TW201723082A - Impact modified polycarbonate composition - Google Patents

Abstract

The present invention relates to a polycarbonate composition, and the process for producing the same. In particular, the present invention relates to an impact modified polycarbonate composition having improved chemical resistance and resistance against coatings.

Description

Impact modified polycarbonate composition

The present invention relates to a polycarbonate composition, a method of making the same, and its use in a cover member for electrical and electronic devices. In particular, the present invention relates to impact modified polycarbonate compositions having improved chemical resistance and coating resistance.

The cover components of most consumer electronic devices, such as mobile phones, require coating after injection molding. Coating materials typically contain a number of chemicals that are detrimental to polycarbonate, dramatically affecting the mechanical properties of the polycarbonate. In general, mobile phone models require a number of cosmetics such as sunscreen and sweat resistance, which contain many types of chemicals that may be undesirable from polycarbonate. Due to the short chain length and intermediate polarity, polycarbonate molecules have high affinity for many organic solvents. Furthermore, since polycarbonate is an amorphous material, it can be easily penetrated by chemicals having a small molecule compared to a semi-crystalline polymeric material such as nylon, PE (polyethylene), PP (polypropylene). And polyester (PBT (polybutylene terephthalate) and PET (polyethylene terephthalate), etc.). All of these factors make polycarbonate a material with degrading resistance.

A common way to improve chemical resistance is to mix polycarbonate with polyester (PBT, PET, or any polyester copolymer). Due to the semi-crystalline structure of many polyesters, chemical resistance can be greatly improved. However, the addition of polyester to the polycarbonate will result in a lower heat distortion temperature which will block several applications requiring high operating temperatures. The lower impact strength at low temperatures is another disadvantage of such polycarbonate/polyester blends.

Therefore, impact-modified polycarbonate materials have been widely used in several equipment housing applications and electrical & electrical devices such as mobile phones, tablet, adapters/chargers, sockets, and switches. These materials provide good toughness and prevent damage from falling and impact. Furthermore, compared with other engineering polymers, such as HIPS (high impact polystyrene), ABS (acrylonitrile butadiene styrene), and polycarbonate/ABS, etc., they also have higher heat resistance. Make it equal to the higher operating temperature that can be withheld in electrical installations.

However, most impact modifiers using ordinary impact modifiers such as MBS, acrylic rubber-based impact modifiers, and core-shell structures based solely on polyoxyn/acrylic rubber. The general coating resistance and chemical resistance of the impact-modified polycarbonate composition are unsatisfactory.

U.S. Patent No. 8,314,168 discloses the addition of a polystyrene (SPS) to a polycarbonate system, modified by MBS or polyoxyxa/acrylate rubber core-shell structure impact modifier. Several phosphate esters such as PX-200 or TPP (triphenyl phosphate) are added to improve fluidity. Chemical resistance is improved due to the SPS crystalline structure which is well miscible with polycarbonate. However, it is expected that the addition of SPS will sacrifice low temperature impact properties.

US 2004/0186233 A1 discloses that an acrylic rubber-based, polyfluorene/acrylate rubber-based core-shell structure impact modifier, SEBS (styrene-ethylene-butylene-styrene), and PP have been found Improved chemical resistance and low temperature impact properties of polycarbonate. The SEBS and PP core-shell impact modifiers based on polyoxyn/acrylate rubber appear to be more effective in improving chemical resistance. However, both of them are expected to be poorly miscible, and it is very impractical to use them.

US 2004/0107262 A1 discloses the incorporation of several small amounts of alkyl diketene into polycarbonate to effectively improve chemical resistance. However, this additive results in poor hydrolytic stability.

Because consumer electronics devices are growing rapidly, especially in the smart phone market in recent years, there is a need for impact-modified polycarbonates that are suitable for the cover of such devices, which generally have good impact properties, good coating resistance and chemical resistance. Sex. The present invention provides a solution to this need.

The present invention relates to an impact modified polycarbonate composition having particular properties, such as improved coating resistance and chemical resistance. In particular, the invention relates to a polycarbonate composition comprising combining different types of impact modifiers. Technical synergistic effects have been observed with polycarbonate compositions with impact modifiers.

The present invention provides a polycarbonate composition comprising a combination of a special impact modifier to provide a beneficial synergistic effect on coating resistance and sunscreen resistance, balancing other properties such as low temperature impact properties.

