JPS59142234A - Organic polymeric material composition of excellent processability and improved surface property of molded product - Google Patents

Abstract

PURPOSE:The titled composition excellent in moldability and capable of providing a molded product of improved surface property, prepared by mixing an organic polymeric material with a partial ester (salt) of a specified hydroxypolycarboxylic acid. CONSTITUTION:100pts.wt. organic high-molecular resin, e.g. PVC, is mixed with 0.01-20pts.wt. preferably, 0.1-3.0pts.wt. partial ester containing at least one carboxylic acid residue in the molecule, obtained by condensing by dehydration a hydroxypolycarboxylic acid or its acetylation product, e.g., (acetylated) malic acid, with an alcohol, e.g., cyclohexanol, or its salt with an alkali (alkaline earth) metal or a Group IV metal in the periodic table, e.g., monooleyl malate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic polymer material that has excellent processability and improved surface properties of molded articles.

When organic polymeric materials, especially thermoplastic polymeric materials, are heat-formed, their fluidity decreases on the metal surface of the molding machine, and in extreme cases, there is almost no flow, resulting in excessive heat from the heating device. Thermal deterioration progresses, and as a result, the surface quality of the molded product is often impaired. In the worst case, it may not even be possible to obtain a molded product. Such a state is said to have poor workability.

Although there are varying degrees of degree depending on the molding method such as rolling molding (calendering), extrusion molding, and injection molding, the fluidity and lubricity between the organic polymer material and the metal surface during heat molding, or the mold releasability, determine the surface quality of the molded product. This has a significant impact on the quality of molded products. As a countermeasure for such cases, lubricants have been added and blended.

Examples of lubricants include metal salts of stearic acid and its derivatives, and esters with alcohols.

Amides or bisamides have been used, and montanic acid wax, behenic acid and its esters, amides, and low molecular weight polyolefins have also been used. However, these conventionally used lubricants have not yet been able to provide completely satisfactory molded products.

In other words, lubricants that improve fluidity, lubricity with metal surfaces, and mold releasability have poor compatibility with organic polymer materials, impairing transparency, and make it difficult to discharge from the surface, so-called blooming and release properties. This impairs the discharge performance and makes it more likely to cause plate-out phenomenon, which is discharge onto a metal surface. As measures to improve these problems, various lubricants have been combined or the amount added has been lowered to the limit that does not impair processability.

In particular, rolling forming (calendering) requires that the melt viscosity, fluidity, and lubricity and mold releasability between the metal surface and the metal surface during processing of the organic polymeric material composition be sufficiently balanced and well-balanced. It seems that only a very limited range of organic polymer materials, mainly made of polyvinyl chloride, are currently being put into practical use.

Olefin-based polymer materials, urethane-based polymer materials, and butadiene-based polymer materials are modified either alone or by blending or graft polymerization with vinyl chloride-based polymer materials, and are further blended with fillers, etc. However, in cases where transparency is required, it is possible to obtain a molded product by rolling after taking measures such as increasing the melt viscosity.
There are limits to the quality range of molded products, and sufficient application has not progressed. This is due to the lack of a lubricant that sufficiently improves the lubricity and mold release properties with metal surfaces and has excellent transparency, discharge properties, and plate-out properties.

As a result of extensive research and consideration, the present inventors have discovered that oxypolyhydric carboxylic acid or its acetylated product is added to 100 parts by weight of an organic polymer material as a method for improving processability and inferior surface properties of molded products. Partial esters with at least one carboxylic acid group remaining in the molecule obtained by dehydration condensation with alcohols, and at least one kind of their salts with alkali metals, alkaline earth metals, and metals from group Ⅰ of the periodic table. Alternatively, it has been found that the object can be achieved by adding two or more of them in an amount of 0.01 parts by weight to 20 parts by weight, or preferably 0.1 parts by weight to 3 parts by weight, and the present invention has been completed.

In the present invention, partial esters of oxypolycarboxylic acids or acetylated polycarboxylic acids, or
: Oxypolycarboxylic acids constituting c-stellate include malic acid, citric acid, tartaric acid, acetylated malic acid,
Examples include acetylated citric acid and acetylated tartaric acid.

