JPS601248A - Styrene polymer composition - Google Patents

Abstract

PURPOSE:To provide a styrene polymer compsn. having excellent adhesion, by blending a styrene polymer with a product obtd. by treating a styrene/butadiene block copolymer with a norbornene ring-contg. carboxylic acid anhydride. CONSTITUTION:100pts.wt. styrene homopolymer, copolymer contg. at least 50mol% of styrene or graft polymer (A) obtd. by graft-polymerizing styrene onto butadiene homopolymer rubber or a butadiene/styrene copolymer rubber is mixed with 1-50pts.wt. product (B) obtd. by treating 100pts.wt. styrene/butadiene block copolymer contg. 1-50wt% butadiene with 0.01-10pts.wt. norbornene ring-contg. carboxylic acid anhydride such as 5-norbornene-2,3-dicarboxylic anhydride in the presence of a crosslinking agent, to obtain the desired styrene polymer compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to a styrenic polymer assembly with excellent adhesive properties. More specifically, styrene-based polymers containing styrene as a main component and (B) styrene-butadiene block copolymers contain carboxylic acids having a norbornene ring such as anhydride of 5-fulbornene-2,3-dicarboxylic acid. This invention relates to a styrenic polymer composition comprising a treated product obtained by treating an anhydride in the absence of a crosslinking agent, and its purpose is to provide a styrenic polymer composition with excellent adhesive properties. It is something to do.

(2) Background of the Invention Polymer compounds that do not have polar groups (eg, olefin polymers and styrene polymers) do not have good adhesion to various substances because they do not have polar groups. To this end, the following methods have been proposed to impart adhesiveness to styrenic polymers with various substances.

(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 adhesiveness of styrenic polymers is improved by the above method, the adhesiveness with various substances is still unsatisfactory. This is because styrenic polymers are hard resins, so the resin layer at the adhesive interface between molded products of the polymer and various substances does not behave in a way that can accommodate the deformation that occurs when the metal is beaded. It is estimated to be.

From the above, by melt-kneading a styrene-butadiene copolymer containing a small amount of butadiene as a styrene-based polymer and the above-mentioned vinyl compound in the presence of an organic peroxide, it is possible to bond the styrene-butadiene copolymer. It is possible to improve the characteristics. However, a crosslinking reaction simultaneously proceeds in the copolymer due to the radicals generated by the organic peroxide used, and the modified copolymer becomes gelatinized, resulting in poor physical properties, appearance, moldability, compatibility, etc. becomes significantly worse.

From the above, it is considered that the styrene-butadiene copolymer and a 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 a vinyl compound onto a styrene-butadiene copolymer, and unreacted vinyl compounds bleed onto the surface of the polymer over time, which not only has an adverse effect on the human body, but also causes adhesion. Causes decreased sexual ability.

2. Structure of the Invention Based on the above, the present inventors conducted various searches to obtain a styrenic polymer composition or a processed product thereof that does not have these drawbacks and has excellent adhesion to metals. As a result, (4) 100 parts by weight of a styrene homopolymer or a copolymer containing at least 50 moles of styrene, or a graft polymerization product obtained by graft polymerizing styrene onto a butadiene homopolymer rubber or a butadiene-styrene copolymer rubber, and (B) 0.00 to 100 parts by weight of a styrene-butadiene block copolymer containing 1.0 to 50% by weight of butadiene.
01 to 10 parts by weight of [5-norbornene-2,3 dicarboxylic acid anhydride, 6-(5-carboxy-bicyclo(2
,2,1)-hebutan-2-enyl)acetic anhydride, 3.
6-methano-1-methyl-1,2,3,6-titrahydrociphthalic anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2,3,4,4a, 5.8.8
a-octahydronaphthalene, 5,8-methano-1,2
, 3,4,4a, 5.8.8a, at least one kind of norbornene selected from the group consisting of -octahydronaphthalene-1,2-dicarboxylic acid anhydride "anhydride of carboxylic acid having a norbornene ring" It has been discovered that a styrenic polymer composition consisting of 10 to 50 parts by weight of a treated product obtained by treating a styrene-based polymer in the absence of a crosslinking agent is a composition with excellent adhesion, and the present invention Reached.

(2) Effects of the Invention The styrenic polymer composition obtained by the present invention, including its production, exhibits the following effects (characteristics).

