JPS6013837A - Treated product of impact-resistant resin - Google Patents

Abstract

PURPOSE:To obtain the titled treated product having remarkably improved adhesivity to metals and high mechanical strength, without causing undesirable effect to the human body nor lowering the moldability of the original resin, by treating an impact-resistant resin such as HIPS resin with a specific carboxylic acid anhydride in the absence of a crosslinking agent. CONSTITUTION:(A) 100pts.wt. of an impact-resistant resin obtained by the graft polymerization of (i) styrene, or styrene and a vinyl compound such as acrylonitrile, methyl methacrylate, etc. to (ii) a butadiene rubber having a butadiene content of >=60wt%, is treated with (B) 0.01-10pts.wt. of a carboxylic acid anhydride selected from 5-norbornene-2,3-dicarboxylic acid anhydride, 6-(5-carboxy- bicyclo[2,2,1]-hept-2-enyl) acetic acid anhydride, 3,6-methano-1-methyl-1,2,3,6-tetrahydro-cis-phthalic acid anhydride, etc., in the absence of a crosslinking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [1] Object of the Invention The present invention relates to a treated impact-resistant resin obtained by treating the impact-resistant resin with a carboxylic acid anhydride in the absence of a crosslinking agent. More specifically, (5) an impact-resistant resin obtained by graft copolymerizing styrene alone or styrene and another vinyl compound to a butadiene non-rubber containing butadiene as a main component, and (B)
5-Norpol-2,3-dicarboxylic anhydride, 6-
(5-Carboxy-bicyclo(2,2,I J-hebut-2-enyl)acetic anhydride, 3,6-methano-1-methyl-I.

2.3.6-Titrahydrocysphthalic anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2,3
゜4+4a+5+8+8a-octahydronaphthalene and 5゜8-methano-1+2+314142+5+8+
Treatment of impact-resistant resin obtained by treating at least one carboxylic acid anhydride selected from the group consisting of 8"-octahydronaphthalene-1,2-dicarboxylic acid anhydride in the absence of a crosslinking agent. The purpose is to provide a treated product with excellent adhesion to metals.

CI'll Background of the Invention Polymer compounds that do not have polar groups (eg, olefin polymers, styrene polymers) do not have good adhesion to metals because they do not have polar groups. For this purpose, the following method has been proposed to impart adhesion to metals of styrene polymers.

(1) A method of graft polymerizing a vinyl compound having a polar group (for example, acrylic acid, methacrylic acid, maleic acid, or anhydride thereof) to a styrenic polymer (including impact-resistant styrenic resin).

(2) A method of copolymerizing styrene and the vinyl compound.

(3) A method of blending a substance (including resin) with adhesive properties into a styrene polymer.

However, even if the adhesion of styrenic polymers is improved by the above method, the adhesion to metals is still unsatisfactory. This is presumed to be because the styrene polymer is a hard resin, so the resin layer at the adhesive interface between the molded product of the polymer and the metal does not behave in a way that can accommodate the deformation that occurs when the metal is beaded. be done.

From the above, it is considered that the adhesion of the impact resistant resin can be improved by melt-kneading the impact resistant resin as a styrenic polymer and the vinyl compound in the presence of an organic peroxide. However, due to the radicals generated by the organic peroxide used, a crosslinking reaction simultaneously proceeds in the impact-resistant resin, and the modified copolymer gels, resulting in poor physical properties, appearance, moldability, and compatibility as a resin. etc. become significantly worse.

