JPS6216979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin composition with significantly improved processability. Specifically, the present invention relates to a synthetic resin composition with significantly improved processability, which contains an imidized product of maleic anhydride-modified α-olefin or maleic anhydride-modified low-molecular-weight polyethylene. In general, synthetic resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and ABS have a high melt viscosity even during heat processing, and may overheat processing machines due to frictional heat, or may stick to processing machines and become difficult to flow. . In addition, the molded product may adhere to the surface of the mold, making it difficult to release from the mold, or the films may adhere to each other, making it difficult to open the mold.
These problems are caused by the lubricity of the resin, and in order to prevent such disadvantages, conventional technology has incorporated processability improving agents such as lubricants, fluidity improvers, mold release agents, slip agents, and anti-blocking agents. I came. The processability improving agent added and blended for this purpose must have an appropriate shape, have good dispersibility in the resin, lubricity, processability, and thermal stability, and maintain the lubricity effect throughout the entire processing process. Does not interfere with the gelation of the formulation, does not inhibit the heat resistance and weather resistance of the resin, does not react with plasticizers, stabilizers, colorants, fillers, or other resin additives, does not bloom, bleed, or devitrify. It is necessary to meet certain conditions such as not causing whitening, etc., and not having an adverse effect on the properties of the product. Conventionally, hydrocarbons such as linear or branched paraffins with a molecular weight of 1000 to 5000 or low molecular weight polyethylene (polyethylene wax), or acid-modified products thereof, stearic acid, and behenic acid have been used to improve processability. , saturated or unsaturated fatty acids with 14 to 40 carbon atoms such as montanic acid, carbon number such as lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, etc.
12 to 32 aliphatic alcohols, or amides, esters, glycerides, metal salts, etc. of the above acids or alcohols are known. Furthermore, inorganic substances such as silicon oxide are also known as anti-blocking agents. However, these processability improving agents are still insufficient and none satisfy the above conditions. For example, stearic acid is prone to blooming and plate-out, and has poor transparency. Esters and amides have insufficient lubricity and poor thermal stability.
Furthermore, amides bloom violently, causing initial coloring and
It also undermines transparency. Paraffins generally tend to bloom, and metal soaps tend to plate out and are often unsuitable for clear formulations. In addition, in recent years, the use of acid-modified products such as polyethylene wax or low molecular weight polyethylene, or their esters or metal salts has been proposed.
Although a slight improvement in releasability was observed, thermal coloration occurred, a tendency to bleed was observed, and roll staining was particularly severe, making it unusable. In addition, the addition of inorganic substances can improve the optical and physical properties of the resin.
It may adversely affect electrical properties and reduce processability. Moreover, none of the above-mentioned known processability improvers improve impact resistance. The inventors of the present invention have made extensive studies to solve these drawbacks, and have found that they have excellent not only lubricity but also thermal stability, transparency, and especially roll releasability, and do not cause bloom, bleed, plate-out, or roll stains. The present invention has been accomplished by discovering a processability improving agent that has almost no adverse effect on optical and electrical properties and also improves impact resistance. That is, in the present invention, based on 100 parts by weight of the synthetic resin, α having 12 or more carbon atoms modified with maleic anhydride is used.
- By reacting an olefin or a low molecular weight polyethylene wax with a molecular weight of 300 to 5000 with an amine represented by the formula R- _NH2 , 50% of the acid anhydride groups in the molecule are reacted.
To provide a synthetic resin composition with improved processability, which contains 0.05 to 5 parts by weight of an imide compound having an imide group represented by the following general formula [] in the molecule obtained by imidizing the above. It is. (In the above formula, R represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.) Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, hexyl, 2-ethylhexyl, heptyl, octyl,
Groups such as isooctyl, nonyl, decyl, isodecyl, lauryl, myristyl, cetyl, stearyl, aracyl, behenyl and the like are preferred. Hydroxyalkyl groups include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxyamyl, 6-hydroxyhexyl, 1-hydroxymethylethyl, 1
-Hydroxy-1-methylethyl, 1-hydroxymethylpropyl, 3-hydroxy-1-methylpropyl, 2-hydroxy-2-methylpropyl, 2-hydroxybutyl, 4-hydroxyamyl and other groups are preferred. Carboxyalkyl groups include carboxymethyl, carboxyethyl, carboxypropyl,
Groups such as 5-carboxyamyl are preferred. The alkoxyalkyl group has 1 to 8 carbon atoms.
Those having an alkoxy group of, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy,
Mention may be made of octoxy-alkyl groups.
In addition, regarding the alkyl group, the above-mentioned alkyl group can be referred to. As a cycloalkyl group, cyclopentyl,
Groups such as cyclohexyl, cycloheptyl, cyclooctyl and the like are preferred. As the aryl group, groups such as phenyl and naphthyl are preferred; as the arylalkyl group, groups such as benzyl, phenylethyl, and phenylpropyl are preferred; as the alkylaryl group, methylphenyl, dimethylphenyl, biphenyl,
Butylphenyl, t-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl,
Groups such as decylphenyl and dodecylphenyl are preferred. More specifically, the α-olefins in the present invention include those having 12 or more carbon atoms, and α-olefins having 12 to 70 carbon atoms are particularly preferred. Examples include dodecene, tridecene, tetradecene, pentadecene, octadecene, nonadecene, eicosene, docosene, hexacosene, and octacosene.
Also, a mixture of the above α-olefins in any proportion, or a predominant amount of the above α-olefins and a lower α-olefin.
- Mixtures with olefins can also be used. Furthermore, the low molecular weight polyethylene in the present invention preferably has a molecular weight in the range of 300 to 5000, and the low molecular weight polyethylene is preferably ethylene (or a minor amount of other α-olefins such as propylene, 1- butene, 1-hexene, etc.) using a Ziegler type catalyst, or high temperature (100 to 300
°C), high-pressure radical polymerization, Fischer-Tropsch synthesis from carbon monoxide and hydrogen, or depolymerization of high molecular weight polyethylene. Furthermore, low molecular weight polyethylene which is produced as a by-product during the synthesis of high molecular weight polyethylene can also be used. The maleic anhydride-modified α-olefin or low molecular weight polyethylene of the present invention is obtained by reacting the above α-olefin/low molecular weight polyethylene with maleic anhydride by a known method to obtain