(1) The composition obtained by the present invention can be kneaded in a molten state using a mixer such as a roll, an extruder, a Banbury mixer, or a kneader, which are commonly used in the field of synthetic resins. Since it can be obtained, the manufacturing method is simple.

(2) Unreacted monomer (carboxylic acid anhydride having a norbornene ring) bleeds onto the surface of the treated product very little, so not only does it have no adverse effects on the human body, but it also maintains adhesive properties over time. There is little decline.

(3) Since gelation and crosslinking reactions of the styrene-butadiene copolymer used do not occur, the moldability and fluidity of the resulting styrenic polymer composition do not deteriorate.

(4) Kneading the resulting composition with metal powder, inorganic filler, or organic filler not only improves dispersibility but also helps prevent these from falling off.

(5) It is possible to react with a resin having an alcoholic hydroxyl group or an amide 7 group, and it can be laminated and blended with these resins.

(6) Since it has good crosstalk properties and moldability, 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 home appliance parts (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) Improved adhesion of resins whose main component is styrene [
■ Detailed Description of the Invention (5) Styrenic Polymer The styrenic polymer used in the present invention is a styrene homopolymer, a copolymer containing at least 50 mol% of styrene, a butadiene homopolymer rubber, or a butadiene-styrene polymer. It is a graft polymerization product obtained by graft polymerizing styrene onto copolymer rubber.

The copolymer is a copolymer of styrene and another organic compound having double bonds. Representative examples of such organic compounds include ethylene, vinyl acetate, maleic anhydride, acrylonitrile and methyl methacrylate. The molecular weight of styrene homopolymers and copolymers containing at least 50 mol% of styrene generally ranges from 30,000 to 30,000.
It's 10,000.

The rubber used to produce the graft polymerization product is a butadiene homopolymer rubber or a copolymer rubber of butadiene and a small amount (usually 40% by weight or less) of styrene. This copolymer rubber may be block copolymer rubber,
Random copolymer rubber may also be used. Among these rubbers, their Mooney viscosity is 2, although it varies depending on the type of rubber.
A value of 0 to 140 is desirable, and a value of 30 to 120 is particularly preferred. Furthermore, these 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, "Synthetic Rubber Handbook 1," written by Shu Kanbara (published by Shokusen Shoten in 1962)].

In producing the above graft polymerization product, graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, and aqueous suspension polymerization, as well as methods that combine these graft polymerization methods (for example, after bulk polymerization, There is a method of aqueous suspension polymerization).

Generally, the amount of rubbery material used to produce 100 parts by weight of styrene resin (B) is 10 to 40 parts by weight, preferably 1.0 to 30 parts by weight, particularly 5.0 parts by weight.
~30 parts by weight is preferred. (Although a relatively large amount of rubbery material may be used to produce a graft polymer containing a large amount of rubbery material, and the above-mentioned styrene homopolymer or copolymer may be mixed with this graft polymer, In this case, the amount of rubber-like material used is calculated based on the mixture). Further, the molecular weight of the monomer (styrene) bonded to the rubber-like material as a graft chain is usually 1,000 to 300,000, and preferably 2,000 to 200,000. In general, complete monomer bonding to the rubber is rare, and there are grafts and homopolymers of monomers that are not bonded to the rubber. These homopolymers are used as they are without separation.

(B) Treated product of styrene-butadiene block copolymer The treated product of the styrene-butadiene block copolymer used in the present invention is a styrene-butadiene copolymer described later in which a carboxylic acid anhydride having a fulbornene ring is added. It can be obtained by processing.

The butadiene content of the styrene-butadiene block copolymer used to produce this treated product is from 10 to
50% by weight, preferably 5.0 to 50% by weight, particularly preferably 5.0 to 40% by weight. If the butadiene content of the styrene-butadiene block copolymer is less than 1.0% by weight, the resulting composition will have poor adhesive properties, which is not preferred.

On the other hand, if the amount exceeds 50% by weight, the rubbery properties will increase, making it impossible to obtain a molded article with satisfactory mechanical properties. In addition, the melt flow rate of this block copolymer (according to ASTM D-'12.38, the temperature is 20
Measured at 0°C and a load of 5kg, below [MFRJ
) is 0.01 to 50g/10 minutes, and 0.01
~3 (L9/10 minutes is desirable, especially 0.1~30
g/10 minutes is preferred. MFR is 0.01, 9/10
If a block copolymer of less than 100% is used, moldability will be significantly deteriorated.