In the present invention, examples of alcohols constituting partial esters or partial ester salts of oxypolycarboxylic acids or acetylated polycarboxylic acids include clohexanol, methanol, butanol, ethanol, furopanol, 2-ethylhexanol. , 1-octatool, 3.5.5-) Limethyl-l-hexanol, tritecanol, instearyl alcohol, isobenzyl alcohol, octatool, lauryl alcohol, 1st
/yl alcohol, caprylic alcohol, isoamyl alcohol, isotecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, H, C0~Q<unsaturated 7 #coal, α-, +trogin ethyl oleyl alcohol, other oxocols 12-1
3. Mixed alcohol 7' products such as Oxycol 7-10 (mixed alcohol manufactured by Yasan Kagaku), Dopanol 23, Dopanol 246, and Dopanol 25 (mixed alcohol manufactured by Mitsubishi Yuka) are praised.

In the present invention, the composition of the present invention may be blended into the organic polymer material as it is during processing, or may be mixed with other additives before processing and then blended into the organic polymer material.

In the present invention, phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers are used as appropriate depending on the application. can.

Adding an antioxidant to the organic polymer material used in the present invention can increase the oxidative deterioration prevention properties of the organic polymer material, so it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur antioxidants, and the like.

By adding a light stabilizer to the organic polymer material used in the present invention, the light stability can be improved, so it is also possible to select and use this as appropriate depending on the purpose of use. These include benzopheno7s, benzotriazoles, saliprates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel, chromium or manganese salts or salts, diamides, piperidine, etc. and triazine series.

In general, metal soaps can be used as stabilizers for organic polymer materials including halogen-containing resins, but in this case, they are often used alone, such as organotin stabilizers and lead soaps. Metal soaps such as , cadmium, barium, zinc, carunium, red sea bream, strontium, sodium, and potassium are often used in combination of two or more of these.For example, Cd-Ba.
, Cd-13a-Zn, F3a-Zn,
Ca-Zn, Ca-Mg, Ca-Mg-Zn, C
d -J3a-organotin, organotin-Ba, organotin-CaS
Zn-8r, Cd-13a-Pri, Ca-8r,
Many combinations are adopted depending on the purpose of use, such as Zn-Na and Zn-K.

Furthermore, in order to obtain a non-toxic organic polymer material composition, a non-toxic halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained by selecting and using a non-toxic metal soap among the above-mentioned ordinary metal soaps. can get.

ゞ゛Others may be added as necessary, such as epoxy stabilizers, organic catalysts, pigments, fillers, blowing agents, antistatic agents, etc.
Antifogging agent, plate-out prevention agent, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifungal agent, antibacterial agent, metal deactivator, photodegrading agent, nonmetallic stabilizer, Evokin resin, boric acid ester,
Thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included.

Organic polymer materials 1 used in the present invention include polyvinyl chloride, polyvinyritine chloride, polybutene, polyethylene, polystyrene, polypropylene, polyvinyl acetate,
Polyacrylonitrile, ethyl-vinyl chloride copolymer, polyurethane, ethylene-propylene copolymer (including E P I M), ethylene-vinyl acetate copolymer Combined, vinyl chloride
Vinyl acetate copolymer, chlorinated polyethylene, polymethyl methacrylate, polyacetal, polycarbonate,
Polyethylenete1. / Lid 1/-t, nylon, ethylene-vinyl acetate-vinyl chloride copolymer, ethyl 1/-vinyl acetate-carbon oxide copolymer (Elvaloy), methacrylic acid-butadiene-styrene copolymer, polybutylene 1/
ntelephthalate, acrylonitrile-butadiene
Styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, polyamide, styrene-acrylonitrile copolymer, chlorinated polyethylene/acrylic. Nitrile-styrene copolymer, polyallyl ether, chloroprene rubber, chloride rubber, neoprene rubber, natural rubber, polyvinyl butyral, a blend of two or more selected from the group consisting of nitrile rubber, block copolymer, graft Copolymers can be mentioned.

Examples of partial esters of oxypolycarboxylic acid or acetylated polycarboxylic acid and hydroquine alkyl or hydroquine alkenyl used in the present invention are as follows, but are not limited thereto.