[Formula] or

[Formula] is introduced. The amount of maleic anhydride introduced is in molar ratio to α-olefin or low molecular weight polyethylene.
0.2 to 2 can be used, preferably 0.3 to 1.5 in molar ratio
It is. The imidized product of maleic anhydride-modified α-olefin or low molecular weight polyethylene according to the present invention is represented by the above acid-modified α-olefin/low molecular weight polyethylene and the general formula RNH ₂ (R is the same as R above). It can be easily obtained by reacting with an amine at a temperature of 100°C or higher. The amount of amine is preferably 0.5 mol or more based on the acid anhydride. Next, a method for synthesizing an imidide according to the present invention will be described.
However, the present invention is not limited to the following example. Synthesis example 1 Dialene 30 (α-olefin manufactured by Mitsubishi Kasei Corporation,
Add 0.1 g of dicumyl peroxide as a catalyst to a mixture of 84.7 g (0.15 mol) of iodine value = 45.0), 22.1 g (0.23 mol) of maleic anhydride, and 80 g of pseudocumene as a carrier, and heat to 140 ° C. in a nitrogen stream.
Stir and react at this temperature for 1 hour. Then cool to room temperature and add dicumyl peroxide 0.1
g and reacted at 140°C for 1 hour. After repeating this operation twice, the reaction was further carried out at 140°C for 1 hour. Next, 13.4g (0.22mol) of monoethanolamine
was added and reacted under reflux of pseudocumene (about 175℃) for about 3 hours, resulting in about 3.7 ml of produced water (theoretical value 4.0
ml) was confirmed. Subsequently, the pressure inside the system was reduced to remove the solvent, and the reaction was carried out for 1 hour at 180° C. and 5 mmHg, and the reaction was completed. The product is a pale yellow solid with an iodine value of 9.2 (softening temperature
70-80°C), and the yield was 113.5g. The following Table 1 (1 to 11) shows imidized products synthesized using α-olefins. Furthermore, imidized products synthesized using commercially available low molecular weight polyethylene are shown in Table 2 (1-30).

