JPH0321654A - Resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to a novel resin composition, more specifically, a novel resin composition containing a polyvinyl chloride resin or a polyvinylidene chloride resin and a polyamideimide elastomer as basic resin components, which is whale resistant and durable. This invention relates to a resin composition that also has antistatic properties.

Conventional technology Conventionally, polyvinyl chloride resins have various hardnesses ranging from soft types to hard types by changing the amount of plasticizer added, and have characteristics such as excellent flame retardancy. From, for example, sheets, pipes, tubes,
It is widely used as a material for films, etc., while polyvinylidene chloride resin is used as a material for films, artificial turf, nets, etc.

However, these polyvinyl chloride resins and polyvinylidene chloride resins have drawbacks such as the fact that their molded products are easily charged with static electricity, and dust and dirt may adhere to the surface. In addition to the inherently desirable properties, there has been a desire to develop a protective material that has antistatic properties.

Conventionally, in order to impart chargeability to the polyvinyl chloride resin or polyvinylidene chloride resin, a surfactant has been mixed in, but in this method, the surfactant tends to bleed out from the resin. , the disadvantage is that the effect is temporary.

On the other hand, blending polyether ester amide with polyvinyl chloride resin gives the resin flexibility, and unlike when plasticizers such as dioctyl phthalate are used, there is no bleed-out and excellent low-temperature and high-temperature properties are imparted. However, a similar method has been disclosed (Japanese Patent Application Laid-Open No. 58-32646).
, there is no mention of antistatic properties.

In this way, there is a desire for a resin that not only retains the excellent flame retardancy characteristic of polyvinyl chloride resin and polyvinylidene chloride resin, but also has permanent antistatic properties added to these resins. The reality is that such a resin composition has not been developed to date.

Problems to be Solved by the Invention Under these circumstances, the present invention provides a polyvinyl chloride resin or polyvinylidene chloride resin composition that has both excellent flame retardancy and durable antistatic properties. It was done for the purpose of

Means for Solving the Problems As a result of extensive research in order to impart permanent antistatic properties to polyvinyl chloride resin and polyvinylidene chloride resin, the present inventors discovered that polyoxyethylene glycol was used as a soft segment. , a polyamideimide elastomer whose hard segment is polyamideimide dicarboxylic acid obtained from caprolactam and an aromatic polycarboxylic acid capable of forming at least one imide ring, such as trimellitic acid or pyromellitic acid, is polychlorinated. It is compatible with vinyl resins and polyvinylidene chloride resins, and is also heat resistant, and when blended in relatively small amounts with the resins,
We have discovered that it is possible to impart lasting antistatic properties without sacrificing its desirable properties, and based on this knowledge, we have accomplished the present invention.

That is, the present invention comprises (A) a polyvinyl chloride resin or a polyvinylidene chloride resin, and (B) (a) Kabukuchi lactam, (b) a trivalent or tetravalent aromatic aromatic compound capable of forming at least one imide ring. group polycarboxylic acids, (c) polyoxyethylene glycol or polyoxyalkylene glycol mixtures based on polyoxyethylene glycol and optionally (d)
A polyamideimide elastomer obtained from at least one diamine having 2 to 10 carbon atoms, containing 40 to 85% by weight of component (c), and having a relative viscosity of 1.5 or more at a temperature of 30°C, by weight. The object of the present invention is to provide a resin composition characterized by containing the resin composition in a ratio of 60:40 to 95:5.

The present invention will be explained in detail below.

Examples of the polyvinyl chloride resin or polyvinylidene chloride resin used as component (A) of the composition of the present invention include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, and vinyl chloride-acrylic acid ester copolymer. Polymers such as vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, and ethylene-vinyl chloride copolymer are used, but from the viewpoint of flame retardancy, the content of vinyl chloride units and vinylidene chloride units is The content is preferably 50 mol% or more.