LV! l], malic acid monooleyl ester2. Malic acid monoinstearyl ester 3, malic acid monobehenyl ester 4, malic acid monolauryl ester 5, acetylated malic acid monooleyl ester 6, acetylated malic acid monoisostearyl ester 7, acetylated malic acid monolauryl ester 8, Acetylated malic acid monoisodecanyl ester 9, linchoic acid mono(tridecanyl) ester], Q malic acid monooleyl ester sodium salt 1 person Malic acid monooleyl ester calcium ester 1'2. Tartrate monooleyl ester 13 Tartrate monostearyl ester 14 Tartrate monocetyl ester 15, tartrate monoisodecanyl ester/l/16, tartrate monooleyl ester potassium salt]7. Tartrate monooleyl ester sodium salt 18, tartrate monolauryl ester sodium salt 19, tartrate monostearyl ester potassium salt 20, tartrate monotritecanyl ester potassium salt 21, tartrate monolauryl ester 22, tartrate monotridecanyl ester B, tartrate monobehenyl ester 24, Tartrate Monoisostearyl Ester Potassium Salt 25, Citric Acid Monooleyl Ester 26, Citric Acid Dioleyl Ester 27, Citric Acid Mono-Instearyl Ester, Citric Acid Mono-oleyl Mono-Isostearyl Ester 29, Citrate Diine Stearyl Ester 30, Monolauryl citrate 31, dilauryl citrate 32, monooleyl monolauryl citrate 33, monooleyl monostearyl citrate 34, monothecanyl citrate 35, didecanyl citrate 36, monocetyl citrate Ester 37, Cicetyl citric acid ester 38, Monooleyl monodecanyl citric acid ester 39, Monostearyl citrate monooctyl ester 40, Monooleyl citrate monooctyl ester 41, Monooleyl citric acid ester sodium salt 42, Dio citric acid Rail ester potassium salt 43, citric acid monoisostearyl ester barium salt 44, citric acid diisostearyl ester sodium salt 45, monooleyl Nisderyl citrate calcium 46,
Citric acid dioleyl ester, <IJ rum salt 47,
Citric acid monoisostearyl ester Zinc Hanawa 48 Citric acid monooctyl monooleyl ester 49 Citric acid monooctyl monoisostearyl ester 5Q Citric acid distearyl ester 51, Citric acid monostearyl monooctyl ester Separation Citric acid monooleyl ester nocurium salt 53, Acetylated citric acid monooleyl ester, Acetylated citric acid dioleyl ester 55, Acetylated citric acid diisostearyl ester 56, Acetylated citric acid mono-1/yl monoinostearyl ester 57, Acetylated citrate monobutyl ester monooleyl ester 58, acetylated monolauryl citrate monoisostearyl ester 59, acetylated monolauryl citrate ester The partial ester of oxypolycarboxylic acid or acetylated carboxylic acid in the present invention is, for example, oxypolycarboxylic acid or acetyl ester. It can be produced by dehydration condensation-disintegration reaction using a known method from a carboxylic acid and an alcohol. In addition, each desired metal salt can be produced from the obtained partial ester and metal oxide by neutralization reaction. However, the compounds of the present invention are not limited by these production methods.

Next, Examples will be given to clarify the superiority of the organic polymer composition of the present invention, but the present invention is not limited by the following Examples.

Of the various tests in the present invention, the adhesion time on a roll is suitable for measuring rolling formability (calendering) and is considered to be the most reliable for evaluating stabilizers and lubricants from a practical standpoint. . In addition, the bloom test was performed at 40°C, R1
(After being left in a 70% atmosphere for 2 weeks, the state of discharge on the film surface was also observed. The evaluation was rated as ◎ if there was no blooming at all, followed by ○, below, ×, and XX if the most significant blooming occurred. Regarding the measurement of plate-out, there is a watch red method, but it lacks reliability as plate-out may disappear during the process or occur during rolling.Therefore, the present inventors They conducted a mouth-to-loop kneading test until it became sticky and observed the occurrence of plate-out7.The evaluation was that there was no plate-out at all until it stuck on the roll.
Disappears within 5 minutes of roll kneading or roll kneading 3
If a small amount occurs after 0 minutes, ○, roll mixing disappears within 10 minutes or roll kneading 2
A case where the plateout occurred after 0 minutes was recorded as △, a case where plateout was observed until it stuck to the roll was recorded as ×, and a more severe case was recorded as XX. Thermal stability was measured using a gear aging tester set at a predetermined temperature and expressed as the time until blackening.

Example 1 In order to see the effect of the present invention on polyvinyl chloride, a roll kneading test was conducted using two rolls with the following formulation (roll adhesion time and plate-out were observed. The sheet was pressed and tested for transparency, heat exchange, and bloom.

The results are shown in Table 2.

<Composition> Polyvinyl chloride [Sumilit 5x-11F] 10 parts by weight Di: Deoctyl phthalate 30 parts by weight Evoquinated soybean oil 3 parts by weight Zn-
Stairley 1' 0.3 parts by weight 13
a-Stearate 0.4 parts by weight 1
3a-nonylphenate 03 parts by weight Diphenyldenlphosphite 0.6 parts by weight Additives (
(including the product of the present invention) 0.3 parts by weight or less Margin Table 2 Roll adhesion time and plate-out measurement conditions 8-inch roll Roll rotation speed Front 2 Q rpm, rear 18 rpm Roll temperature 180°C Film thickness Q, 25 mm Thermal stability Measuring conditions Gear type aging tester 180°C Bloom measuring conditions Floating device Temperature 40'C: Humidity I (870% Duration 14 days Example 2 Next, ethylene-vinyl acetate-carbon oxide ternary copolymer resin and skinless In order to examine the effect of the present invention on a blend system with polyvinyl chloride, a kneading test was conducted using two rolls using the following formulation.The results are shown in Table 3.