The present invention provides a polycarbonate composition comprising: A) at least one thermoplastic, aromatic polycarbonate, in an amount ranging from 85% by weight to 97% by weight based on the total weight of the composition; and B) at least two impact modifiers selected from the group consisting of ethylene acrylate copolymers, preferably from 3 to 5 weight percent %, based on the total weight of the composition; B2) a poly-oxygen-acrylate rubber having a core-shell structure, preferably used in an amount of from 3% by weight to 6% by weight based on the total weight of the composition; B3) acrylate The rubber-based core-shell impact modifier is preferably used in an amount of from 2.5% by weight to 3.4% by weight based on the total weight of the composition; the total amount of the impact modifiers B1, B2 and/or B3 is Up to 3 to 15% by weight based on the total weight of the composition.

The present invention also provides a polycarbonate composition comprising: A) at least one thermoplastic, aromatic polycarbonate in an amount ranging from 85% to 97% by weight based on the total weight of the composition; and B) at least two The impact modifier B1) ethylene acrylate copolymer of the group consisting of the following is selected from the range of 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, particularly preferably 3% by weight to 5 % by weight, based on the total weight of the composition; B2) Poly-oxygen-acrylate rubber having a core-shell structure, in an amount ranging from 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, to constitute The total weight of the material is the benchmark; B3) the acrylate rubber-based core-shell impact modifier, the amount ranging from 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, particularly preferably 2.5% by weight to 3.4% by weight, based on the total weight of the composition; the premise is that the impact modifiers B1, B2 and/or B3 are used in an amount of 3 to 15% by weight, based on the total weight of the composition.

Preferred compositions comprise the following composition: A) at least one thermoplastic, aromatic polycarbonate, in an amount ranging from 85% to 97% by weight based on the total weight of the composition; and B) at least two selected from The impact modifier B1) ethylene acrylate copolymer of the group consisting of the following ranges from 1% by weight to 8% by weight, Preferably, from 3% by weight to 6% by weight, particularly preferably from 3% by weight to 5% by weight, based on the total weight of the composition; B2) a polyfluorene oxide-acrylate rubber having a core-shell structure in an amount ranging from 1% by weight Up to 8% by weight, preferably 3% by weight to 6% by weight, based on the total weight of the composition; provided that the impact modifiers B1 and B2 are used in an amount of from 3 to 15% by weight, based on the total weight of the composition .

Another preferred composition comprises the following composition: A) at least one thermoplastic, aromatic polycarbonate, in an amount ranging from 85% to 97% by weight based on the total weight of the composition; and B) at least two The impact modifier B1) ethylene acrylate copolymer of the group consisting of the following is selected from the range of 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, particularly preferably 3% by weight to 5 % by weight, based on the total weight of the composition; B3) acrylate rubber-based core-shell impact modifier, in an amount ranging from 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, Preferably, it is from 2.5% by weight to 3.4% by weight based on the total weight of the composition; provided that the impact modifiers B1 and B3 are used in an amount of from 3 to 15% by weight based on the total weight of the composition.

Another preferred composition comprises the following composition: A) at least one thermoplastic, aromatic polycarbonate, in an amount ranging from 85% to 97% by weight based on the total weight of the composition; and B) at least two The impact modifier B2) of the group consisting of the following consists of a poly-oxygen-acrylate rubber having a core-shell structure in an amount ranging from 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight. , based on the total weight of the composition; B3) acrylate rubber-based core-shell impact modifier, the amount ranging from 1% by weight to 8% by weight, preferably 3% by weight to 6% by weight, particularly good 2.5 % by weight to 3.4% by weight based on the total weight of the composition; The premise is that the impact modifiers B2 and B3 are used in a total amount of 3 to 15% by weight based on the total weight of the composition.

Since the impact modifiers amount to a total of 15% by weight, it is obvious that the amounts of the impact modifiers B1, B2 and/or B3 must be selected accordingly. When "8 wt%" is referred to as the upper limit, it is only the maximum amount of each group of impact modifiers in the composition described in the previous paragraph.

In another aspect, the invention provides a cover for an electrical or electronic device component made from the above polycarbonate composition.

The objects and advantages of the invention will be better understood from the following detailed description. A person skilled in the art will appreciate that various forms and details can be varied therein without departing from the scope of the invention as set forth in the appended claims.

One aspect of the present invention provides a polycarbonate composition comprising A) polycarbonate and B) at least two impact modifiers selected from the group consisting of components B1), B2) and/or B3).

Component A

For the purposes of the present invention, thermoplastic, aromatic polycarbonates are not only homopolycarbonates, but also copolycarbonates; it is well known that polycarbonates can be linear or branched polycarbonates, polyester-carbonate copolymers, and oximes. Oxyalkane-carbonate copolymer.

The thermoplastic, aromatic polycarbonate has an average weight-average molecular weight (Mw, calibrated using polycarbonate and dichloromethane as the eluent, as measured by GPC) of 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, Very good 24,000 to 32,000 g/mol.

