JPS6234936A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved heat resistance, flame retardance, impact resistance and improved molding and processing properties, obtained by blending a specific imidated polymer with a specific amount of a rubber-modified imidated polymer, etc. CONSTITUTION:10-80wt% of (A) animidated polymer obtained by reacting a copolymer consisting of an aromatic vinyl monomer, maleic anhydride and a vinyl monomer copolymerizable with them with ammonia and/or a primary amine and/or (B) an imide group-containing rubber modified imidated polymer obtained by subjecting B1 3-40pts.wt. rubber-like polymer and B2 60-97pts.wt. monomer blend of an aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride, etc., to graft polymerization and reacting the graft polymer with ammonia, etc., is blended with (C) 10-60wt% graft copolymer obtained by copolymerizing C1 3-80pts.wt. rubber-like polymer with C2 20-97pts.wt. mono mer mixture such as aromatic vinyl monomer, etc., (D) 0-60wt% copolymer consisting of an aromatic vinyl monomer, vinyl cyanide monomer, etc., and (E) 0-20wt% polyvinyl chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a PVC thermoplastic resin composition having excellent heat resistance, flame retardance and impact resistance.

BACKGROUND OF THE INVENTION Polyvinyl chloride resins are inherently flame retardant and are inexpensive compared to other plastics, so they are used in many applications. However, vinyl chloride resin has the major disadvantage of being brittle and having low impact resistance, especially at low temperatures.

As a means to improve the drawbacks of polyvinyl chloride, AB
S, thermoplastic polyurethane, nitrile rubber, ethylene-
It has been proposed to melt and knead a vinyl acetate copolymer or the like. In fact, a combination of ABS and polyvinyl chloride is used as a flame-retardant ABS resin to make flame-retardant housings for various electrical equipment such as televisions, office automation equipment, cash registers, and audio products, but it has a low softening temperature. However, its use was restricted due to the risk of thermal deformation during use or deformation in the hold of a ship during export.

Problems to be Solved by the Invention The present invention provides a PVC thermoplastic resin that has excellent heat resistance, flame retardancy, and impact resistance, and is easy to mold by injection molding, extrusion, vacuum forming, etc. It is something.

Means for Solving the Problems The present invention consists of the following components (A), (B), (C) and (E), and the weight of component (A) and/or component (B) is 10 to 80%. %, component (C) is 10 to 60% by weight,
Component (D) is 0-60% by weight, component (E) is 30-80%
% by weight of a thermoplastic resin composition.

Component A: A copolymer consisting of 50 to 80% by weight of an aromatic vinyl monomer, 5 to 40% by weight of maleic anhydride, and 0 to 30% by weight of a vinyl monomer copolymerizable with these, and ammonia and/or An imidized polymer obtained by reacting a primary amine.

Component B: 50 to 80% by weight of aromatic vinyl intermediate, 5 to 40% by weight of unsaturated dicarboxylic acid anhydride, and 0 vinyl monomer copolymerizable with these, based on 3 to 40 parts by weight of the rubbery polymer. A rubber-modified imidized polymer having imide groups, which is obtained by graft-polymerizing 60 to 97 parts by weight of a monomer mixture containing 30% by weight with ammonia and/or a primary amine.

Component C: 3 to 80 parts by weight of rubbery polymer, 40 to 100% by weight of aromatic vinyl intermediate, 0 to 40% by weight of vinyl cyanide monomer, and 0 vinyl monomer copolymerizable with these. A graft copolymer obtained by copolymerizing 20 to 97 parts by weight of a monomer mixture consisting of 40% by weight.

Component D: A copolymer consisting of 40 to 100% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these.

Component E: polyvinyl chloride resin containing 0 to 20% by weight of a copolymer component.

action Hereinafter, the constituent elements of the present invention will be explained together with their effects.

First, component (A) is an imidized polymer, and component (B) is a rubber-modified imidized polymer. These ingredients improve the softening point of the composition. Component (A) and/or component (B) should be present in the composition in an amount of 10 to 80% by weight.

Examples of the aromatic vinyl monomer in each component include α-methylstyrene, vinyltoluene, t-butylstyrene,
Representative examples include halogen-substituted styrene, styrene, and mixtures thereof.

Examples of unsaturated dicarboxylic anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
Maleic anhydride is particularly preferred.

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and acrylic monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate. Acid ester monomers, methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, acenaphthylene and N- Vinyl carbazole, etc., among which acrylonitrile, acrylic ester, methacrylic ester, acrylic acid,
Monomers such as methacrylic acid are preferred.

Ammonia and primary amines used in the imidization reaction of the present invention may be in either an anhydrous or aqueous solution state, and examples of primary amines include methylamine, ethylamine, n-propylamine, and 1so-propylamine. , butylamine, pentylamine, cyclohexylamine, and other alkylamines; chloro- or bromine-substituted alkylamines; aromatic amines such as aniline, tolylamine, naphthylamine; and halogen-substituted aromatic amines such as chloro- or bromine-substituted aniline.

Regarding the component (A) and the component (B), for example, Japanese Patent Application Laid-Open No. 57-55801, Japanese Patent Publication No. 5111-43494,
It can be manufactured by the method disclosed in Japanese Patent Application No. 58-218514.