<Formulation> Polyvinyl chloride [Vinicron 2000M] 100 parts by weight Ethylene-vinyl acetate-carbon oxide copolymer resin [Elvaloy 7421 100 parts by weight Epoxidized soybean oil 4 parts by weight Zinc stearate salt
04 parts by weight barium stearate salt o7
Part by weight Diphenyloctylbosphite 07 Part by weight 2.6-di-1-butyl-p-cresol 03 Overlapping part Additive (including the product of the present invention) 20 parts by weight or less Margin Table 3 ) 8) ) ) Δ) ) Roll adhesion time and plate-out measurement conditions 8-inch roll Roll rotation speed Front 20 rpm + n, rear 1 grpm・-ru''
Temperature 175°C Film thickness Q, 25+++m Thermal stability measurement conditions Gear type aging tester 190°C Bloom measurement conditions Floating device Temperature 40°C Humidity R1-170% Period 14 days Example 3 Next, ethylene-vinyl acetate - The effect of the present invention in tin compounding in a carbon oxide ternary copolymer resin and skinless polyvinyl chloride blend system was tested in the following formulation. The results are shown in Table 4.

<Formulation> Polyvinyl chloride [Vinicron 2000 M] 1100
Part by weight tyrene-vinyl acetate ternary copolymer resin [Elvaloy 4
+741] 40 parts by weight dibutyltin malate ester 3.0 weight 4i
0.2 parts by weight of calcium stearate 0.5 parts by weight of processing aids (Metablen P-700) Additives (including products of the present invention) 1.0 parts by weight or less
Margin Table-4 □ Roll adhesion time and full / - door measurement conditions 8 inch roll Roll rotation speed Front 20 rpm, rear 18 rpm Roll temperature 180°C Film thickness 0.25 +++ Expansion Heat stability measurement conditions Gear type aging tester Temperature 200°C Bloom measurement conditions Egg floater Temperature/1.00G Humidity 1 (1-170% Duration 14 days Example 5 Next, a blend of vinyl chloride-ethylene copolymer and ethylene-vinyl acetate terpolymer A roll cross-wire test was conducted using two rolls using a high-order formulation to examine the effects of the present invention in a system.The results are shown in Table ○.

<Formulation> Vinyl chloride-ethylene copolymer resin CPVC-VB-u ] ]100
Parts by weight Ethylene-vinyl acetate ternary copolymer resin Elvaloy #742) 60 parts by weight Epoxidized soybean oil 6 parts by weight Zinc stearate 03 parts by weight Calcium stearate 0.7 parts by weight Trisnonylphenyl phosphite 1. (l parts by weight additives (including products of the present invention)
i, o overlapping area and below Margin Table 6 01 Adhesion time and plate out measurement conditions 8 inch roll Roll rotation speed Front 20 rpm, rear 18 rpm Roll temperature 165°C Film thickness 025 Thermal stability measurement conditions Gear type Aging tester Temperature 180°C Bloom measurement conditions Egg floater Temperature 40°C Humidity RI - 170% Duration 14 days Example 6 In order to see the effect of Honrakumei on thermoplastic and plastic polyurethane distomers, the following formulation was tested.

The results of e are shown in Table 7.

(Formulation) Urethane 9-vinyl chloride copolymer resin [Aron NP 3000] 100
Parts by weight Carbonate [Hakuyahana CC3120 Parts by weight Calcium stearate 05 parts by weight Trisnonylferonyl phosphite 1.0 Parts by weight Antioxidant [
Antigen BBM) 0.5 parts by weight Processing aid [
Metablen P-700) 0.5 parts by weight Additive (
(including the product of the present invention) 0.5 parts by weight Table 7 0.1 roll adhesion time and plate-out measurement conditions 8 inch roll Roll rotation speed Front 20 r l] 11, rear 18 rpm
Roll temperature: 165°C Film thickness: 0.25 Thermal stability measurement conditions Gear type aging tester Temperature: 220'C Blue measurement conditions: Egg floater: Temperature: 40'C Humidity: R870% Duration: 14 days Example 7 Next In order to see the effect of the present invention on elastomer El)I)M, tests were carried out using the following formulation. The results are shown in Table 8.