【table】

【table】

[Table] The blending amount of the imidide according to the present invention is 0.05 to 5 parts by weight per 100 parts by weight of the resin. If the amount is less than this, no sufficient effect will be observed, and if it is more than 5 parts by weight, it will become too slippery and cannot be kneaded. Preferably 0.1~
2 parts by weight. The imidide according to the present invention may be blended into the resin as it is during processing, or may be mixed with other additives before processing. Adding an antioxidant to the composition of the present invention increases the oxidative deterioration prevention properties of the present invention, and therefore it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, and the like. By adding an ultraviolet absorber to the composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenone series, benzotriazole series, succilate series, substituted acrylonitrile series, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine series, and the like. Others as necessary, such as stabilizers, plasticizers, pigments, fillers, foaming agents, antistatic agents, antifogging agents, flame retardants, surface treatment agents, fluorescent agents, antifungal agents, metal deactivators. , photodegradants, bactericidal agents, organic chelators, thiourea derivatives, boric acid esters, plate-out inhibitors, or other processability improving agents. Examples of the synthetic resin according to the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer,
Vinyl chloride - propylene copolymer, vinyl chloride -
Styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer,
Vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-
Halogen-containing synthetic resins such as acrylic ester copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, polyethylene, α-olefin polymers such as polypropylene, polybutene, poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof;
polystyrene, polyvinyl acetate, acrylic resin,
Styrene and other monomers (e.g. maleic anhydride,
butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, methacrylate resins such as polymethyl methacrylate, Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, or phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. I can do it. Further, rubbers such as natural rubber, isoprene rubber, butadiene rubber, acrylonitrile, butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. Next, the present invention will be explained using Examples, but the present invention is not limited thereto. Example 1 In order to examine the effect of the processability improver according to the present invention as a lubricant for polyvinyl chloride resin, a kneading test was conducted using a calendar roll using the following formulation, and the time at which adhesion started on the roll and the staining of the roll were examined. . We also conducted a transparency test.
The results are shown in Table 3 below. However, cases where roll stains were present were indicated by –, and cases where there were no rolls were indicated by -. <Formulation> Polyvinyl chloride resin (Geon 103EP-8) 100 parts by weight dibutyltin bis(butylmalate) 3.0 Sample compound (Table 3) 0.5

[Table] Example 2 An extrusion test (190°C) was conducted using a Brabender Plastograph using the following formulation. The results are shown in Table 4. <Measurement conditions> Screw: L/D12, compression ratio 1285, rotation speed
60rpm Cylinder: Inner diameter 15.2m/m Nozzle: Diameter 3.0m/m Heating: Silicone oil reflux type <Composition> Polyvinyl chloride resin (Geon 103 EP)
100 parts by weight Barium stearate 1.2 Zinc stearate 0.3 Dioctyltin bis(2-ethylhexyl thioglycolate) 0.5 parts by weight Sample compound (Table 4) 0.5

[Table] Example 3 The effects of the processing aid according to the present invention were investigated using a blended resin. The results obtained are shown in Table 5 below. <Composition> ABS resin 50 parts by weight PVC resin 50 Calcium stearate 1.0 Diptyltin β-mercaptopropionate
3.0 Sample Compound (Table 5) 3.0 The above formulation was thoroughly mixed and then a compound was prepared at 190°C using an extruder. The resulting compound was subjected to a spiral flow test at 200° C. and an injection pressure of 475 Kg/cm ² .

[Table] Example 4 To examine the thermoplastic fluidity improvement effect of the present compound on various resins, 0.5, 1.0, and 2.0 parts by weight of the present compound (Table 1 No. 1) were added to 100 parts by weight of the resin. The thermoplastic fluidity of the resin was measured using a melt indexer at 200°C and a load of 5 kg. The results are shown in Table 6.

[Table] Example 5 The compound of the present invention produced effects equivalent to those of the previous example in the molding process of polycarbonate resin, epichlorohydrin rubber, polymethyl methacrylate, polybutylene terephthalate resin, etc. Example 6 The compound of the present invention also showed excellent lubricity in ethylene-vinyl acetate copolymer resin. The peelability was examined under the following formulation and conditions. The results obtained are shown in Table 7 below. <Formulation> EVAFLEX 560 (manufactured by Mitsui Polychemicals, ethylene-vinyl acetate copolymer) 100 parts by weight Trisnonyl phenyl phosphite 0.2 Sample compound (Table 7) 0.2 <Conditions> Roll temperature: 150°C Roll rotation speed: 30 rpm Roll time: min

【table】

Claims (1)

[Scope of Claims] 1. Based on 100 parts by weight of synthetic resin, α-olefin having 12 or more carbon atoms modified with maleic anhydride or low molecular weight polyethylene wax having a molecular weight of 300 to 5000 and represented by the formula R-NH ₂ An imide compound having an imide group represented by the following general formula [I] introduced into the molecule obtained by imidizing 50% or more of the acid anhydride groups in the molecule.
A synthetic resin composition with improved processability, comprising parts by weight. (In the above formula, R represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.)