Next, component (C) is a rubbery graft copolymer, which mainly imparts impact resistance to the composition. ([E) in the composition
The blending ratio of the components is 10 to 60% by weight. If the blending ratio of component (C) is less than 10% by weight, the impact resistance decreases and becomes brittle, making it impractical. Moreover, if it exceeds 60% by weight, the flammability or heat resistance will decrease, and the purpose will not be achieved.

Component (D) is used to adjust the fluidity of the entire system, and can be used in an amount of 0 to 60% by weight in the composition.

The aromatic vinyl monomers and copolymerizable vinyl monomers used for component (C) and (D) ji can be the same as those exemplified for (A) ji.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, and ethylene-
Propylene copolymers, ethylene-propylene-diene copolymers, block copolymers of butadiene and aromatic vinyl, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable with them. Combination etc. are used.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred.

Vinyl monomers that can be copolymerized with these include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate;
Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acidamide, acenaphthylene and N
-Vinyl carbazole and the like. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred.

Component (C) and component (D) are, for example,
It can be manufactured by the method disclosed in No. 3494.

Next, the polyvinyl chloride resin of component (D) refers to a vinyl chloride homopolymer or a copolymer containing up to 20% by weight of other components.

Typical examples of the other components mentioned above include vinyl acetate, vinylidene chloride, and olefin. Commercially available polyvinyl chloride resins can be used. It is added in an amount of 30 to 80% by weight in the composition to impart flame retardancy.

Next, as a preferred method for producing the composition of the present invention, A, B,
A thermoplastic resin composition consisting of components C, D, and E is applied to a part between the feedro and the ventro, and a cylinder whose cross section perpendicular to the axis is polygonal or has a pseudo-polygonal shape consisting of a partial surface;
It is possible to present a manufacturing method using an l-axis special extruder having a kneading zone consisting of a pseudo-polygonal screw with a polygonal or partially curved screw cross section at a corresponding position.

The softening point of each polymer component of the composition of the present invention is
In terms of the Vicat softening temperature in the case of g, for example, component A: about 160°C, 33tt, 130°C, below room temperature, D: about 85°C, E // about 75°C, which are different and widely separated from each other.

If these components are mixed in an ordinary l-screw extruder consisting of a cylinder with a circular cross section, the low softening point components such as component D and E will melt first, and the components A and B will melt first.
Since the high softening point components, such as , are in a state where they float like stones, the high softening point components are not sheared and remain undissolved, making it difficult to obtain a homogeneous mixture.

Therefore, the heat resistance of the obtained composition was insufficient, the impact resistance was also low, and flash caused by unmelted materials occurred during actual molding. Therefore, after considering various mixing methods, we decided to use an extruder with a mixed line mechanism consisting of a polygonal screw/cylinder immediately after the feeder, so that the fed powder could be strongly kneaded into a semi-gelled state immediately. It was found that a homogeneous mixture could be obtained by Applicable extruders are, for example, NVC
Examples include a die extruder (Nakatani Kikai) and a Mitsubishi HM extruder (Mitsubishi Heavy Industries).

The present invention will be explained below with reference to Examples. Note that all parts in the examples are expressed in parts by weight.

Example 1 Experimental example (1) Production of component A (a) Production of aromatic vinyl-maleic anhydride copolymer After charging 75 parts of styrene into an autoclave equipped with a stirrer and replacing the inside of the system with nitrogen gas. It was heated to a temperature of 80°C. A solution of 25 parts of maleic anhydride and 0.3 parts of benzoyl peroxide dissolved in 50 parts of methyl ethyl ketone was added to this over 10 hours. Another 2 hours after addition, temperature 8
It was kept at 0°C. A portion of the viscous reaction solution was sampled and unreacted monomer was quantified by gas chromatography to calculate the polymerization rate and the content of maleic anhydride in the polymer. Add methyl ethyl ketone 15 to the remaining reaction solution.
The mixture was cooled to room temperature, poured into 800 parts of methanol with vigorous stirring, filtered and dried to obtain a white powdered maleic anhydride copolymer.

(b) Production of imidized polymer 30 parts of the maleic anhydride copolymer obtained in (a) and 0.3 parts of triethylamine were dissolved in 70 parts of methyl ethyl ketone in an autoclave, and 1 Add 8.68 parts of aniline of 0.05 times molar equivalent to 13
The reaction was carried out at 0°C for 7 hours. The reaction solution was cooled to room temperature, poured into 300 parts of vigorously stirred methanol, separated and dried to obtain an imidized polymer. NMR analysis showed that the conversion rate of acid anhydride groups to imide groups was 98%.

Experimental Example (2) Production of Component B (a) Production of a copolymer in which an aromatic vinyl-maleic anhydride system is grafted onto a rubbery polymer Styrene (hereinafter referred to as St.
75 parts of methyl ethyl ketone (hereinafter abbreviated as MEK)
After charging 100 parts of polybutadiene cut into small pieces and purging the system with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After setting the temperature to 80°C, 6 parts of a solution of 25 parts of maleic anhydride (hereinafter abbreviated as MAH) and 0.2 parts of benzoyl peroxide dissolved in 30 parts of MEK was added.
It was added continuously over time. After the addition, the temperature was increased to 8 for another 2 hours.
It was kept at 0°C.