From the above, it is considered that the impact-resistant resin and the vinyl compound having a polar group (for example, maleic anhydride) are melt-kneaded in the absence of an organic peroxide. However, it is difficult to completely graft-polymerize vinyl compounds onto impact-resistant resins, and unreacted vinyl compounds bleed onto the surface of the polymer over time, which not only has a negative impact on the human body but also reduces adhesive properties. causes a decline.

l] Structure of the Invention Based on the above, the present inventors have conducted various searches to obtain a composition of a styrene polymer or a processed product thereof that has excellent adhesion to metals without resolving these drawbacks. Impact resistant resin 100 obtained by graft copolymerizing styrene alone or styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate to a butadiene rubber containing at least 60% by weight of butadiene. Parts by weight and (B) 5-norbornene-2,3-dicarboxylic anhydride, 6-(5-carboxy-bicyclo[2°2.1]-
hebut-2-enyl) acetic anhydride, 3,6-methano-1
-Methyl-1,2,3,6-titrahydrociphthalic anhydride, 2-oxa-1,4-nidioxo-5,8-methano-1,2,3,4,4'a, 5,8 , 8a-octahydronaphthalene and 5°8-methano-1,2,3,
4,4a,5,8.8a-octahydronaphthalene-1
, 2-dicarboxylic acid anhydride. However, it has been discovered that a treated product not only has excellent adhesion to metals but also solves the above-mentioned drawbacks, and has thus arrived at the present invention.

[Previous] Effects of the Invention The treated product obtained by the present invention, including its production, exhibits the following effects (characteristics).

(1) The processed product of the present invention can be used in rolls, extruders, Banbury mixers, etc., which are used in the field of general synthetic resins.
Since it is obtained by kneading it in a molten state using a mixer such as a kneader, the manufacturing method is simple.

(2) Bleeding of unreacted monomer (carboxylic acid anhydride) onto the surface of the treated product is extremely rare, so not only is there no adverse effect on the human body, but there is also little deterioration in adhesive properties over time. .

(3) Since gelation and crosslinking reactions of the impact-resistant resin used do not occur, moldability and fluidity do not deteriorate.

(4) By kneading the obtained treated product with metal powder, inorganic filler, or organic filler, it not only improves the dispersibility but also helps prevent these from falling off.

(5) It has good compatibility with resins containing styrene as a product, and can influence the adhesive properties of these resins.

(6) It can be reacted with resins having alcoholic hydroxyl groups and amine groups, and can be laminated and blended with these resins.

(7) Since the wire crosstalk property and moldability are good, it can be molded into molded products having various shapes and has various excellent mechanical strengths.

The present invention can be used in a wide variety of ways to achieve the effects (features) described above. Typical uses are shown below.

(1) Various articles for automobiles (including motorcycles) (2) Various parts for home appliances (3) Various containers and daily necessities (4) Laminates with resins whose main component is styrene (5)''
Office equipment parts (6) Dispersibility improver for powdered, flaky and fibrous materials such as various metals, inorganic fillers and organic fillers (7) Improvement of adhesion of resins whose main component is styrene ~〕
Detailed Description of the Invention Impact-resistant resin The impact-resistant resin used in the present invention is obtained by graft copolymerizing styrene alone or styrene and another vinyl compound to the butadiene rubber described below. .

(1) Butadiene-based rubber The butadiene-based rubber is a rubber whose main component is butadiene (60% by weight or more). .

NBR). The copolymer rubber of butadiene and styrene may be a block copolymer rubber or a mata random copolymer rubber.

In producing the impact-resistant resin of the present invention, among the above-mentioned butadiene rubbers, those having a Mooney viscosity of 20 to 140 are preferable, and those having a viscosity of 30 to 120 are preferable, although this varies depending on the type of rubber. Furthermore, these butadiene rubbers are widely produced industrially and are used in a wide variety of fields. Their manufacturing methods, properties and uses are widely known. [For example, Shu Kanbara, "Synthetic Rubber/.../Dobtsuku N" (published by Asakura Shoten in 1962)] 0 (2) Production of impact-resistant resin The impact-resistant resin used in the present invention is made by adding styrene to the above-mentioned rubber. It is produced either alone or by graft polymerization of styrene and at least one of other vinyl compounds (acrylonitrile, methyl methacrylate). Graft polymerization methods include bulk polymerization, solution polymerization, and emulsion polymerization. There are also aqueous suspension polymerization methods and methods that combine these graft polymerization methods (for example, bulk polymerization followed by aqueous suspension polymerization).Generally,
The amount of butadiene rubber used to produce 100 parts by weight of impact resistant resin is 3 to 40 parts by weight,
5 to 35 parts by weight is preferred, particularly 5 to 30 parts by weight. (Although a relatively large amount of butadiene rubber may be used to produce a graft polymer containing a large amount of rubber, and the above-mentioned homopolymer resin of styrene, acrylonitrile, and methyl methacrylate is mixed with the graft polymer, In this case, the amount of rubber-like material used is calculated based on the mixture). In addition, the molecular weight of the seven polymers (styrene, acrylonitrile, methyl methacrylenide) bonded to the butadiene rubber as graft chains is usually 1,000 to 30.
There are 0,000 te, especially 2,000 to 200. O
CIO is preferred. In general, it is rare for monomers to be completely bonded to butadiene rubber, and there exist monopolymers or copolymers of monomers that do not bond to the rubber.