On the other hand, if a styrene-butadiene block copolymer exceeding 50 g/lO is used, a treated product with sufficient physical properties cannot be obtained.

The styrene-butadiene block copolymer can be produced by block copolymerizing styrene and butadiene, generally by either solution polymerization or bulk polymerization. Furthermore, it is also possible to manufacture by combining these methods (eg, bulk polymerization followed by solution polymerization). The catalyst used to make this copolymer is an organolithium compound (e.g. n
-butyllithium) or transition metal compounds (e.g., titanium-containing compounds) or transition metal compounds on carriers (e.g., magnesium compounds, processed products thereof) and organometallic compounds (e.g., organic aluminum compounds) (so-called Ziegler catalysts) are common. The method for producing this styrene-butadiene block copolymer is well known, and is industrially produced and used in a wide variety of fields. There are several types of block copolymerization methods, and block copolymers produced by any of these methods can be used.

In producing the treated styrene-butadiene block copolymer used in the present invention, treatment methods include a solution method and a melt method.

In the solution method, styrene-butadiene block copolymer and 5-norbornene-2 are mixed in a nonpolar organic solvent.
, 3-dicarboxylic anhydride and the mixture is generally heated to room temperature (
15°G) to 150°C (preferably 15°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 having a melting point of 03°C or less, and those having a boiling point of 30 to 250°C are preferable. If a solvent whose melting point exceeds 0°C is used, solidification tends to occur. On the other hand, the boiling point is 30
If an organic solvent with a boiling point of less than 250°C is used, it will easily vaporize during the treatment, and if an organic solvent with a boiling point of over 250°C is used, it will be difficult to completely remove the solvent from the treated product after the treatment is completed. It is. For these reasons, representative examples of preferred inert organic solvents include methyl acetate, ethyl acetate,
Mention may be made of benzene, hexane, chlorobenzene, toluene, xylene, chloroform, tetrachlorinated hydrocarbons, octane and heptane.

Furthermore, when treating a styrene-butadiene block copolymer with a carboxylic acid anhydride having a norbornene ring by a melt method, a melt kneader (for example, an extruder) used in the field of general synthetic resins is used. It can be obtained by melt-kneading the block copolymer and the carboxylic acid anhydride having a norbornene ring. At this time, the kneading temperature varies depending on the type of styrene-butadiene block copolymer used, but is at least the melting point of the block copolymer used.
The temperature is 280°C or less. However, if the treatment is carried out at a temperature exceeding 280°C, a part of the block copolymer used may be thermally degraded, and even if there is no thermal deterioration, rapid processing (reaction) will occur, resulting in poor performance. The processed product cannot be obtained.

The treatment ratio of carboxylic acid anhydride having a norbornene ring to 100 parts by weight of styrene-butadiene block copolymer is 0.01 to 10 parts by weight, and 0.01 to 10 parts by weight.
Parts by weight are desirable, particularly 0.05 to 10 parts by weight. 5 for 100 parts by weight of block copolymer
- If the treatment proportion of the carboxylic acid anhydride having a norbornene ring is less than 0.01 parts by weight, a treated product having excellent adhesive strength cannot be obtained. On the other hand, if the amount exceeds 10 parts by weight, the adhesion will not increase, but rather the physical properties will significantly deteriorate, 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 producing the treated product of the present invention, the melting method is preferred.

Furthermore, in this melting method, the shear rate is 50 to 20
It is desirable to carry out the test under conditions of 0/sec (preferably 100 to 200/sec).

In producing the treated product of the present invention, an important point is that the process is carried out in the absence of a crosslinking agent, even when carried out by any of the above-mentioned methods.

On the other hand, if the treated product of the present invention is produced in the presence of a crosslinking agent (for example, an organic peroxide) during treatment, a crosslinking reaction will occur due to the double bonds present in the styrene-butadiene copolymer, resulting in gel formation. This results in poor kneading properties during production of the composition.

Since the carboxylic acid anhydride having a 5-norbornene ring used in the production of the treated product of the present invention is a sterically bulky compound, unlike the commonly used maleic acid and its anhydride, it is It does not act as a splashing agent. Therefore, gelation does not occur, and therefore fluidity (melt viscosity) and moldability hardly decrease.