A portion of the viscous reaction solution was sampled and unreacted monomer was quantified by gas chromatography to calculate the polymerization rate and the MAR content in the polymer. 150 parts of MEK was added to the remaining reaction solution, cooled to room temperature, poured into 800 parts of vigorously stirred methanol, precipitated, filtered, and dried to obtain a white powdery graft copolymer.

(b) Production of rubber-modified imidized copolymer 30 parts of the graft copolymer obtained in (a) was subjected to MEK in an autoclave.
70 parts of the maleic anhydride group.
02 times the molar equivalent of aniline (7.12 parts) and triethylamine (0.1 part) were added, and the mixture was reacted at 140°C for 6 hours. The reaction solution was cooled to room temperature and stirred vigorously with methanol 3.
00 parts, precipitated, filtered, and dried to obtain an imidized polymer. NMR analysis showed that the conversion rate of acid anhydride groups to imide groups was 89%.

Experimental example (3) Production of component C Production of rubber modified copolymer 65 parts of polybutadiene latex (solid content 50%, average particle size 0.35 pL, gel content 80%), 1 part of sodium stearate, sodium 0.1 part of formaldehyde sulfoxylate, 0.03 part of tetrasodium ethylenediamine tetraacetic acid, 3 parts of 6 parts of ferrous sulfate, and 200 parts of water were heated to 65°C, and acrylonitrile (hereinafter referred to as AN) was added to the mixture. 35 parts of a monomer mixture consisting of 30% St and 70% St, 0.14 t-dodecyl mercaptan
1 part and 0.1 part of cumene hydroperoxide were continuously added over 4 hours, and after the addition was completed, polymerization was further carried out at 65°C for 1.5 hours. The polymerization rate reached 86%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder.

Experimental example (4) Production of components Production of thermoplastic copolymer containing aromatic vinyl as an essential component 25 parts of AN, 75 parts of St, 2.
5 parts, 0.6 parts of t-dodecyl mercaptan and 25 parts of pure water
The mixture to which 0 part was added was heated to 70°C, and 0.05 part of potassium persulfate was added thereto to initiate polymerization. Five hours after the start of polymerization, 0.03 part of potassium persulfate was further added, and the temperature was raised to 75° C. and maintained for 3 hours to complete polymerization. The polymerization rate reached 97%.

The obtained latex is coagulated with calcium chloride.

After washing with water and drying, a white powder copolymer was obtained.

Experimental example (5) (A) component, (B) component, (C) component, (D) component, (
E) Component (Denkavinyl 5S-Y) was blended in the amount ratio of the polymer component shown in Table 1, and the polymer component 100%
1 part of octyl tin malate (manufactured by Katsuta Kako, TM-IE185), 1.5 parts of composite lubricant (manufactured by Henkel, GH-4), and 1.0 part of lubricant (manufactured by Hoechst). , OP Kenax) 0.2 parts Octadecyl-3-(3,5-sitashary-butyl-4
-Hydroxyphenyl)propionate 0.2 parts This blend was extruded using an extruder and pelletized.

The physical properties of the pellet thus obtained are shown in Table 1.

Experimental Example (θ) The blend obtained in Experimental Example (5) was stirred and mixed in a Henschel machine, and then pelletized in an extruder as shown in the table below. As shown above, the composition of the present invention has the following effects: The effect of the invention is remarkable, as it exhibits excellent heat resistance, impact strength, and flame retardancy in a well-balanced manner depending on the amount blended.

Claims (1)

[Scope of Claims] Consisting of the following components (A), (B), (C), (D) and (E), the blending ratio of which is component (A) and/or component (B). is 10 to 80% by weight, component (C) is 10 to 60% by weight, component (D) is 0 to 60% by weight,
A thermoplastic resin composition containing 30 to 80% by weight of component (E). Component A: A copolymer consisting of 50 to 80% by weight of an aromatic vinyl monomer, 5 to 40% by weight of maleic anhydride, and 0 to 30% by weight of a vinyl monomer copolymerizable with these, and ammonia and/or An imidized polymer obtained by reacting a primary amine. Component B: 3 to 40 parts by weight of rubbery polymer, 50 to 80% by weight of aromatic vinyl monomer, 5 to 40% by weight of unsaturated dicarboxylic acid anhydride, and 0 vinyl monomer copolymerizable with these. A rubber-modified imidized polymer having imide groups, which is obtained by graft-polymerizing 60 to 97 parts by weight of a monomer mixture containing 30% by weight with ammonia and/or a primary amine. Component C: 3 to 80 parts by weight of rubbery polymer, 40 to 100% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and 0 vinyl monomer copolymerizable with these. A graft copolymer obtained by copolymerizing 20 to 97 parts by weight of a monomer mixture consisting of 40% by weight. Component D: A copolymer consisting of 40 to 100% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these. Component E: polyvinyl chloride resin containing 0 to 20% by weight of a copolymer component.