Next, the polyamideimide elastomer as component (B) of the composition of the present invention contains (a) Kabukuchi lactam, (b) trivalent or tetravalent polycarboxylic acid, and (c) polyoxyethylene glycol or polyoxy Component (c) is composed of a mixture of ethylene glycol and polyoxyalkylene glycol, and furthermore, a polyamideimide which becomes a hard segment is obtained from components (a) and (b), and this is a so7to segment. It is a multi-pack type copolymer that is linked with glycols through ester bonds.

As the Iff component (b), a trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring, or an acid anhydride thereof is used.

(b) As the trivalent tricarboxylic acid used as the component, specifically, 1.2.4-}limellitic acid, 1.2
．． 5-naphthalene tricanoleponic acid, 2.6.7-naphthalene tricarponic acid, 3.3',4-diphenyltricarboxylic acid, penzo7enone-3.3',4-tricarboxylic acid, dipheninoles Nolehon-3.3',4-
} IJ canoleponic acid, diphenylinoleate 3.
Examples include 3'4-trivalent noleponic acid.

In addition, as the tetravalent tetracarboxylic acid, specifically,
Pyromellitic acid, diphenyl-2.2',3.3'tetracanolebonic acid, betazophenone ~2.2'. 3.3'
Tetracarboxylic acid, di7enyl sulfone-2.2'. 3
．． 3'-tetracarboxylic acid, diphenyl ether-2.
2'. Examples include 3.3'-tetracarboxylic acid.

These polycarboxylic acids are used in substantially equimolar amounts, that is, 0.9 to 1.1 times the molar amount to the glycol (c).

Polyamideimide, which is a hard segment, is involved in the heat resistance, strength, hardness, and compatibility with polyvinyl chloride resin and polyvinylidene chloride resin of the elastomer.
The polyamideimide content in this elastomer is 15
It is necessary that the amount is 601 L%. If this content is less than 15% by weight, it becomes difficult to manufacture the elastomer.
; it is undesirable because it lowers the strength of the elastomer, and if it exceeds 60% by weight, the compatibility deteriorates;
This is not preferred because the melting point becomes high and it becomes difficult to knead with polyvinyl chloride resin or polyvinylidene chloride resin.

In addition, the number average molecular weight of polyamideimide is 500 or more,
It is preferably 2000 or less, more preferably 5
00 or less, and 1500 or less. If the number average molecular weight of polyamide-imide is less than 500, the melting point will be low and the heat resistance will be reduced, and if it exceeds 2000, the melting point will be high and the kneadability with polyvinyl chloride resin or polyvinylidene chloride resin will be poor. If the kneading temperature is increased, the polyvinyl chloride resin or polyhynylidene chloride resin will be more likely to decompose, which is not preferable.

In the composition of the present invention, when diamine (d) is used in combination to roughly introduce imide rings into polyamideimide in order to improve heat resistance, the polycarboxylic acid glycol component (c) and diamine or It is used in an amount of 0.9 to 1.1 times the total number of moles of (d).

This (d) certain diamines include ethylene diamine, tetramethylene diamine, hexamethylene diamine,
Examples include phenylenediamine. The amount used is preferably at most 1 mole of glycol (c); if more than this is used, it will be difficult to obtain a homogeneous elastomer, and the compatibility with polyvinyl chloride resin and polyvinylidene chloride resin may be affected. This is not preferable because it reduces the

As the (c) R component in the polyamideimide elastomer, polyoxyethylene glycol or a mixture of polyoxyethylene glycol and a polyokine alkylene glycol other than polyoxyethylene glycol is used.

The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is preferably within the range of 500 to 5,000. If it is less than 500, it is not preferable because the melting point may become low and heat resistance may be insufficient, although it depends on the composition of the elastomer. Also, 5000
Exceeding this is not preferable because it makes it difficult to maintain the tough elastomer shape.

The polyoxyalkylene glycol that can be used in combination with polyoxyethylene glycol is less than 50% by weight of the glycol component and has a number average molecular weight of 500 to 50%.
00 polyoxytetramethylene glycol, modified polyoxinetetramethylene glycol, polyoxybrobylene glycol, etc. can be used.