(C) Composition ratio In producing the composition of the present invention, the ratio of styrene-butadiene block copolymer to 100 parts by weight of the above-mentioned styrene polymer (styrene homopolymer, styrene copolymer, graft polymerization product) The composition ratio of the treated material is 1.0~
The amount is preferably 50 parts by weight, preferably 5.0 to 50 parts by weight, and particularly preferably 5.0 to 30 parts by weight. If the composition ratio of the treated product of the copolymer to 100 parts by weight of the styrene polymer is less than 1.0 parts by weight, a composition with excellent adhesive properties, which is the object of the present invention, cannot be obtained. On the other hand, if the amount exceeds 50 parts by weight, the characteristics originally possessed by the styrenic polymer will be low, which is not preferable in any case.

0 Composition production, properties, molding method, etc. In producing the composition of the present invention, stabilizers against oxygen and heat, metal deterioration inhibitors, flame retardants, commonly used in the field of styrenic resins, Processability modifiers, fillers and lubricants may also be added.

The composition of the present invention may also be triblended using a mixer such as a Henschel mixer commonly used in the styrenic resin industry, such as a Banbury mixer, kneader, roll mill, or screw extruder. It can be obtained by melt-kneading using a mixer such as. At this time, a homogeneous composition can be obtained by tri-blending in advance and melt-kneading the resulting composition (mixture). In this case, the mixture is generally melt-kneaded, then molded into pellets, and subjected to the molding described later.

The treated product used in the present invention has a reactive acid anhydride group and thus has strong bonds with metals, inorganic compounds, and organic compounds. When kneaded with solid or flake, it not only improves various physical properties, but also improves various physical properties.
When these are used as additives such as fillers, they have excellent dispersibility with styrenic polymers. therefore,
It is possible to prevent the additive from falling off from a molded article of a styrenic polymer in which the additive used in the present invention has been kneaded with the treated product.

Furthermore, 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.

In addition, it is possible to produce laminates with metals (for example, iron, aluminum, copper, stainless steel), and the surface of the molded product of the composition of the present invention can be coated with acrylic paint or urethane paint. can be improved.

The styrenic polymer composition obtained by the present invention has excellent moldability, so it can be formed into various shapes by molding methods such as extrusion molding and steam molding, which are commonly used in the field of styrenic resins. Molded articles can be manufactured. Examples of shapes include film-like objects, sheet-like objects, board-like objects, plate-like objects, pipe-like objects, rod-like objects, container-like objects, box-like objects, spherical objects, and other complex shapes. It will be done. Even in the case of melt-kneading and molding, it must be carried out at a temperature above the softening point of the styrenic polymer and the material to be treated.
If carried out at high temperatures, processing products and other polymers may deteriorate. Therefore, melt kneading and molding are generally carried out at a humidity range of 150-280°C.

As described above, the composition obtained according to the present invention has excellent adhesive properties and can be bonded to shapes of various substances. This substance may include metals (for example,
aluminum, iron, copper, their alloys), glass, paper,
Examples include la fiber, wood, leather, rubbers (e.g., neoprene rubber, urethane rubber, butadiene rubber, natural rubber), polar group-containing resins (e.g., ABS resin, polyester, polyamide, polyacrylonitrile), and styrene polymers. . As described above, the composition obtained according to the present invention has excellent adhesion properties with shapes of various materials, so it can be used by laminating (may be two layers, three or more layers) with shapes of these materials. be able to. moreover,
It is also possible to use a molded product of the composition by coating it with an acrylic paint or a urethane paint.

M Examples and Comparative Examples The present invention will be explained in more detail with reference to Examples below.

In the Examples and Comparative Examples, the adhesive strength was determined by preheating the obtained composition or pretreatment product and aluminum foil (thickness: 0.05 mm) at 230°C press humidity for 2 minutes, and applying 150 kg at this temperature. Press molding was performed for 1 minute under pressure conditions of /7. Each of the obtained press molded products (width: 10 mm) was peeled off from the adhesive surface in a direction of 180° C. using a Tensilon at a peeling speed of 50 mrrt for 1 minute.

Moreover, tensile strength was measured according to ASTM D-638. Furthermore, the flexural modulus was measured according to AS, TMD-790. Further, Izot impact strength (notched) was measured according to ASTM D-256.

