JPS6351186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin composition with improved processability. Specifically, the present invention relates to a synthetic resin composition with improved processability, which is obtained by adding an α,β-monoethylenically unsaturated carboxylic acid alkyl ester oligomer modified with a polyhydric alcohol. 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 or blended for this purpose must have an appropriate shape, have long dispersibility in resin, lubricity, processability, and thermal stability, and maintain a lubricity effect throughout the entire processing process. Does not interfere with the gelation of the compound, does not inhibit the heat resistance and weather resistance of the resin, does not react with plasticizers, stabilizers, colorants, fillers and other resin additives, does not cause bloom, bleed, devitrification, It is necessary to meet certain conditions such as not causing whitening or having any adverse effect on the properties of the product. Examples of conventional processability improving agents include fatty acids such as stearic acid, their metal soaps, esters, amides, higher alcohols such as stearyl alcohol, paraffins, and waxes. .
In addition, it is also known to add inorganic substances such as silicon oxide 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, impairing initial coloring and transparency. Paraffins generally tend to bloom, and metal soaps tend to plate out and are often unsuitable for clear formulations. Furthermore, the addition of inorganic substances always has an adverse effect on the optical, physical, and electrical properties of the resin, and in many cases even reduces processability. Moreover, these processability improving agents hardly improve impact resistance. In recent years, it has good compatibility with resins and does not impair transparency.
Acrylic oligomers or modified products thereof have been proposed as lubricants that do not cause bloom, bleed, or plate-out. However, in general, the compatibility or transparency of lubricants and the strength of lubricity are contradictory properties, and these oligomers are no exception. That is, although the oligomer-type lubricants have excellent transparency, they do not have sufficient lubricity, and their industrial use is limited. Lubricity can be improved to some extent by increasing the polymerization degree of the oligomer, using a long-chain alkyl ester, or introducing a polar group, but all of these results in a decrease in transparency. As a result of extensive studies in view of the above points, the inventors of the present invention have found that the processing method not only does not cause bloom, bleed, or plate-out, but also achieves a process that harmonizes the conflicting properties of compatibility, transparency, and slipperiness. We have succeeded in finding a sex improving agent and have arrived at the present invention. That is, the present invention provides at least one group represented by the following formula [] in the molecule. (In the formula, R represents a trivalent to hexavalent polyhydric alcohol residue, R' represents a carboxylic acid residue, a = 1 to 6,
b=0-5, c=0-4, a+b=2-6 and a
+b+c=3 to 6. The present invention relates to a synthetic resin composition with improved processability, which is obtained by adding an oligomer whose main monomer is an alkyl ester of α,β-monoethylenically unsaturated carboxylic acid having the following formula or a modified oligomer thereof. Examples of the polyhydric alcohol residue represented by R in the formula [] according to the present invention include trimethylolethane, trimethylolpropane, triethanolamine, triisopropanolamine,
Glycerin, tris(hydroxyethyl)isocyanurate, pentaerythritol, N,N,
Examples include residues of trihydric or higher polyhydric alcohols such as N,N,-tetrakis(2-hydroxypropyl)ethylenediamine, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, sorbitan monopalmitate. Also included are residues of alcohols obtained by adding ethylene oxide or propylene oxide to the above alcohols. The carboxylic acid residues represented by R′ include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, 2-ethylhexylic acid, pelargonic acid, lauric acid, stearic acid, undecylenic acid, oleic acid, linoleic acid, linoleic acid, isostearic acid, methoxyacetic acid, ethoxy Examples include residues of aliphatic monocarboxylic acids such as ethoxypropionic acid, poxytriethoxypropionic acid, hexoxyethoxyethoxypropionic acid, octylthioacetic acid, and laurylthiopropionic acid. In the oligomer whose main monomer is an alkyl ester of an α,β-monoethylenically unsaturated carboxylic acid having a group represented by the above formula [] or its modified oligomer, an α,β-olefin system constituting the monomer Examples of unsaturated carboxylic acids include acrylic acid,
Examples include methacrylic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and itaconic acid. The alkyl may be straight chain, branched, cyclic, or substituted with one or more carbon atoms, such as methyl, ethyl,
Isopropyl, n-butyl, isobutyl, tertiary
Butyl, pentyl, cyclohexyl, hexyl,
Examples include groups such as n-octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, etc., and the oligomer according to the present invention has at least one monomer selected from these groups as the main monomer. Depending on the purpose, other vinyl monomers such as ethylene, propylene, butene-1, etc.
Olefin, styrene, chlorstyrene, acrylonitrile, acrylamide, vinyl acetate, butadiene, vinyl alcohol, vinyl butyral,
It may also contain monomer units such as vinyl acetal. Examples of modified oligomers include the aforementioned oligomers in which groups represented by the following formulas are directly bonded to the oligomer skeleton. -COOH, -COOM ¹ 1/k,