As the modified polyoxytetramethylene glycol, ordinary polyoxytetramethylene glycol = (cHz
) Examples include those in which a-0- is partially replaced with -R-0-. Here, R is an alkylene group having 2 to IO carbon atoms, such as ethylene group, 1,2-propylene group, 1
．． Examples include a 3-propylene group, a 2-methyl-1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, a pentamethylene group, and a hexamethylene group. There is no particular restriction on the amount of modification, but it is usually selected within the range of 3 to 50% by weight. The amount of modification and the type of alkylene group are appropriately selected depending on the required properties of the polyvinyl chloride resin or polyvinylidene chloride resin composition, such as low-temperature impact resistance and heat resistance.

This modified polyoxytetramethylene glycol can be produced, for example, by copolymerization of tetrahydro-7rane and diol using a heteropolyacid as a catalyst, or by copolymerization of diol or a cyclic ether which is a condensation product of diol and butanediol. I can do it.

Regarding the method for producing the polyamide-imide elastomer used in the composition of the present invention, any method may be used as long as it can produce a homogeneous amide-imide elastomer, and for example, the following method may be used.

Caprolactam component (a), aromatic polycarbonate component a (b) and glycol component (c) are combined into component (b) and (
c) Mixing the components in a substantially equimolar ratio, while maintaining the water content in the raw polymer at 0.1 to itt%,
150-300'O, more preferably 180-280°
This is a method of polymerizing with C. In this method, the reaction temperature can also be raised stepwise during dehydration condensation.

At this time, some of the Kabukuchi lactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture.

The reaction mixture after removing unreacted caprolactam can be further polymerized by post-polymerization under reduced pressure at 200 to 300° C., preferably 230 to 280° C., if necessary.

In this reaction method, esterification and amidation occur simultaneously during the dehydration condensation process to prevent coarse phase separation, thereby producing a homogeneous and transparent elastomer. This has excellent compatibility with polyvinyl chloride resin and polyvinylidene chloride resin, and when kneaded with polyvinyl chloride resin and polyvinylidene chloride resin, it exhibits excellent antistatic effects and mechanical properties.

The esterification reaction and the polymerization of Kabukuchi lactam are caused simultaneously, and each reaction rate is controlled.
In order to obtain a transparent and homogeneous elastomer, the water produced is removed from the system and the water content of the reaction system is maintained in the range of 0.1 to 1% by weight during polymerization. is preferable. When this water content exceeds 1% by weight, polymerization of Kabukuchi lactam takes priority and coarse phase separation occurs, while when it is less than 0.1% by weight, esterification takes priority and Kabukuchi lactam does not react, resulting in the desired reaction. Unable to obtain elastomer. This water content is appropriately selected within the above range depending on the desired physical properties of the elastomer.

Furthermore, in this reaction, the water content in the reaction system may be gradually reduced as the reaction progresses, if desired.

This water content can be controlled, for example, by controlling reaction conditions such as the reaction temperature, the flow rate of inert gas introduced, and the degree of vacuum, or by changing the reactor structure.

The degree of polymerization of the polyamideimide elastomer used in the composition of the present invention can be changed as desired, but
Preferably, the relative viscosity measured at 30'O at 0.5% (weight/volume X) in metacresol is greater than or equal to 1.5. If it is lower than 1.5, sufficient mechanical properties cannot be exhibited, and even when kneaded with polyvinyl chloride resin or polyvinylidene chloride resin, mechanical properties may be insufficient.

When diamine (d) is used in combination, the reaction can be carried out either in one step or in two steps. The former consists of caprolactam (a), a polycarboxylic acid component (b), a glycol component (c), and a diamine component (d
) are simultaneously prepared and reacted. The latter is a polycarboxylic acid component (b) and a diamine component (d)
This is a method in which caprolactam (a) and glycol (c) are reacted together.

