JPH01170655A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition especially suitable as a marking film, having excellent heat resistance, volatility resistance and weather resistance irrespective of nonrigid or rigid field, by blending a thermoplastic resin with a specific epoxy ester compound. CONSTITUTION:(A) A thermoplastic resin is blended with (B) an epoxy ester compound shown by the formula (R is 3-22C alkyl or alkenyl; X is 2-13C alicyclic carboxylic acid containing neither aliphatic group nor epoxy ring wherein n is 1-4 or aromatic carboxylic acid wherein n is 2-3 and when n is >=2, at least one of R contains 1-2 epoxy rings) prepared by epoxidizing an unsaturated bond-containing ester synthesized from a carboxylic acid component (e.g., adipic acid or tetrahydrophthalic acid) and an unsaturated alcohol (e.g., allyl alcohol or sorbyl alcohol) to give a thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition, regardless of whether it is hard or soft, that has excellent properties such as heat resistance and weather resistance.

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

However, since conventional stabilizers have poor compatibility with polymers and cannot be used in large amounts, there are limits to the stabilization of products.

In addition, when applying ester-based secondary materials, they are required to have properties such as compatibility with resin, volatility resistance, transparency, bleedability, and migration resistance, but it is necessary to have all properties in a well-balanced manner. What it does have has not yet been proposed.

Conventionally, epoxy ester compounds have been widely used as auxiliary materials with excellent heat resistance and weather resistance, but there is still room for improvement in terms of their properties.

For example, epoxy hexahydrophthalate di(2-ethylhexyl) (hereinafter abbreviated as rE-PSJ) has excellent heat resistance, weather resistance, compatibility with resins, transparency, bleedability, water resistance, etc. , volatility resistance, and migration resistance are not satisfactory.

In addition, epoxidized soybean oil (hereinafter abbreviated as rEsBOJ)
) has excellent thermal stability, light stability, volatility resistance, migration resistance, etc., but it is difficult to be compatible with resins and bleeds easily.
Also, they tend to lack water resistance.

In order to develop thermoplastic resin compositions with excellent heat resistance, volatility resistance, and weather resistance, the present inventors conducted various studies on epoxy-based ester compounds as auxiliary materials for resins, regardless of whether they are soft or hard. As a result, they discovered that the desired objective could be achieved by blending an ester compound with a specific structure, and based on this knowledge, they completed the present invention.

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 the problems] The thermoplastic resin composition according to the present invention has the following general formula (I
It is characterized by containing an ester represented by >.

X+C-0R). (I> (wherein, R represents an alkyl group or alkenyl group having 3 to 22 carbon atoms; X is an aliphatic or aromatic group having 2 to 13 carbon atoms; represents a carboxylic acid residue.

When X is an aliphatic or alicyclic carboxylic acid residue, n is 1 to
Represents an integer of 4. When X is an aromatic carboxylic acid residue,
n represents an integer of 2 to 3. When n is 2 or more, each R may be the same or different, but at least one of the groups must have one or more epoxy rings. ) Carboxylic acid components serving as raw materials for the esters according to the present invention include aliphatic bases such as 2-ethylhexylic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, oleic acid, lylunic acid, and ricinoleic acid. Acids, aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanniic acid, citric acid, butanetetracarboxylic acid, or their anhydrides, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc. aromatic polybasic acids or their anhydrides, alicyclic polybasic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, or their anhydrides can be exemplified.

On the other hand, examples of the alcohol component include allyl alcohol, hexenyl alcohol, turuvyl alcohol, octenyl alcohol, undecenyl alcohol, dodecenyl alcohol, octadecenyl alcohol, oleyl alcohol, elaidyl alcohol, lysyl alcohol, Examples include unsaturated alcohols such as lysyl alcohol.

Any of these carboxylic acid components and alcohol components can be used alone or in combination of two or more.

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

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

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

For example, when the thermoplastic resin is a chlorine-containing resin,
It is suitably selected in the range of 1 to 100 parts by weight or 3 to 50 parts by weight based on 100 parts by weight of the resin.

Here, the chlorine-containing resin used is one produced from vinyl chloride or a comonomer copolymerizable with vinyl chloride by a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, or the like. The average degree of polymerization of such resin is 400 to 1.
An example is about 0000.

Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters, methacrylic esters, maleic esters, vinyl ethers, α-olefins,
Examples include vinylidene chloride and vinyl halides other than vinyl chloride.

In addition, when the thermoplastic resin is a polyamide resin,
The amount is appropriately selected within the range of 1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the resin.

Furthermore, when the thermoplastic resin is a polyolefin resin, it is appropriately selected in the range of 1 to 10 parts by weight per 100 parts by weight of the resin.

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

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

The thermoplastic resin composition according to the present invention includes diheptyl phthalate, di(2-ethylhexyl phthalate) (rDO
It will be abbreviated as PJ. ), diisononyl phthalate, diindecyl phthalate, di(2-ethylhexyl) adipate,
Other esters used as general-purpose or secondary plasticizers or processing aids, such as tri(2-ethylhexyl trimellitate), epoxidized soybean oil, and tricresyl phosphate, can be used in combination as appropriate.

In this case, as long as the desired effect is achieved, the blending amount is appropriately selected, but the total amount of the ester compound is 10% of the resin.
The amount is up to about 100 parts by weight compared to 0 parts by weight. If the amount exceeds this range, bleeding or whitening phenomenon will occur, which is not preferable.

Furthermore, stabilizers, lubricants, flame retardants, antioxidants, ultraviolet absorbers, fillers, colorants, mold release agents, antifogging agents, antistatic agents, and crosslinking agents, which are usually used as auxiliary materials for resins. , an antibacterial agent, an antifungal agent, an antialgal agent, a foaming agent, and the like can be appropriately blended.