A portion of the polycarbonate (up to 80 mol%, preferably 20 mol% to 50 mol%) of a suitable polycarbonate according to the invention may be replaced by an aromatic dicarboxylate group. Such polycarbonates which incorporate not only acid groups derived from carbonic acid but also acid groups derived from aromatic dicarboxylic acids into the molecular chain are referred to as aromatic polyester carbonates. Briefly, the present application encompasses it within the term "thermoplastic, aromatic polycarbonate".

The polycarbonate is produced from known methods by diphenols, carbonic acid derivatives, and optionally chain terminators and optionally branching agents. The production of polyester carbonates herein involves the use of aromatic dicarboxylic acids or dicarboxylic acid derivatives. The partial carbonic acid derivative is substituted, in particular, to the extent that the aromatic dicarboxylate structural unit is intended to replace the carbonate structural unit in the aromatic polycarbonate.

The amount of polycarbonate added to the composition of the present application ranges from 85 to 97% by weight of the total composition species, preferably from 90 to 95% by weight of the total composition.

Suitable for the manufacture of polycarbonate dihydroxy aryl compounds (2), HO-Z-OH (2)

Wherein Z is an aromatic group having 6 to 30 carbon atoms, and the group may contain one or more aromatic groups which are substituted and contain an aliphatic or cycloaliphatic group and/or an alkylaryl group or a hetero atom as a bridging member. ring.

In the formula (2), Z is preferably a group (3) group,

Wherein R 6 and R 7 are each independently H, C ₁ - to C ₁₈ -alkyl, C ₁ - to C ₁₈ -alkoxy, halogen such as Cl or Br, or optionally substituted aryl or aralkyl, It is preferably H or C ₁ - to C ₁₂ -alkyl, more preferably H or C ₁ - to C ₈ -alkyl, very preferably H or methyl, and X is a single bond, -SO ₂ -, - SO-, -CO-, -O-, -S-, C ₁ - to C ₆ -alkylene, C ₂ - to C ₅ -alkylene, or may be C ₁ - to C ₆ -alkyl ( Preferred is a methyl or ethyl) substituted C ₅ - to C ₆ -cycloalkylene group, or a C ₆ - to C ₁₂ -exylaryl group optionally fused with a further hetero atomic aromatic ring, X Preferred as a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylene, C ₅ - to C ₆ -cycloalkylene, -O-, -SO-, -CO- , -S-, -SO ₂ -, or (3b),

Examples of diphenols suitable for the manufacture of polycarbonates according to the invention include hydroquinone, resorcinol, dihydroxybiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)sulfide , bis(hydroxyphenyl)ether, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl)anthracene, bis(hydroxyphenyl)arene, alpha, alpha'- Bis(hydroxyphenyl)diisopropylbenzene, and also alkylated, cyclo-alkylated and cyclic-halogenated compounds thereof.

Preferred diphenolic 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane , 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl) -2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)anthracene, 2,2-bis(3,5- Dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene and 1 , 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).

Tetradiol is 4,4'-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2- Bis(3,5-dimethyl-4-hydroxyphenyl)propane 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-3,3, 5-trimethylcyclohexane (bisphenol TMC).

In the case of the homopolycarbonate, only one diphenol is used; in the case of the copolycarbonate, two or more diphenols are used. The diphenols used, as well as all other auxiliaries and chemicals added to the synthesis, may be derived from impurities contaminated by their own synthesis, handling and storage. However, I want to operate with extremely pure raw materials.

When a monofunctional chain terminator is required in order to adjust the molecular weight, a phenol or an alkylphenol, especially phenol, p-third butanol, isooctylphenol, isopropyl phenol, a chlorocarbonate or a monocarboxylic acid, and / or a mixture of such chain terminators.

The branching or branching agent mixture is selected from the group consisting of trisphenols, quater phenols or tricarboxylic acid or tetracarboxylic acid, or other mixtures of polyphenols or hydrazine.

Examples of aromatic dicarboxylic acids suitable for the manufacture of polyester carbonates include o-nonanoic acid, p-nonanoic acid, isodecanoic acid, tert-butyl isophthalic acid, 3,3'-biphenyldicarboxylic acid, 4,4'- Biphenyldicarboxylic acid, 4,4-diphenyl ketone dicarboxylic acid, 3,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl Dicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane and trimethyl-3-phenylnonane-4,5'-dicarboxylic acid. Among the aromatic dicarboxylic acids, a particularly good user is tannic acid and/or isophthalic acid.