In addition, in Examples and Comparative Examples, the manufacturing method and physical properties of the treated products of the styrene resin and styrene-butadiene block copolymer used are shown below.

[(4) Styrenic polymer (PS)] As a styrene polymer, styrene was suspended in water, an emulsifier and a catalyst were added, and polymerization was carried out at a temperature of 90°C. As a result, the melt flow index (measured according to JIS' K-6870 at a temperature of 200°C and a load of 5 kg) was 130 g/10 min.
sJ) was manufactured and used.

[(B) Styrenic polymer (HIPS)] As the styrene polymer, 8.1 parts by weight of styrene-butadiene random copolymer rubber [styrene content 25.3% by weight, Mooney viscosity (ML +4) 25 Hereinafter referred to as “SBR”]
92 parts by weight of styrene was graft-polymerized to form a melt.
High impact polystyrene (hereinafter referred to as "HIPS") having a flow index of 13.0 g/10 minutes was manufactured and used.

C (C) Processed product of styrene-butadiene block copolymer] Styrene-butadiene block copolymer with an MFR of 7.0 g/10 min (butadiene content: 29% by weight,
100 parts by weight of 5-norbornene-2,3-dicarboxylic acid anhydride having a norbornene ring (hereinafter referred to as "acid anhydride"), the amount of which is shown in Table 1. Acid anhydride [hereinafter referred to as "anhydride (1)"], 6-(5-carboxy-bicyclo[
2,2,1)-hebut-2-enyl)acetic anhydride [hereinafter referred to as "anhydride (2)"], 3,6-methano-1-methyl-1,2,3,6-titrahydro Cisphthalic anhydride [hereinafter referred to as "anhydride (3)"], 2-oxa-1,4
-dioxo-5,8-methano-1,2,3,4,4a,
5,8,8a,-octahydronaphthalene [hereinafter referred to as "anhydride (April")] or 5,8-methano-1,2,3
, 4, 4a, 5.8.8 a-octahydronaphthalene-1,2,''-, dicarboxylic acid anhydride [hereinafter referred to as "anhydride (5)"] using a twin screw extruder (diameter 30 mm) A pellet was manufactured by kneading the mixture under the conditions that the cylinder temperature was 190° C. and the average residence time of the resin was 4 minutes.

Table 1 shows the MFR and abbreviations of each pellet obtained.

Table Examples 1 to 10. Comparative Examples 1 to 4 The styrenic polymer and treated material whose compounding amounts are shown in Table 4 were mixed in advance using a Henschel mixer at 50% each.
A tri-blend was performed for a minute.

Each of the obtained mixtures was extruded using a twin-screw extruder (diameter 30-) at a resin temperature of 230° C. while melt-kneading, thereby producing pellets (compositions).

Rinse each pellet and cool at 230°C.
A sheet with a thickness of 3 mm was formed using a sheet forming machine set to The results obtained are shown in Table 3.

From the results of the above Examples and Comparative Examples, it is clear that the compositions obtained by the present invention not only have excellent adhesion to metals but also have good processability, and also have various mechanical strengths (for example, impact resistance). It is clear that the material has excellent properties (strength, tensile strength, and flexural modulus), and therefore, it is clear that it is promising for the above-mentioned uses.

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

Claims (1)

[Scope of Claims] (4) A graft obtained by graft polymerizing styrene onto a styrene homopolymer, a copolymer containing at least 50 mol% of styrene, or a butadiene homopolymer rubber or a butadiene-styrene 7 copolymer rubber. Polymerization product 100 parts by weight (B) 0.0.
01 to 10 parts by weight of 5-norbornene-2,3-dicarboxylic acid anhydride, 6-(5-carboxy-bicyclo[2
,2,1:]-to]butar2-en=l) acetic anhydride,
3.6-methano-1-methyl-1,2,3,6-titrahydrociphthalic anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2,3,4, 4a, 5
．． At least one selected from the group consisting of 8.8a-octahydronaphthalene, 5.8-methano-1,2,3,4,4a, and 5.8.8a-octahydronaphthalene-1,2-dicarboxylic acid anhydride. A styrenic polymer composition comprising 1.0 to 50 parts by weight of a treated product obtained by treating a carboxylic acid anhydride having a fulbornene ring in the absence of a crosslinking agent.