Compound> Elastomer No. 1 PI) M (TPE-SB 750
0 J-3] 100jlj parts by weight Ca-8t 0.5 parts by weight trisnonylphenylbosphite (15, M i
- Anti-shrinking agent (Antigen BHT) 0.
3 Electric sewing part 1 Processing aid [Metaprene P-551] 0
0.5 parts by weight Additives (including products of the present invention) 1.0 parts by weight Table -
8 Voice interest 1 f′i :l! L-Rule viscosity time and plate out measurement conditions 8-inch roll Roll rotation speed Front 20 rpm, rear 18 rpm Roll temperature 175°C Film thickness 025 External stability measurement conditions Gear type aging tester Temperature 200°C 7°C Measurement conditions Egg floatation device Temperature 40°C 1 Humidity Old -170 Period 14 days Example 8 In order to see the effect of acrylonitrile-butadiene-styrene technology composite resin (ABS) and polyvinyl chloride in a predated system, There is one test with the following combination. The results are shown in Table-9.

Polyvinyl chloride [Sumirit 5X-4G: 1100 dense parts 100 parts by weight dibutyltin malate polymer [KS-1'':] 55 parts by weight dibutyltin mercapto polymer 1<8-42B-6v12] 1.
5 parts aluminum stearate 10 parts
Part by weight Magnesium stearate 10 parts by weight Additives (including products of the present invention) 20 parts by weight *1, *2 Manufactured by Kyodo Yakuhin (2) or less Inch roll Roll rotation speed: Front 20 rpm, Rear 18 rpm Roll temperature 175°C Film thickness 0.25mm Thermal stability measurement conditions Gear type aging tester Temperature 220°C Bloom measurement conditions Floating part device Temperature 40°C Humidity R1-170% Period 14-day Example 9 Next, in order to examine the effect of the present invention on a blend system of polyvinyl chloride and methacrylate ester-butadiene-styrene copolymer (MBS), a test was conducted with the following formulation. The results are shown in Tables 1 and 0.

<Formulation> Polyvinyl chloride [Sumirit Si, -7GK] 100 parts by weight MBS resin [Creno BTA-1 [, s:]
20 parts by weight Dioctyl phthalate 7 parts by weight Epoxidized soybean oil 3 parts by weight KV
-39A-5 [Kyodo Yakuhin Cd-Ba liquid stabilizer] 2 parts by weight Cadmium stearate 03 parts by weight Barium stearate 03 parts by weight Lead stearate 02 parts by weight Additives (including products of the present invention) 02 parts by weight Below is a margin Table 10 8-inch roll Roll rotation speed 2 orpm before 18 rpm after 1 Roll temperature 185°C Film thickness 025 Thermal stability measurement conditions Gear type aging tester Temperature 190'C Blue measurement conditions Floating part temperature 40'C Humidity R870% Period 14 days Patent applicant Kyodo Yakuhin Co., Ltd. Procedural amendment (voluntary) 1 Indication of the case 1982 Patent Application No. 15918 2 Name of the invention Excellent workability and improved surface properties of molded products Organic polymer composition 3 Relationship with the case of the person making the amendment Patent applicant address 5-38-5-4 Kyodo 5-chome, Isitaya-ku, Tokyo 156 Date of amendment order Initiation

Claims (1)

[Scope of Claims] 1. IOO parts by weight of an organic polymeric material obtained by dehydration condensation of an oxy/polycarphonic acid or an acetylated product thereof and an alcohol, leaving at least one carboxylic acid group in the molecule. Partial esters thereof and their alkali metal, alkaline earth metal organotin and periodic table 1V
At least one or two or more salts with group metals 00
1 part by weight to 20 parts by weight, preferably 01 parts by weight to 3 parts by weight
An organic polymer material containing 0 parts by weight. 2 Oxypolyhydric nonorboxylic acid is malic acid, tartar (Ill
An organic polymer material composition according to claim 1, in which the organic polymer material composition is 3. The organic polymer material composition according to claim 1, wherein the oxypolycarboxylic acid is citric acid. 4. The organic polymeric material composition according to claim 2, wherein the alcohol is a saturated or unsaturated aliphatic alcohol. 5. The organic polymeric material composition according to claim 3, wherein the alcohol is a saturated or unsaturated aliphatic alcohol. 6. The organic polymeric material composition according to claim 2, wherein the alcohol is an unsaturated aliphatic alcohol having 10 to 22 carbon atoms. 7. The organic polymer material composition according to claim 3, wherein the alcohol is an unsaturated aliphatic alcohol having 10 to 22 carbon atoms.