When producing a polyamideimide elastomer, an esterification catalyst can be used as a polymerization promoter.

Examples of the polymerization accelerator include phosphoric acid, polyphosphoric acid,
Phosphorus compounds such as metaphosphoric acid; Tetraalkyl orthotitanate such as tetrabutyl orthotitanate; Tin-based catalysts such as dibutyltin oxide and dibutyltin laurate; Manganese-based catalysts such as manganese acetate; Antimony-based catalysts such as antimony trioxide; Lead acetate, etc. A lead-based catalyst is suitable. The catalyst may be added at the initial stage of polymerization or at the middle stage of polymerization.

Second, in order to increase the thermal stability of the obtained polyamide-imide elastomer, stabilizers such as various heat-resistant anti-aging agents and antioxidants can be used. It may be added at any stage. Also,
It can also be added after polymerization and before kneading with polyvinyl chloride resin or polyvinylidene chloride resin.

Examples of the heat-resistant stabilizer include N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxycinnamic acid amide), 4,4'-bis(2,6-di-t-
various hindered phenols 11 [: N,N'-bis(β-naphthyl)-p-7enylenediamine, Aromatic amines such as N,N'-diphenyl-p-7enylenediamine and poly(2.2.4-trimethyl-1.2-dihydroquinoline); Copper salts such as copper chloride and copper iodide; Examples include sulfur compounds and phosphorus compounds such as lauryl thiodipropionate.

In the composition of the present invention, the weight ratio of the polyvinyl chloride resin or polyvinylidene chloride resin as the component (A) and the polyamide-imide elastomer as the component (B) is 60:40 by weight.
It is necessary to be within the range of 95:5 to 95:5, and (
B) If the FR content is less than this, a sufficient antistatic effect cannot be obtained, and if it is more than this, flame retardancy will be insufficient, depending on the composition of the polyvinyl chloride resin or polyvinylidene chloride resin.

In the composition of the present invention, it has been found that when a polyamidoimide elastomer and an electrolyte such as sodium dodecinolevenzene snolephonate are used in combination, a remarkable synergistic effect is exhibited in terms of antistatic effect.

Examples of organic electrolytes that exhibit such effects include acid organic ammonium salts and organic phosphonium salts. Examples of the organic compound having an acidic group or its metal salt include dodecylbenzenesnorefonic acid, p-tonoleenesnorefonic acid, dodecyl diphenyl ether disulfonic acid, na7talene snolephonic acid, a condensate of na7talene snolephonic acid and honolemaline, Aromatic sulfonic acids such as sodium polystyrene sulfonate, alkyl sulfonic acids such as lauryl sulfonic acid, organic carboxylic acids such as stearic acid, lauric acid, and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate, and their Examples include alkali metal salts and alkaline earth metal salts.

Although it is effective even in the form of a free acid, it is preferable to use it in the form of an alkali metal or alkaline earth metal salt.
For example, sodium, potassium, lithium, magnesium, and calcium salts are preferred.

Examples of organic ammonium salts include organic compounds having a trimethylic group or metal salts thereof, or quaternary ammonium salts such as fluoroctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and trioctylmethylammonium bromide. Examples of organic phosphonium salts include quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide.

On the other hand, as an inorganic electrolyte, for example, NaCQ sNaB
r, KCQ1KBr, LICQSLiBr, KN
CS%LiNO,, KNO3, CaCl22, MgCf
f. Examples include.

The amount of these electrolytes added is usually 0.01 parts by weight per 100 parts by weight of the total amount of components (A) and (B). -10!
i parts, preferably in the range of 0.1 to 5 parts by weight. This amount is 0. If it is less than 1 part by weight, the effect of addition is not sufficiently exhibited, and if it exceeds 10 parts by weight, it may cause corrosion of the mold or deterioration of appearance and strength, which is not preferable.

Further, among these electrolytes, organic electrolytes are more preferable than inorganic electrolytes in terms of mold corrosion resistance and appearance.