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[Formula] (In the formula, R ¹ , R ² and R ³ represent alkyl, aryl, or a substituted group thereof, and R ⁴ and R ⁵ each represent a hydrogen atom, alkyl, aryl, or a substituted group thereof. , R ⁶ represents alkyl, aryl, alkylene, arylene or a substituted group thereof, R ⁷ represents ethylene or propylene, M ₁ represents Na, K, Mg, Ca, Sr, Ba, Zn, Sn
, M ₂ represents Mg, Ca, Sr, Ba, Zn, Sn or (R ¹ ) ₂ Sn, X ¹ represents an oxygen atom or a sulfur atom, and X ² represents an oxygen atom, a sulfur atom, or a dibasic acid. residue,
Represents a mercaptocarboxylic acid residue or a dimercaptan residue, and X ³ is -S-, -O-, -NH- or -
COO-, k indicates the valence of M ₁ , 1 is 0
~3, m represents 4 to 50, and n represents 1 or 2. ) The polyhydric alcohol-modified oligomer having a group represented by the formula [] according to the present invention can be prepared by adjusting the degree of polymerization with an initiator, polymerization in an active solvent, ionic low polymerization,
Transesterification of an oligomer easily obtained by a known method such as low polymerization with an organometallic complex or an oligomer further modified as necessary with a polyhydric alcohol or a partial ester thereof, or
obtained by esterification or transesterification of a mixture of oligomers and monocarboxylic acids or their esters with polyhydric alcohols or partial esters thereof;
Although it can be easily obtained by using a polyhydric alcohol unsaturated carboxylic acid ester as a part of the monomer during oligomer synthesis, it is not limited by the manufacturing method. The polyhydric alcohol-modified oligomer according to the present invention may be used as an unmodified oligomer or a mixture with other oligomers, or may be diluted with a solvent. The degree of polymerization of the individual oligomers or modified oligomer components bonded by polyhydric alcohol in the polyhydric alcohol-modified oligomer according to the present invention is
The number is preferably 50 or less, and the total number of each oligomer constitutional unit is preferably 150 or less. Synthesis examples of polyhydric alcohol-modified oligomers are shown below, but the present invention is not limited by these synthesis examples. Synthesis Example 1 Synthesis of No. 1 Compound (Table 1) 100 g of n-butyl acrylate oligomer (n = 7) using pseudocumene as a telogen, 19.2 g of dipentaerythritol dioleate, and 0.06 g of isopropyl titanate were placed in a flask and heated under a nitrogen stream. The n-butanol was removed by reaction at 200°C for 3 hours in a medium atmosphere and at 200°C at 3 mmH for 1 hour, followed by filtration through Celite. 8.7g (theoretical amount = 7.29g) of liquid mainly composed of n-butanol was distilled out, OHV = 0.2
108.2 g of a pale brown viscous liquid was obtained. Synthesis Example 2 Synthesis of Compounds No. 12 to No. 16 100 g of 2-ethylhexyl acrylate oligomer (n=12) synthesized by anionic polymerization using sodium methoxide as an initiator, 0.77 g of pentaerythritol, and isopropyl titanate.
Place 0.05g in a flask and incubate at 220°C in a nitrogen stream for 30 minutes.
The 2-ethylhexanol was removed by a reaction at 3 mmHg and 220° C. for 1 hour, followed by filtration through Celite. 3.5g (theoretical amount = 2.95g) of liquid mainly composed of 2-ethylhexanol was distilled out, OHV = 0.1
96.3 g of slightly yellow viscous liquid was obtained. Thereafter, using the above pentaerythritol condensation oligomer, sodium salt, zinc salt,
Calcium salt and dioctyltin salt were synthesized. Synthesis Example 3 Synthesis of Compound No. 5 100 g of n-butyl acrylate, 1.53 g of pentaerythritol tetraacrylate, and 180 g of p-cymene were placed in a flask and heated to reflux temperature (157 to 175
℃) for 4 hours, further reacted at 175℃ for 2 hours,
After removing the solvent for 1 hour to mmHg200℃, 130-140
It was filtered through Celite at ℃. 179g of p-cymene was recovered, a colorless transparent viscous liquid with a viscosity of 18500cP (25℃)
94.5g was obtained. n-Butyl acrylate, which was synthesized in exactly the same way except without using pentaerythritol tetraacrylate, had a viscosity of 7200 cP (25
℃), n=15 (vapor pressure equilibrium method). A dibutyltin salt was obtained by a conventional method using the above pentaerythritol condensation oligomer. The compounds shown in Table 1 were synthesized in the same manner.