These homopolymers and copolymers are used as they are without separation.

(3) Typical examples of impact-resistant resins Typical examples of impact-resistant resins produced as described above include butadiene homopolymer rubber or block or random copolymer rubber of styrene and butadiene (SBFt).
impact-resistant styrene resin (1-IPS resin) obtained by kraft copolymerization of styrene alone, butadiene homopolymer rubber, SBR, or acrylonitrile and butadiene copolymer rubber (NBR) with styrene and acrylonitrile. Acrylonitrile-butadiene-styrene ternary copolymer resin ('A, BS resin) obtained by graft copolymerization, butadiene homopolymer rubber or SBR obtained by graft copolymerization of styrene and methyl methacrylate Examples include methyl methacrylate-butadiene-styrene ternary copolymer resin (MBs resin).

(B) Treatment method In carrying out the present invention, the above impact resistant resin is treated with [5-norbornene-2,3-dicarboxylic anhydride, 6-(5-carboxy-bicyclo(2,2,I J- but-2-enyl)acetic anhydride, 3,6-methano-1-methyl-1,
2,3,6-titrahydrocysphthalic anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2,3
,4+4a,5,8.8a-octahydronaphthalene and 5,8-methano-1,2,3,4,4a,5,8.
This can be achieved by treating ``8a-octahydronaphthalene-1,2-dicarboxylic anhydride'' (hereinafter referred to as ``carboxylic anhydride''). Examples of the treatment method include a solution method and a melt method.

In the solution method, the impact-resistant resin and carboxylic acid anhydride are added to a non-polar organic solvent and heated generally at room temperature (15°C) to 150'O (preferably 15°C).
This method involves processing at temperatures ranging from 120°C to 120°C. Inert organic solvents used in this method include organic acids consisting of saturated aliphatic carboxylic acids, their anhydrides and esters, and their derivatives, as well as aliphatic and aromatic hydrocarbons and their halides. Among these inert organic solvents, those with a melting point of 0°C or less,
Those having a boiling point of 30 to 250°C are preferred. Melting point is O'
If a solvent exceeding C is used, it tends to coagulate.

On the other hand, if an organic solvent with a boiling point of less than 30°C is used, it will easily vaporize during the treatment, and if an organic solvent with a boiling point of more than 250°C is used, the solvent will be removed from the treated product after the treatment is finished. is difficult to completely remove. For these reasons, representative examples of preferred inert organic solvents include methyl acetate, ethyl acetate, benzene, hexano, chlorobenzene, toluene, xylene, chloroform, hydrocarbon tetrachloride, octane and heptane.

Furthermore, when treating an impact-resistant resin with a carboxylic acid anhydride by a melting method, the impact-resistant resin and carboxylic acid It can be obtained by processing an anhydride while melt-kneading it. At this time, the crosstalk temperature varies depending on the type of impact-resistant resin used, but it is higher than the melting point of the impact-resistant resin used, but it is 2.
The temperature is below 80°C. However, if processing is carried out at temperatures exceeding 280°C, some of the impact-resistant resins used may undergo thermal deterioration, and even if no thermal deterioration occurs, rapid processing (reactions) will occur, resulting in poor performance. Processed product cannot be obtained.