The method of blending the resin composition components according to the present invention is not particularly limited in the order of addition or equipment, but commonly used extruders, heating rolls, Henschel mixers, blenders, ribbon blenders, Banbury mixers, etc. This is done by mixing for a predetermined period of time using a kneader such as a blender.

The thermoplastic resin composition thus obtained can be used for window frames, signboards,
Hard products such as telephones, tubs, plates, pipes, flooring materials,
Roofing materials, packaging materials, leather, agricultural vinyl films, general-purpose films, wallpaper, hoses, electric wires, paste-sol molded products,
It is useful in various fields of soft products such as tents, sheets, curtains, and sealants.

In particular, resin compositions for marking films are required to have excellent properties such as volatility resistance, weather resistance, heat resistance, migration resistance, water resistance, and adhesion, and to be free from bleeding. The thermoplastic resin composition exhibits excellent performance in the field and is prized.

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

Examples 1 to 4 A vinyl chloride resin composition having the following composition was subjected to roll cross-wiring (conditions: 163-b thickness 0.8#) and press molding (conditions: 165°C
A test sheet was prepared and its heat resistance, volatility resistance, weather resistance, and water resistance were evaluated. The results obtained are shown in Table 1.

Composition of resin composition (parts by weight) - Vinyl chloride resin 100 [Geo
nlolEP (degree of polymerization = 145D): manufactured by Nippon Zeon ■]・Ester 50・Calcium stearate 0.3・Zinc stearate 0.2 The physical properties of the resin composition were evaluated by the following method.

(1) Heat coloring test (evaluation of heat resistance) The molded sheet was heated in a gear oven at 170°C, and the discoloration of the test piece was visually observed at regular intervals, and the heat resistance was evaluated based on the degree of coloration of the sheet. did.

In addition, ◎ indicates that the color does not change, and O indicates that it becomes pale yellow.
1. The case where the color changed to blackish brown is indicated as ×.

(2) Weight loss of the plasticized resin composition during the volatile heat coloring test (
Volatility loss (weight %) was measured to evaluate the degree of volatility.

(3) Weather resistance An accelerated weather resistance test was performed using a sealed ultraviolet carbon arc type weather meter (newly manufactured by Toyo Seiki Seisakusho), and the degree of discoloration of the resin composition was visually observed to determine whether the weather resistance was good or bad. Specifically, the black panel temperature was set at 60 to 70° C., and the water spraying conditions were a 102-minute light irradiation followed by an 18-minute water spray cycle that also served as light irradiation.

(4) The water-resistant molded sheet was immersed in the hottest water for one week, then air-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■: 9.10-■boxyoctadecylcarvone l-9,10
-Epoxyoctadecyl ester■: Di(9,10-epoxyoctadecyl) adipate Ester■Nibutanetetracarboxylic acid tetra(9,10-epoxyoctadecyl) Ester lv: 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 Characteristics when ESBO was applied were evaluated according to Example 1. The results obtained are shown in Table 2.

Examples 5-B A polyamide composition having the following composition was molded under a molding pressure of 80
0 Kg/cti, mold temperature 50℃, molding temperature 210
The heat resistance, weather resistance, and water resistance of the molded product obtained by injection molding under the conditions of 'C were evaluated. The results obtained are shown in Table 2.

Composition of resin composition (parts by weight) - Nylon 11 (manufactured by Nippon Rilzan ■) 100-layer ester 5 - Ethylene bisstearic acid amide 2 - Calcium stearate 1 Comparative example 3 Characteristics when E-PS is applied are shown in Example 5 The results were shown in Table 2.

Comparative Example 4 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 pressure of 800 K! l/ctA, heat resistance of a molded product obtained by injection molding under the conditions of a mold temperature of 60°C and a molding temperature of 230°C,
Weather resistance and bleedability were evaluated. The results obtained in the third
Shown in the table.

The bleedability was evaluated by visually observing the presence or absence of oil droplets on the surface of the molded product after leaving the molded product at room temperature for 3 days.

Composition of resin composition (parts by weight) - Polypropylene 100 (homopolymer A)! -3. (Made by Mitsubishi Yuka) / Ester
5. Calcium stearate
0.05 Comparative Example 5 The characteristics when E-PS was applied were evaluated according to Example 9. The results obtained are shown in Table 3.

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

[Effects of the Invention] The polyvinyl chloride, polyamide, and polypropylene resin compositions of the present invention have particularly good heat resistance, weather resistance, water resistance,
It has well-balanced characteristics in terms of bleed resistance. Specifically, it has better volatility resistance and heat resistance than E-PS, a general-purpose epoxy ester compound, and has better water resistance and bleed resistance than a composition containing epoxidized soybean oil. have.

Patent applicant: Shin Nihon Rika Co., Ltd.

Claims (1)

[Scope of Claims] 1. A thermoplastic resin composition characterized by blending an ester represented by the following general formula (I) into a thermoplastic resin. There are mathematical formulas, chemical formulas, tables, etc. I) (wherein, R represents an alkyl group or alkenyl group having 3 to 22 carbon atoms; X is an aliphatic or aromatic group having 2 to 13 carbon atoms, or an alicyclic group containing no epoxy ring; Represents a carboxylic acid residue. When X is an aliphatic or alicyclic carboxylic acid residue, n is 1 to
Represents an integer of 4. When X is an aromatic carboxylic acid residue,
n represents an integer of 2 to 3. When n is 2 or more, each R may be the same or different, but at least one of the groups must have one or more epoxy rings. )