid tetra (9,10-epoxyoctadecyl) ester VI : Di (9,10-epoxyoctadecyl phthalate) Comparative Example 1 The characteristics when E-PS was applied were evaluated according to Example 1. The results obtained are shown in Table 1.

Comparative Example 2 The characteristics when ESBO was applied were evaluated according to Example 1. The results obtained are shown in Table 2.

Examples 5 to 8 A polyamide composition having the following composition was molded at a molding pressure of 800K.
The heat resistance, weather resistance and water resistance of the molded product obtained by injection molding under the conditions of g / cm ² , mold temperature of 50 ° C. and molding temperature of 210 ° C. were evaluated. The results obtained are shown in Table 2.

Composition of resin composition (parts by weight) ・ Nylon 11 (manufactured by Nippon Rilsan Co., Ltd.) 100 ・ Ester 5 ・ Ethylenebisstearic acid amide 2 ・ Calcium stearate 1 Comparative Example 3 The characteristics when E-PS was applied It evaluated according to 5. The results obtained are shown in Table 2.

Comparative Example 4 The characteristics when ESBO was applied were evaluated according to Example 5. The results obtained are shown in Table 2.

Examples 9 to 12 A polypropylene composition having the following composition was molded at a molding pressure.
The heat resistance, weather resistance and bleeding property of the molded product obtained by injection molding under the conditions of 800 kg / cm ² , mold temperature 60 ° C., molding temperature 230 ° C. were evaluated. The results obtained are shown in Table 3.

The bleeding property was evaluated by visually observing the presence or absence of oil droplets on the surface of the molded product after allowing the molded product to stand at room temperature for 3 days.

Composition of resin composition (parts by weight) -Polypropylene 100 (Homopolymer AM-3, manufactured by Mitsubishi Petrochemical Co., Ltd.)-Ester 5-Calcium stearate 0.05 Comparative Example 5 The characteristics when E-PS is applied are shown in Example 9 It was evaluated according to. The results obtained are shown in Table 3.

Comparative Example 6 The characteristics when ESBO was applied were evaluated according to Example 9. The results obtained are shown in Table 3.

[Effect of the Invention] Each of the polyvinyl chloride, polyamide, and polypropylene resin compositions according to the present invention has heat resistance, weather resistance, water resistance,
It has well-balanced bleed resistance. Specifically, it has excellent volatility and heat resistance as compared with E-PS, which is a general-purpose epoxy ester compound, and has excellent water resistance and bleeding performance as compared with a composition containing epoxidized soybean oil. Have

Claims (1)

[Claims] 1. A thermoplastic resin having the following general formula (I):
A thermoplastic resin composition comprising an ester represented by: (In the formula, R represents an alkyl group or an alkenyl group having 3 to 22 carbon atoms. X represents a fatty acid or aromatic group having 2 to 13 carbon atoms, or an alicyclic carboxylic acid residue containing no epoxy ring. When X is an aliphatic or alicyclic carboxylic acid residue, n is an integer of 1 to 4. When X is an aromatic carboxylic acid residue, n is an integer of 2 to 3. n
When R is 2 or more, each R may be the same or different, but at least one of them is 1 or 2
It must have at least one epoxy ring. )