In the composition of the present invention, other polymers may be blended in addition to the components (A) and (B). For example, (A
In order to increase the compatibility between components () and (B), polystyrene resins containing carpoxyl groups, acrylic nitrile-butadiene styrene resins (ABS resins), acrylic resins, etc. can be used. Further, in order to improve impact resistance, ABS resin, acrylic resin, etc. can be blended.

Furthermore, the composition of the present invention may contain various additives as desired, such as plasticizers such as dioctyl phthalate for imparting flexibility, pigments, dyes, reinforcing agents, etc., as desired, to the extent that the object of the present invention is not impaired. , a filler, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, an antistatic agent, a mold release agent, etc. can be contained in any process such as a kneading process or a molding process.

The composition of the present invention is prepared by mixing a certain mixture of the above-mentioned component (A), (B) to some extent, an electrolyte used as necessary, and various additive components using a known method such as a Panbury mixer mixing roll, single screw or double screw. It can be prepared by kneading using an extruder or the like. The kneading temperature at this time is 160~200℃! It is preferable to carry out within the range of .

The resin composition of the present invention thus obtained can be processed by known methods generally used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, vacuum molding, etc. Can be molded.

Effects of the Invention The resin composition of the present invention contains polyvinyl chloride resin or polyvinylidene chloride resin and polyamideimide elastomer as basic resins, and has the inherent advantages of polyvinyl chloride resin and polyvinylidene chloride resin. In addition to maintaining flame retardancy, it also has permanent antistatic properties.
It has excellent characteristics and is suitably used as a material for, for example, sheets, pipes, hoses, tubes, panel boards, record boards, films, etc.

Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.

The physical properties of the composition and elastomer were determined according to the following methods.

(1) Tensile breaking strength and tensile elongation of elastomer: AS
The measurement was carried out in an absolutely dry state using a dumbbell piece with a thickness of 1 mm according to TM D638.

(2) Relative viscosity of elastomer: 30°0% 0-5wt/vol% in metacresol
Measured under the following conditions.

(3) Thermal decomposition temperature of elastomer: The weight loss temperature was determined using a differential thermal balance at a heating rate of 10'c/
Measured in minutes.

(4) Electrostatic voltage test: 3KV with static osmosis meter (manufactured by Shishido Shokai)
An electrostatic voltage was applied, and after the voltage was removed, the time required for the charged voltage of the sample to be reduced by half was measured at 23° C. and 155% RH.

Production example l Production of polyamide-imide elastomer (B-1) In a 10Q stainless steel reaction vessel equipped with a stirrer, nitrogen inlet, and distillation tube, 2680 g of polyoxyethylene glycol (number average molecular weight 1980) and trimellitic anhydride were added. 259.4 g, Kabuchi lactam 1707 g
and pentaerythrityltetrakis [3-(3.5-
8.0 g of a 1=1 blend product (trade name: Irganox B 225: antioxidant) of di-L-butyl-4-hydroxyphenyl) flobionate] and tris(2,4-di-t-butyl-7enyl) phosphite. Preparation, 10
The pressure was reduced to 1 Torr at 0'o, and the mixture was stirred for 1 hour to remove moisture from the raw materials. After that, nitrogen was introduced and
While maintaining the pressure at around 100 ℃, the temperature was raised to 260℃.
Polymerization was carried out for a period of time, and the pressure was gradually reduced at the same temperature to distill off unreacted Kabukuchi lactam.

Next, nitrogen was introduced again to maintain the pressure at 200 Torr, and a solution of 4.0 g of tetrabutyl orthotitanate dissolved in 100 g of Kabukuchi lactam was added.
The pressure was reduced to Torr, and polymerization was carried out at the same temperature for 7 hours.

The obtained polymer is discharged into a cooling belt in the form of a gut.
Pelletized elastomer was obtained by pelletizing.

This elastomer is light brown and transparent, contains 67% by weight of polyoxyethylene glycol, and has a relative viscosity of 2.
．． 18, the tensile strength and elongation are each 310 kg/
cm”, 850%.