The treatment ratio of carboxylic acid anhydride to 100 parts by weight of impact-resistant resin is 0.01 to 10 parts by weight, and 0.02 to 1 parts by weight.
0 parts by weight is desirable, and 0.05 to 50 parts by weight is particularly preferred. If the treatment ratio of the carboxylic acid anhydride to 100 parts by weight of the impact-resistant resin is less than 0.001 parts by weight, a treated product with excellent adhesive strength cannot be obtained. On the other hand, 10.
If the amount exceeds 0 parts by weight, there will be no increase in adhesion, but rather the physical properties will be markedly deteriorated, which is not desirable.

Among the above-mentioned treatment methods, in the solution method, it is necessary to substantially completely remove the non-polar organic solvent used from the resulting treated product after the treatment is completed. Therefore, in carrying out the present invention, the melting method is preferable. Furthermore, in this melting method, the shear rate is 50 to 20
It is desirable to carry out the process under conditions of 0/sec (preferably 100 to 200/sec).

An important point of the present invention is that even when carried out by any of the above-mentioned methods, it is carried out in the absence of a crosslinking agent. However, if the present invention is carried out in the presence of a cross-linking agent (e.g., an organic peroxide) during processing, the double bonds present in the impact-resistant resin will cause a cross-linking reaction, resulting in gelation and molding problems. This is undesirable because the properties and fluidity are reduced.

(0) Physical properties of the treated product Representative examples of the physical properties of the treated product obtained by the present invention include A. The melt flow rate (VFR) measured according to STM D-1238 is 0.01 to 60 g/10 minutes; Density measured according to ASTM D-792 is 0.90-1', 20 g/d. Also, AST
Tensile strength measured according to MD-638 is 200
~350kg/ffl, elongation rate is 10~500%
It is. Furthermore, the flexural modulus measured according to ASTM D-790 is 8000-20. OO' Okg
/crA, and the Izot impact strength (notched) measured according to ASjM D-256 is 10-50k.
It is 1 g cm. Moreover, the Rockwell hardness (D scale) measured according to ASTM D-2240 is 70 to 85. These physical properties vary depending on the types of impact-resistant resin and carboxylic acid anhydride used in the production of the treated product, their usage ratio (processing ratio), and the processing conditions.

Since the carboxylic acid anhydride used in the present invention is a sterically bulky compound, unlike the commonly used maleic acid and its anhydride, it does not serve as a crosslinking agent for the crosslinking reaction. Therefore, gelation does not occur, and therefore fluidity (melt viscosity) and moldability hardly decrease.

■ Utilization, molding method, etc. The resulting treatment product has a reactive acid anhydride group and therefore has strong bonds with metals, inorganic compounds, and organic compounds. When kneaded together, they not only improve various physical properties, but when used as additives such as fillers, they have excellent dispersibility with resin-like materials and rubber-like materials. Therefore, it is possible to prevent additives from falling off from a molded article of a resin or rubber material into which additives have been kneaded with the treated product obtained by the present invention.

Furthermore, it has extremely good compatibility with styrene homopolymers, copolymers containing styrene as a main component, and graft polymers obtained by graft polymerizing styrene alone or styrene and other vinyl compounds. Therefore, it is easy to knead (mix) these polymers. Therefore, not only can the adhesion of these polymers be improved, but also a coupling effect can be imparted to these polymers by kneading them together with various additives. Therefore, the physical properties of these polymers to which additives are blended can be improved.

In addition, it is possible to react with polymers having alcoholic hydroxyl groups and amine groups (e.g., saponified ethylene-vinyl acetate copolymer, amide resin), making it easy to stack and bond these polymers. It is.

It is also possible to produce laminates with metals (e.g. iron, aluminum, copper, stainless steel), and in addition acrylic on the surface of moldings of the treated products of the invention or compositions with said polymers. The paintability of paints and urethane paints can be improved.