The dicarboxylic acid derivatives are dicarboxylic acid dihalides and dicarboxylic acid dialkyl esters, especially dicarboxylic acid dichlorides and dimethyl dicarboxylates.

The replacement of the carbonate with an aromatic dicarboxylate group occurs substantially stoichiometrically and quantitatively, and thus the reactant molar ratio is also found in the intact polyester carbonate. The combined aromatic dicarboxylate groups can occur randomly or in blocks.

A preferred mode of producing a polycarbonate according to the invention (including a polyester carbonate) is a known interfacial process and a known melt transesterification process (see, for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A). In the first case, the acid derivative is preferably phosgene and, as the case may be, dicarboxylic acid dichloride; in the latter case, it is preferably diphenyl carbonate and, if appropriate, dicarboxylic acid diester. Catalysts, solvents, work up, reaction conditions, and the like, which are manufactured from polycarbonate and polyester carbonate, have been widely described and are well known in both cases.

The polycarbonates, polyestercarbonates and polyesters can be worked up in a known manner and processed into any desired type of moulding, for example by means of extrusion or injection moulding.

Component B

Component B is at least two modifiers selected from the group consisting of B1) ethylene acrylate copolymer, preferably ethylene-alkyl (meth) acrylate copolymer, B2) having a core-shell structure Poly-oxygen-acrylate rubber, B3) acrylate rubber-based core-shell impact modifier.

B1) ethylene acrylate copolymer

For the purposes of the present invention, component B1) is preferably an alkyl (meth) acrylate copolymer of formula (I),

Wherein R ₁ is methyl or hydrogen, R ₂ is hydrogen or C ₁ - to C ₁₂ -alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, second butyl, Tributyl, isobutyl, hexyl, isopentyl, or a third amyl group, each of x and y is independently polymerized (integer), and n is an integer of >=1.

The ratio of x to y polymerization ratio is preferably in the range of x: y = 1:300 to 90:10.

The ethylene-alkyl (meth) acrylate copolymer can be a random, block or multi-block copolymer or a mixture of such structures. In a preferred embodiment, branched and unbranched ethylene-alkyl (meth) acrylate copolymers, particularly linear ethylene-alkyl (meth) acrylate copolymers, are used.

Preferably, component B1 is an ethylene-methyl acrylate copolymer, or alternatively, one of ethylene-methyl acrylate copolymer components B1. For example, component B1) is selected from ethylene acrylate copolymers comprising Elvaloy AC1820, AC1224, AC1125, AC1330 from Dupont, and Lotyl 18MA02, 20MA08, 24MA02, 24MA005, 29MA03, 30BA02, 35BA40, 17BA04, 17BA07, etc. from Arkema. The objects form a group.

The melt flow rate (MFR) of the ethylene-alkyl (meth) acrylate copolymer (measured at 190 ° C to 2.16 kg load, ASTM D1238) preferably ranges from 0.5 to 40.0 g / (10 minutes), particularly preferably from 0.5 to 10.0 g / (10 minutes), the most excellent range of 2.0 to 8.0 g / (10 minutes).

The component B1) to which the composition is added in the present application preferably ranges from 1% by weight to 8% by weight, preferably from 1% by weight to 6% by weight, more preferably from 3% by weight to 6% by weight, particularly preferably 3% by weight. Up to 5% by weight based on the total weight of the composition.

B2) Poly-oxygen-acrylate rubber with core-shell structure

For the purposes of the present invention, component B2) is a polyfluorene-acrylate rubber having a core-shell structure.

Preferably, the composite rubber having a graft active site contains 10% by weight to 90% by weight of the polyoxyn-rubber component and 90% by weight to 10% by weight of the polyalkyl (meth) acrylate-rubber component The two components penetrate each other in the composite rubber such that they are essentially inseparable from each other.

The polyoxyxene rubber is preferably produced by emulsion polymerization using a decyloxymonomer unit, a crosslinking or branching agent (IV) and optionally a grafting agent (V).

Using dimethyl methoxy oxane or cyclic organo oxane having at least a 3-membered ring (preferably 3 to 6 membered rings), for example and preferably as a decane-monomer structural unit, for example and preferably hexamethyl Cyclotrioxane, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexene A siloxane, a trimethyltriphenylcyclotrioxane, a tetramethyltetraphenylcyclotetraoxane, an octaphenylcyclotetraoxane.

The organooxane can be utilized singly or in a mixture of two or more such monomers. The polyoxyxene rubber preferably contains not less than 50% by weight and particularly preferably not less than 60% by weight of the organodecane, relative to the total weight of the polyoxy-rubber component.