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[Table] Although the amount of the above-mentioned oligomer or its modified oligomer according to the present invention is not particularly limited,
It is preferably 0.005 to 5 parts by weight per 100 parts by weight. In the present invention, phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate ester plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers are used depending on the application. It can be used as appropriate, and a specific example is JP-A-49
Various plasticizers such as those disclosed in Japanese Patent No.-57052 can be used. Adding an antioxidant to the composition of the present invention increases the oxidative deterioration prevention properties of the present invention, so it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, etc.
Various antioxidants such as those disclosed in Japanese Patent No. 78692 can be used. 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 benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazines, piperidines, etc. It is disclosed in Publication No. 1978-78692. Generally, when metal soaps are used as stabilizers for halogen-containing synthetic resins, some are often used alone, such as organotin stabilizers and lead soaps, but cadmium, barium, zinc, calcium, etc. Metal soaps such as magnesium, strontium, potassium, and sodium are often used in combination of two or more of these. for example,
Cd―Ba, Cd―Ba―Zn, Ba―Zn, Ca―Zn, Ca
―Mg, Ca―Mg―Zn, Cd―Ba―Organic tin, Cd―
Many combinations are adopted depending on the purpose of use, such as Ba-Pb, Ca-Sr, Zn-X, and Zn-Na. Others as necessary, such as epoxy stabilizers, organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, other lubricants, anti-hardening agents, flame retardants. , light stabilizers, ultraviolet absorbers, luminescent agents, fungicides, fungicides, metal deactivators, photodegradants, nonmetallic stabilizers, epoxy resins, borate esters, thiourea derivatives, processing aids, release agents, A molding agent and the like can be included. 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 to the following examples. Example 1 In order to examine the effect of the compound according to the present invention on soft polyvinyl chloride resin as a lubricant, a kneading test was conducted using a calendar roll using the following formulation, and the onset time of adhesion on the roll and the occurrence of coloring were investigated. . In addition, thermal stability testing, transparency,
Peelability and roll staining tests were conducted. The results are shown in Table 2 below. The transparency is visually evaluated in five stages, and the lower the number, the better the transparency. <Composition> PVC (Geon103EP) 100 parts by weight DOP 60 Epoxidized soybean oil 2 Ba-nonyl phenate 0.5 Zn-toluate 0.5 Octyl diphenyl phosphite 0.5 Lubricant (Table 2) 0.3

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[Table] Example 2 In order to examine the effect of the compound of the present invention on hard PVC, the adhesion time to the roll was measured in the same manner as in Example 1 using the following formulation, and the peelability was also examined. The results are shown in Table-3. <Composition> PVC (Geon103EP-8) 100 parts by weight dibutyltin bis (butyl malate)
2.0 Lubricant (Table-3) 0.3

[Table] Example 3 In order to examine the effect of the compound according to the present invention on a polymer blend of PVC resin and ABS resin, the following formulation was kneaded for 5 minutes on a heated roll at 160°C.
The peelability from the roll was checked. The results are shown in Table 4 below.
Shown below. <Composition> PVC (Geon103EP-8) 50 parts by weight ABS (Toyorak 102) 50 dibutyltin mercaptopropionate
1.5 Additives (Table-4) 1.0

[Table] Example 4 In order to see the effect of the processing aid of the present invention, rubber-modified polystyrene resin (Dialex
HT886: Mitsubishi Monsanto) 1.0 part by weight of a processing aid was added to 100 parts by weight, and a spiral flow test was conducted using an injection molding machine at 200°C and 800 kg/ ^cm2 . The results are shown in Table 5 below.

[Table] Example 5 After mixing 2 parts by weight of the processing aid listed in Table 6 with 100 parts by weight of commercially available ABS resin, a test piece was prepared by injection molding. Next, the Izot value was measured using an impact tester, and the flow characteristics were measured using a spiral flow using an injection molding machine.
The results are shown in Table-6.

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[Table] Example 6 In order to examine the processability of the ethylene-vinyl acetate copolymer resin composition of the present invention, a compound consisting of the following formulation was kneaded on a roll (roll temperature 130°C, roll gap 0.3 mm, rotation The peelability from the roll after 5 minutes (several 30 rpm) was examined. The results are shown in Table-7. <Composition> Ethylene-vinyl acetate copolymer resin (vinyl acetate content 14%) 100 parts by weight BHT 0.1 Additives (Table 7) 0.4

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[Table] Example 7 In order to examine the lubricity effect of the processability improving agent system according to the present invention, a resin compound obtained by adding 1.0 parts by weight of a lubricant (Table 8) to 100 parts by weight of the resin was subjected to a highly improved formula. The amount of plunger descent (mm/sec) was measured using a flow tester. The results are shown in Table 8. The measurement conditions for the Koka type flow tester are as follows. PE: 120℃ 50Kg/cm ² PS (GP): 190 〃 PP: 200 〃 PMMA: 200 〃 Below, unless otherwise specified, the following abbreviations and products were used for resins. PE: Polyethylene (Shorex 6050, manufactured by Nippon Olefin Chemical Co., Ltd.), PS (GP): GP polystyrene (Copal 8, manufactured by Nippon Olefin Chemical Co., Ltd.),
PP: Polypropylene (Profax 6501, manufactured by Hercules), PMMA: Polymethyl methacrylate resin (Acrypet M, manufactured by Mitsubishi Rayon)

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Claims (1)

[Claims] 1. At least one group represented by the following formula [] in the molecule (In the formula, R represents a trivalent to hexavalent polyhydric alcohol residue, R' represents a carboxylic acid residue, a = 1 to 6,
b=0-5, c=0-4, a+b=2-6 and a
+b+c=3 to 6. 1. A synthetic resin composition with improved processability, which comprises adding an oligomer whose main monomer is an alkyl ester of an α,β-monoethylenically unsaturated carboxylic acid having the following formula or a modified oligomer thereof.