In addition, the thermal decomposition start temperature, 10% weight loss temperature, and 30% weight loss temperature of this elastomer are 353°C and 353°C, respectively.
It was 377'0, 394°C.

Production example 2 Boryamideimide elastomer (B-2)
500r equipped with stirrer, nitrogen inlet and distillation tube
40g of caprolactam in aQ separate flask
, polyoxyethylene glycol (number average molecular weight 204
0) 9 1g, trimellitic anhydride 11.2g, hexamethylene diamine 1.5g (molar ratio to polyoxyethylene glycol 0.3), phosphoric acid 0.15g and "Nocrac 224J 0.2g" were prepared, and the mixture was heated at 260°C.
The reaction was carried out for 4 hours while flowing nitrogen at 70 aQ/min. Next, unreacted lactam was distilled off under reduced pressure, and then 0.3 g of tetraisopropyl orthotitanate was added and reacted at 1 Torr for 5 hours to obtain a yellow transparent elastomer.

This elastomer is made of polyoxyethylene glycol 7
2% by weight, relative viscosity 1.90, tensile strength 29
5 kg/cm" and tensile elongation of 1020%, and the thermal decomposition start temperature, 10% weight loss temperature, and 30% weight loss temperature were 350°C, 403°C, and 438°C, respectively.

Examples 1 to 6 Polyvinyl chloride resin or polyvinylidene chloride resin and polyamideimide elastomer, optionally other resins, and electrolytes were blended at room temperature in the proportions shown in the table, and the mixture was placed in a single screw extruder equipped with a Dalmage-type screw. After kneading at 180℃, cylinder temperature 180℃ 1 mold temperature 60℃
Test samples were made using a 'O injection molding machine.

The charging voltage test results and appearance are also listed in the table.

Example 7 The test pieces prepared in Examples 2.3 and 4 were heated at 23°C and 55°C.
After being left for 3 months under conditions of %RH, a charging voltage test was conducted, and the charging voltage was 6 and 8.2 seconds, respectively, the same as the initial value.

Comparative Examples 1 to 3 For comparison, a withstand voltage test was conducted on a soft vinyl chloride resin and a hard vinyl chloride resin. The results are shown in the table.

Note that the resin symbols used in Examples and Comparative Examples have the following meanings.

A-1: Polyvinyl chloride resin plasticized with about 33 wt% dioctyl 7-thalerate (average degree of polymerization about 1300) A-2: Polyvinyl chloride mB'ilc average degree of polymerization about 13
00) A-3: Vinylidene chloride-vinyl chloride copolymer (molar ratio 80:20, number average molecular weight 2000) C-1: Copolymer resin of 90 parts by weight of methyl methacrylate and 10 parts by weight of methacrylic acid C-2= Methyl methacrylate resin [Delpet 80N, manufactured by Asahi Kasho Kogyo Co., Ltd.]

Claims (1)

[Scope of Claims] 1 (A) polyvinyl chloride resin or polyvinylidene chloride resin, (B) (a) caprolactam, (b) trivalent or tetravalent aromatic compound capable of forming at least one imide ring The content of component (c) is 40 to 85% by weight, obtained from polycarboxylic acid and (c) polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, and the relative value at a temperature of 30 ° C. A resin composition comprising a polyamideimide elastomer having a viscosity of 1.5 or more in a weight ratio of 60:40 to 95:5. 2 (A) polyvinyl chloride resin or polyvinylidene chloride resin, (B) (a) caprolactam, (b) trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, (c ) polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, and (d) a diamine having 2 to 10 carbon atoms, and the content of component (c) is 40 to 85% by weight. % and a polyamideimide elastomer having a relative viscosity of 1.5 or more at a temperature of 30°C in a weight ratio of 60:40 to 95:5. 3. The resin composition according to claim 1 or 2, comprising at least one electrolyte selected from organic electrolytes and inorganic electrolytes.