Crosslinking agents having 3 or 4 functionalities (extra. 4) based on decane are preferably used via crosslinking or branching agent (IV). Preferred below are trimethoxycarbane, triethoxybenzocane, tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane and tetrabutoxydecane. The crosslinking agent can be utilized alone or in a mixture of two or more such reagents. Tetraethoxydecane is particularly preferred.

The crosslinking agent is used in an amount of from 0.1 to 40% by weight based on the total weight of the polyoxy-rubber component. The amount of the crosslinking agent is selected in such a manner that the degree of swelling of the polyoxyxene rubber (measured in toluene) is from 3 to 30, preferably from 3 to 25, particularly preferably from 3 to 15. The degree of swelling is defined as the weight ratio of the amount of toluene absorbed by the polyoxyethylene rubber to the amount of dry polyoxyxene rubber when saturated with toluene at 25 °C. The determination of the degree of swelling is described in detail in EP 0 249 964 A2.

If the degree of swelling is less than 3, that is, if the content of the crosslinking agent is too high, the polyoxymethylene rubber cannot exhibit appropriate rubber-like elasticity. If the degree of swelling is greater than 30, the polyoxymethylene rubber cannot form a domain structure in the matrix polymer, and thus the impact strength cannot be improved; thus the effect will be similar to the simple addition of polydimethyloxane.

The tetrafunctional crosslinker is preferred over the trifunctional crosslinker because the degree of swelling is then readily controlled within the above limits.

It is suitable as a grafting agent (V) to form a compound conforming to the following formula: CH ₂ =C(R ² )-COO-(CH ₂ ) _p -SiR ¹ _n O _(3-n)/2 (V-1 )

CH ₂ =CH-SiR ¹ _n O _(3-n)/2 (V-2) or HS-(CH ₂ ) _p -SiR ¹ _n O _(3-n)/2 (V-3)

Wherein R ¹ represents C ₁ -C ₄ -alkyl (preferably methyl, ethyl or propyl), or phenyl, R ² represents hydrogen or methyl, n is 0, 1 or 2, and p is a number 1 To 6.

Propylene decyl decane or methacryl decyl decane is particularly suitable for forming the aforementioned structure (V-1) and has high grafting efficiency. As a result, the graft chain can be efficiently formed, which is advantageous for the impact strength of the resulting dendritic composition.

The following are preferred: β-methacryloxy-ethyldimethoxymethyl-decane, γ-methylpropenyloxy-propylmethoxydimethyl-decane, γ-methylpropene醯oxy-propyldimethoxymethyl-decane, γ-methylpropenyloxy-propyltrimethoxy-decane, γ-methylpropenyloxy-propylethoxydiethyl- Decane, γ-methylpropenyloxy-propyldiethoxymethyl-decane, δ-methacryloxy-butyldiethoxymethyl-decane or a mixture thereof.

The polyoxymethylene rubber can be produced by emulsion polymerization as described in US Pat. No. 2,891,920 and US Pat. In this case, a polyoxyxene rubber is obtained in the form of an aqueous latex. In this case, a mixture comprising an organic oxoxane, a crosslinking agent and optionally a grafting agent is mixed in the presence of an emulsifier such as a sulfonic acid (for example an alkylbenzenesulfonic acid or an alkylsulfonic acid), for example by means of homogenization. The device, which is sheared with water, is polymerized to form a polyoxyethylene rubber latex. It is particularly suitable for the alkylbenzene sulfonic acid because it acts not only as an emulsifier but also as a polymerization initiator. In this case, it is advantageous to combine a metal salt of a sulfonic acid with an alkylbenzenesulfonic acid or a metal salt of an alkylsulfonic acid because the polymer is stabilized by this means during the subsequent graft polymerization.

After the polymerization, the reaction mixture is neutralized by adding an aqueous alkaline solution to terminate the reaction, for example, an aqueous solution of sodium hydroxide, potassium hydroxide or sodium carbonate.

The poly(meth)acrylic acid alkyl ester-rubber component suitable for polyoxyxa-acrylate rubber can be produced from alkyl methacrylate and/or alkyl acrylate, crosslinking agent and grafting agent. Demonstrated in this regard and preferred alkyl methacrylate and/or alkyl acrylate C ₁ - to C ₈ -alkyl esters, such as methyl, ethyl, n-butyl, tert-butyl, n-propyl, hexyl Ester, n-octyl ester, n-lauryl ester and 2-ethylhexyl ester; haloalkyl esters, preferably halogen C ₁ - to C ₈ -alkyl esters, such as chloroethyl acrylate, and mixtures of such monomers. Particularly preferred is n-butyl acrylate.