The processed product obtained according to the present invention is the! However, it may also be used as a composition by mixing with any one of styrene homopolymers, copolymers, and graft polymers. Furthermore, depending on the intended use of the treated product or composition, these treated products or compositions may further contain stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, flame retardants, colorants, electrical property improver,
Additives such as fillers, antistatic agents, lubricants, processability improvers, and tack improvers may be mixed with the mixtures obtained according to the present invention, provided that they do not impair the properties of the mixtures of the present invention. To mix the treated product with the polymer and/or additives, tri-blending may be performed using a mixer such as a Henschel mixer commonly used in the general synthetic resin industry; It can also be produced by melt-kneading using a mixer such as a mixer, kneader, roll mill, or screw extruder. At this time, a more uniform mixture can be obtained by triblending in advance and further melt-kneading the resulting mixture.

As mentioned above, the processed products of the present invention can be produced by various molding methods, such as core extrusion molding, injection molding, inflation molding, and press molding, which are commonly used in the field of synthetic resins due to their excellent molding properties. A molded article having the shape of can be manufactured. In addition, the shapes include film-like objects, sheet-like objects, board-like objects,
Examples include plate-like objects, pipe-like objects, rod-like objects, container-like objects, compositions, spherical objects, and other objects with complex shapes. Both melt-kneading and molding must be carried out at a temperature above the softening point of the treated product or composition, but if carried out at a high temperature, the treated product and other polymers may May deteriorate. Therefore, melt kneading and molding are generally carried out at temperatures between 150 and 280°C.
It is carried out in the temperature range of

As mentioned above, the treated product obtained according to the present invention has excellent adhesive properties and can be bonded to shapes of various materials. These substances include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, fibers, wood, leather, rubbers (e.g. neosolene rubber, urethane rubber, butadiene rubber, natural rubber),
Examples include polar group-containing resins (for example, A, BS resins, polyesters, polyamides, and polyacrylonitrile), and the above-mentioned styrene monopolymers, homopolymers, copolymers containing styrene as a main component, and graft polymers. As described above, the treated product obtained by the present invention has excellent adhesion to shapes of various materials, so it can be used by laminating (may be two layers, three or more layers) with shapes of these materials. can do. Furthermore, a molded product of the treated product or composition may be used by coating it with an acrylic paint or a urethane paint.

(To) Examples and Comparative Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, adhesive strength (thickness
0.05 mm) was preheated at a press temperature of 230° C. for 2 minutes, and press-molded at this temperature for 1 minute under a pressure condition of 1501 i/−. Each of the obtained press-formed products (width: 10 mm) was peeled in a direction of 1°8σ from the adhesive surface using a Tensilon at a peeling rate of 50 mm/min. In addition, melt flow rate (hereinafter referred to as "MFRJ")
was measured according to JISK-6870 at a temperature of 200°C and a load of 5.0 kg.

In addition, in the Examples and Comparative Examples, impact-resistant resins manufactured in advance as described below were used.

[Styrenic resin (HIPS)] As the styrene resin, 8.1 parts by weight of styrene-butadiene random copolymer rubber [Styrene content 25.3
Weight %, Mooney viscosity (ML++4) 25, hereinafter 1'
-8BRJ] was graft-polymerized with 92 parts by weight of styrene to produce impact-resistant polystyrene (hereinafter referred to as JHIPSJ) with a melt flow rate of 13.0 I/10 minutes.

[However) AB8 resin] Styrene-butadiene copolymer rubber (butadiene content 80% by weight, rubber gel content 80%) 280.0g (as solid content) in a 201 stainless steel autoclave
, 2.0 g ammonium persulfate, 8'O,OF disproportionated sodium rosinate, 210 J lauryl mercaptan, and 8. Added 100 ml of water and stirred uniformly. Add to this 2520g of styrene as a monomer and 1200.9g of styrene as a monomer.
of acrylonitrile was added and stirred, and then the temperature was raised to 70°C while stirring. Polymerization was carried out at this temperature for 10 hours with stirring. Next, an aqueous solution of 50% aluminum sulfate was added to the polymer obtained as described above (
(grafted material) and the resulting grafted material was coagulated. The coagulum was washed with about 524 g of an aqueous solution of about 1% sodium hydroxide and an additional amount (about 30 g) of 70° C. hot water. This graft material was dried at about 80° C. under reduced pressure all day and night. As a result, 3785 g of a white powdery graft material was obtained. The content of the rubbery material of the obtained graft product was 733% by weight. Hereinafter, this grafted material [A
It's called BsJ.