A monomer having more than one polymerizable double bond can be used as the poly(meth)acrylic acid alkyl ester-rubber component crosslinking agent for the polyfluorene oxide-acrylate rubber. Preferred examples of the crosslinking monomer are esters of an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and an unsaturated monohydric alcohol having 3 to 12 carbon atoms, or 2 to 4 OH groups and 2 to 20 An ester of a saturated polyol of carbon atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol Acrylate and 1,4-butanediol dimethacrylate. The crosslinking agent can be used singly or as a mixture of at least two crosslinking agents.

Exemplary and preferred grafting agents are allyl methacrylate, triallyl cyanurate, triallyl isocyanurate or mixtures thereof. Allyl methacrylate can also be used as a crosslinking agent. The grafting agent can be used singly or as a mixture of at least two grafting agents.

The amount of the crosslinking agent and the grafting agent is from 0.1% by weight to 20% by weight based on the total weight of the polyalkyl (meth) acrylate-rubber component of the polyoxyxa-acrylate rubber.

Polyoxymethylene-acrylate rubber is produced in the form of an aqueous emulsion. This latex is then enriched with alkyl methacrylate and/or alkyl acrylate, crosslinker and grafting agent and polymerized. Preference is given to priming initiated emulsion polymerizations, for example by peroxide initiators, azo initiators or redox initiators. Particularly preferred are the use of redox initiator systems, especially hydrocarbon sulfate initiator systems made from a combination of ferric sulfate, methylene diamine tetraacetate, insurance powder and hydroperoxide.

The grafting agent used to make the polyoxyxene rubber causes the polyalkyl (meth) acrylate-rubber component to be covalently bonded to the polyoxy-rubber component. During the polymerization, the two rubber components penetrate each other and form a composite rubber, which is not separated into its constituent components after polymerization.

The poly(oxy) acrylate rubbers which are preferably used are described in JP 08259791 A, JP 07316409 A, EP-A 0315035, US Patent No. 4,963, 619, and EP 315 035, the disclosure of which is incorporated herein by reference.

Preferably, component B2) is selected from the group consisting of a polystyrene-acrylate rubber grafted with a styrene-acrylonitrile copolymer (e.g., Metablen SX-006 and Metablen SRK200 from Mitsubishi Rayon Co. Ltd.).

In the present application, the component B2) is added in an amount ranging from 1% by weight to 8% by weight based on the total weight of the composition, preferably from 1% by weight to 6% by weight, particularly preferably from 3% by weight to 6% by weight. %, based on the weight of all components.

Polyoxy- acrylate rubbers are known and described, for example, in U.S. Patent No. 5,807,914, EP 430 134, and U.S. Patent No. 4,888,388, the entire disclosure of which is incorporated herein by reference.

B3) Acrylate rubber-based core-shell impact modifier

For the purposes of the present invention, component B3) is an acrylate rubber-based core-shell impact modifier.

Preferably, component B3) is selected from the group consisting of methyl acrylate grafted acrylate rubber, including Paraloid® EXL 2311, EXL 2313, EXL 2315, EXL 2300, EXL 2390 from Dow Chemical, and from Arkema. Durastrength® 410, 440 and 480.

In the present application, the component B3) is added in an amount ranging from 1% by weight to 8% by weight based on the total weight of the composition, preferably from 1% by weight to 6% by weight, particularly preferably from 2.5% by weight to 3.4% by weight. %, based on the total weight of the composition.

Component C-additive

The polycarbonate composition may also be blended with customary additives of conventional thermoplastics, such as flame retardant fillers, antioxidants, heat stabilizers, antistatic agents, colorants and pigments, mold release agents, UV absorbers, and IR absorbers. Agent.

The amount of the additive is preferably up to 5% by weight, more preferably from 0.01 to 3% by weight, based on the total composition.

Examples of suitable antioxidants or heat stabilizers are alkylated monophenols, alkylthiocresols, hydroquinones and alkylated hydroquinones, tocopherols, hydrogenated thiodiphenyl ethers, alkylene bisphenols, O-, N - with S-benzyl compound, hydroxybenzylated malonate, aromatic hydroxybenzyl compound, triterpenoid compound, decyl phenol, β-(3,5-di-t-butyl-4-hydroxyl Phenyl)propionate, β-(5-tert-butyl-4-hydroxy-3-tolyl)propionate, β-(3,5-di-cyclohexyl-4-hydroxyphenyl)propionic acid Ester, 3,5-di-tert-butyl-4-hydroxyphenyl acetate, β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid decylamine, suitable for sulfur Synergists, secondary antioxidants, phosphites and phosphonites, benzofuranones and porphyrins.

Preferably, an organic phosphite such as triphenylphosphine, trimethylphosphine or 2,4,6-tris-tert-phenyl-2-butyl-2-ethylpropane-1,3-diester is administered. Phosphonates and phosphines, generally the organic group consists wholly or partly of an optionally substituted aromatic group.

Particularly suitable additives are IRGANOX® 1076 (3,5-di-t-butyl-4-hydroxyhydrocinnamate octadecyl ester, CAS No. 2082-79-3) and also triphenylphosphine (TPP).

Examples of suitable release agents are esters or partial esters of mono to hexahydric alcohols, more particularly glycerol, neopentyl alcohol or Guerbet alcohol.

Monohydric alcohols are, for example, stearyl alcohol, palmitol and Guerbet alcohol. The glycol is, for example, ethylene glycol; the trihydric alcohol is, for example, glycerin; the tetrahydric alcohol is, for example, neopentyltetraol and mesobutanol; and the pentavalent alcohol is, for example, arabitol, ribitol, and xylitol; The alcohols are, for example, mannitol, sorbitol and galactitol.

Preferred ester-based monoesters, diesters, triesters, tetraesters, pentaesters and hexaesters or mixtures thereof, and more particularly based saturated aliphatic C ₁₀ - to C ₃₆ - hydroxyalkyl monocarboxylic acids and optionally monocarboxylic acids, more ₁₄ best saturated aliphatic C - to C ₃₂ - a statistical mixture of monocarboxylic acids and optionally monocarboxylic acid of hydroxyl.

Commercially available fatty acid esters (especially neopentyl alcohol and glycerol) may contain <60% of various partial esters as a result of the preparation process.

Examples of saturated aliphatic monocarboxylic acids having 10 to 36 carbon atoms are citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachidic acid, abietic acid, tetracosic acid, and Hexadecaic acid and octadecanoic acid.

PETS (neopentitol tetrastearate) is a typical release agent for polycarbonate resins that promotes mixing methods and assists in the release of molded parts from the mold.

The polycarbonate compositions of the present invention can be prepared by conventional methods known to those skilled in the art, for example, by the following steps: 1) premixing impact modifiers with other additives such as lubricants and antioxidants; 2) compounding polycarbonate a blend of resin and premix; 3) pelletized to obtain pellets.

Another aspect of the present invention provides a molded part obtainable from the above polycarbonate composition, preferably a cover of electrical and electronic parts.

In an embodiment of the invention, the cover is a cover component of a mobile phone, laptop, adapter, charger, outlet, or switch.

In the present invention, a number of typical coating materials for mobile phone covers from the market and Nivea sunscreen lotions are used as general chemical for chemical resistance and chemical resistance.

Method and materials: Composition preparation steps (general introduction):

On the Coperion ZSK26MS extruder, the barrel temperature was 240 ° C to 265 ° C and the output was 32 to 35 kg / h, and the mixing was performed.

Impact modifiers and other additives (release agents) are commercially available. Paraloid® EXL-2650A is a MBS (methyl methacrylate-butadiene-styrene) from Dow Chemical. Paraloid® EXL-2311 is an acrylate-based core-shell impact modifier from Dow Chemical. SX-006 is a poly-oxygen-acrylate rubber with a core-shell structure from Mitsubishi Rayon Co. A series of ethylene methyl acrylate copolymers (EMA) having different comonomer contents and melt flow were used, including Elvaloy® AC1820, AC1125 and AC1330 from Dupont.

Materials and reagents:

experiment method:

1. The impact strength of the IZOD method of the examples and comparative examples was measured according to ISO 180/A:2000 at two different temperatures. The sample rod was cut at a size of 80 nm x 10 nm x 3 nm. The notch radius is 0.25 mm. Ten samples were tested for each experimental condition. The impact strength values are shown in Tables 3 and 4 together with the type of fracture (P or C). P stands for partial fracture, which symbolizes ductile behavior, and C stands for complete fracture, corresponding to brittle behavior. The results of the examples and comparative examples are shown in Tables 3 and 4, respectively.

2. Characteristic Coating Resistance The difference in breakdown energy was measured in a multiaxial impact (MAI) test before and after both the coating examples and the comparative examples. Coating materials are obtained from the market. The relative change (%) in breakdown energy was calculated for each of the examples and the comparative examples, and is shown in Tables 3 and 4.

Tables 3 and 4 show the performance comparison between the examples and the comparative examples regarding the notched impact properties and the coating resistance characterized by the MAI breakdown energy change after coating.