((C) MBS resin) Aqueous dispersion 120 containing butadiene-styrene copolymer rubber (Mooney viscosity 50) 138051 consisting of 76.5% by weight of butadiene and 23.5% by weight of styrene.
1 was placed in a 201 stainless steel autoclave.

Under a nitrogen stream, while maintaining the temperature at 60°C, 480 g of dihydrate of sodium formaldehyde sulfoxylate was added to about 2
．． An aqueous solution of 41 dissolved in water and 16 (l of cumenno.
Hydrocarbon oxide was added thereto, and the mixture was stirred for 1 hour. Next, a mixed solution of 768 (l) of methyl methacrylenide and 320 g of cumene hydroperoxide was added to carry out polymerization. After about 7 hours, the polymerization softening rate reached 918 h. Styrene and 32.0g
A mixture of the above and cumenohydroboroxide was added to carry out polymerization. After about 6 hours, the polymerization softening rate was 93.
It reached 396. An aqueous solution of hydrochloric acid and sodium chloride (salt) was added to this liquid to solidify it. Next, this precipitate was filtered, thoroughly washed with warm water, and heated to about 80°C.
Drying was carried out for one day and night under reduced pressure at a temperature of . As a result, a white powdery polymer (graft product) was obtained. The rubbery material content of this grafted product (hereinafter referred to as MBSJ) was 966% by weight.

Examples 1 to 10, Comparative Examples 1 to 4 100 parts by weight of the above-mentioned impact-resistant resin (types are shown in Table 1) and 5-norbornene- as a carboxylic acid anhydride.
2,3-dicarboxylic anhydride [hereinafter referred to as "anhydride (5)"L6-(5-carboxy-bicyclo(2,2,1'
]-hebut-2-enyl) acetic anhydride [hereinafter referred to as “anhydride (
3,6-methano-1-methyl-1,2
, 3,6-titrahydrocysphthalic anhydride [hereinafter referred to as "anhydride ρ"], 2-oxa-1,4-dioxy-
5,8-methano-1,2,3゜4 + 4a + 5
+ 8.8a-octahydronaphthalene [hereinafter referred to as "anhydride ■"] and 5,8-methano-1,2,3゜4
+4a+5+8.8a-octahydronaphthalene-1,
2-Dicarboxylic acid anhydride [hereinafter referred to as "anhydride"]
(Amounts and types used are shown in Table 1) Using a twin-screw extruder (diameter 30 mm), the cylinder temperature was 19.
The pellets were made while kneading at 0'O and a resin average residence time of 4 minutes. Each of the resulting pellets was adhered to aluminum foil as described above, and the adhesive strength was measured. Table 1 shows the MFR and adhesive strength of each pellet obtained.

From the results of the above Examples and Comparative Examples, it is clear that the treated products obtained by the present invention not only have good adhesion to metals but also excellent moldability.

Patent applicant: Showa Denko Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Scope of Claims] Securing) Graft copolymerization of styrene alone or styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methylmethanocrate to a butadiene rubber containing at least 60% by weight of butadiene. ioo parts by weight of impact-resistant resin obtained by (B) 5-norpolone-2,3-dicarboxylic anhydride, 6-(5-carboxyne-bicyclo[2,2,1]-
hebut-2-enyl) acetic anhydride, 3,6-methano-1
-Methyl-1,2,3,6-titrahydrosysfucuric anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2+3+4.4a, 5+8.8a-octahydronaphthalene and 5,8-methano-1°2+3.4.
4a,5,8.8a-octahydronaphthalene-1,2
- A treated impact-resistant resin obtained by treating 0.01 to 10 parts by weight of at least one carboxylic acid anhydride selected from the group consisting of dicarboxylic acid anhydrides in the absence of a crosslinking agent.