As clearly shown in Table 4, the polycarbonate modified with MBS (EXL-2650A) (Comparative Examples 1 and 2) lost a lot of breakdown energy after application of the coating, suggesting its poor coating resistance. As indicated in Table 4, further increasing the MBS loading in polycarbonate to 5% (all wt%, based on the total composition) did not improve coating resistance. For the acrylate rubber-based impact modifier EXL-2311, the coating resistance is similar to MBS, although some improvements can be observed, but not significant enough. Increasing the EXL-2311 load by 6% also had a limiting effect on improved coating resistance (Comparative Example 4). For the polyoxymethylene-acrylate rubber-based impact modifier SX-006 (SAN graft), a 3% loading (Comparative Example 5) resulted in improved coating resistance with an increased load of 6% (Comparative Example 6) ) will further improve coating resistance. However, at 3% and 6% of both SX-006 loads, the notched impact properties at -20 °C are not ductile. For Evaloy® AC1820 (EMA), a 3% load at -20 °C notch impact performance is not ductile and coating resistance is also unsatisfactory. Negative at 6% AC1820 The ductility can be achieved at -20 °C. However, the MAI breakdown energy will drop significantly from the original 51.8J to 32J at 3%, but the breakdown energy level can be maintained after coating. Therefore, for all of the impact modifiers mentioned in these comparative examples, equilibrium properties cannot be achieved.

Interestingly, as shown in Table 3, the examples using several combinations of impact modifiers showed significantly improved coating resistance and ductile behavior at -20 °C. The ratio of change in MAI breakdown energy after coating can be kept below 10%, while the original breakdown energy level can still be maintained above 44J. Metablen® SX-006 can be combined with Elvaloy® resins (AC1820, AC1125, and AC1330) with different structures and flow levels to achieve excellent coating resistance and good ductility at low temperatures. It also works very well with Paraloid® EXL-2311 (Example 7). For Paraloid® EXL-2311, it can also be operated with Elvaloy® AC1820 for very good coating resistance and low temperature ductility. Therefore, from the three types of impact modifiers (core-shell structure-based polyfluorene-acrylate rubber, and acrylate rubber-based core-shell structure impact modifier, and ethylene acrylate) Any combination of two impact modifiers of copolymer resin) can be used in polycarbonate systems to achieve superior coating resistance and good low temperature impact properties (-20 ° C).

Claims (9)

A polycarbonate composition comprising: A) at least one thermoplastic, aromatic polycarbonate in an amount ranging from 85% to 97% by weight based on the total weight of the composition; and B) at least two selected from the group consisting of A group of impact modifiers B1) ethylene acrylate copolymer, in an amount ranging from 1% by weight to 8% by weight based on the total weight of the composition; B2) having a core-shell structure Polyoxyl-acrylate rubber, in an amount ranging from 1% by weight to 8% by weight based on the total weight of the composition; B3) Acrylate rubber-based core-shell impact modifier, in an amount ranging from 1 weight % to 8% by weight, based on the total weight of the composition; provided that the impact modifiers B1, B2 and/or B3 are used in an amount of from 3 to 15% by weight, based on the total weight of the composition. The polycarbonate composition according to claim 1, wherein B1 is a copolymer of the formula (I) ethylene-(meth)acrylate, Wherein R ₁ is methyl or hydrogen, R ₂ is hydrogen or C ₁ - to C ₁₂ -alkyl, and each of x and y is independently polymerized (integer), and n is an integer of >=1. A polycarbonate composition according to claim 2, wherein R ₂ is methyl, ethyl, propyl, isopropyl, butyl, t-butyl, t-butyl, isobutyl, hexyl, Isoamyl, or a third amyl group. A polycarbonate composition according to any one of the preceding claims, wherein the component B1) is included in an amount ranging from 1% by weight to 6% by weight based on the total weight of the composition. A polycarbonate composition according to any one of the preceding claims, wherein the component B2) is contained in an amount ranging from 1% by weight to 6% by weight based on the total weight of the composition. A polycarbonate composition according to any one of the preceding claims, wherein the component B3) is contained in an amount ranging from 1% by weight to 6% by weight based on the total weight of the composition. The polycarbonate composition according to any one of claims 1 to 3, wherein the component B1) is contained in an amount ranging from 3% by weight to 5% by weight based on the total weight of the composition. The amount of B2) is from 3% by weight to 6% by weight based on the total weight of the composition, and the amount of the component B3) is from 2.5% by weight to 3.4% by weight based on the total weight of the composition. The amounts of impact modifiers B1, B2 and/or B3 are up to 3 to 15% by weight based on the total weight of the composition. An electric/electronic device component prepared by the polycarbonate composition according to any one of claims 1 to 7. An electrical/electronic device component according to item 8 of the patent application, wherein the electrical/electronic device component is a cover member of a mobile phone, a laptop, an adapter, a charger, a socket, or a switch.