KR101160844B1 - The additive composition for flame retardant plastics with improved transparency and manufacturing method thereof and composition for flame retardant thermoplastic resin using the same - Google Patents

Abstract

PURPOSE: A flame-retardant plastic additive composite, a manufacturing method thereof, and a flame retardant thermoplastic resin composition using thereof are provided to enhance heat resistance, dispersibility, transparency, and scratch resistance by micro-encapsulating outside of polytetrafluoroethylene with a methacrylic copolymer resin. CONSTITUTION: A flame-retardant plastic additive composite contains polytetrafluoroethylene. Outside of polytetrafluoroethylene is micro-encapsulated with branched methacryl-based copolymer. The branched methacryl-based copolymer is manufactured by polymerizing alkyl(meth)acrylate-based monomers and branched acrylic monomers. The branched acrylic monomer is aromatic group or cycloaliphatic methacrylate which has a refractive index of 1.555-1.595 and is represented by chemical formula 2b.

Description

The additive composition for flame retardant plastics with improved transparency and manufacturing method such and composition for flame retardant thermoplastic resin using the same}

The present invention relates to a flame-retardant plastic additive composition with improved transparency, a method for producing the same, and a flame-retardant thermoplastic resin composition using the same, and more specifically, to a branched methacrylic copolymer resin having a high refractive index and a high molecular weight outside the polytetrafluoroethylene. Due to the micro-encapsulation, it relates to a flame-retardant plastic additive composition, a method for producing the same, and a flame-retardant thermoplastic resin composition using the same as well as excellent heat resistance and dispersibility.

Due to the social demand for fire safety, the proportion of flame retardant products is gradually increasing.

Products requiring flame retardant properties are mainly electrical and electronic products, and the plastics used are PC, PC / ABS, PC / PBT, PBT, ABS, PP and PMMA.

Conventionally, many halogen-based flame retardants have been used, but environmentally-friendly phosphorus- or melamine-based flame retardants are rapidly increasing due to restrictions on the use of halogen-based flame retardants that generate toxic gases in case of fire.

Since the possibility of carcinogens of halogenated compounds has been raised in Europe since the mid-1980s, the toxicity of halogen-based flame retardants has been controversial until now, and environmental certification agents such as Blue Angel in Germany and TCO in Sweden are The use of flame retardants has become more difficult.

Restriction of the use of Haxardous substances (HRO) includes mercury, cadmium, lead and hexavalent chromium, as well as polybrominated biphenyl (PBB) and polybrominated diphenylether (PBDE). Some halogen-based flame retardants are PBDE.

Decabrominated diphenylether (DECA) is a representative PBDE-based flame retardant, which was exempted from RoHS in 2006 by a long-term hazard assessment, but it is still a subject of controversy.

In general, electric and electronic companies prefer halogen-free flame retardant resins, and non-halogen flame-retardant resins are used to promote environmentally friendly concepts.

The present inventors have developed a patent application for developing a flame-retardant plastic additive composition coated with an alkyl (meth) acrylate-based resin capped at the end of polytetrafluoroethylene. (Korean Patent Registration No. 10-0852159) The flame retardant plastic additive composition has an advantage of excellent heat resistance and dispersibility, but has a problem of insufficient transparency.

The present inventors not only have excellent heat resistance and dispersibility but also improve transparency due to microencapsulation of polytetrafluoroethylene outside with high refractive index and high molecular weight branched methacrylic copolymer resin and alkyl (meth) acrylate resin. An additive composition was developed.

KR 10-0852159 (registration number) 2008.08.13.

An object of the present invention is a flame-retardant plastic additive composition and a method for producing a transparent and improved transparency as well as excellent heat resistance and dispersibility by microencapsulating the outside of the polytetrafluoroethylene into a branched methacrylic copolymer resin having a high refractive index and high molecular weight; It is to provide a flame retardant thermoplastic resin composition using the same.

In order to achieve the above object, the present invention provides the following means.

The present invention comprises polytetrafluoroethylene (PTFE), and the outside of the PTFE is characterized in that the microencapsulated with a branched methacrylic copolymer resin.

The branched methacrylic copolymer resin is characterized in that it is produced by polymerization of a branched acrylic monomer and an alkyl (meth) acrylate monomer.

The branched acrylic monomer is an aromatic or alicyclic methacrylate having a refractive index of 1.555 to 1.595, and is a compound represented by the following Chemical Formula 2b.

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[Formula 2b]

In Formula 2b, Y is oxygen (O) or sulfur (S), Z is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group , Phenylphenyl group and benzylphenyl group.

The alkyl (meth) acrylate monomers are methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-butyl acrylate (n-butyl acrylate), i-butyl acrylate (i-butyl acrylate), 2-ethylhexyl acrylate , Any one selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and i-butyl methacrylate Or a mixture of two or more.

The transparency-enhanced flame retardant plastic additive composition is characterized in that a microcapsule is obtained by agglomerated flock.

In addition, the present invention provides a flame-retardant thermoplastic resin composition with improved transparency comprising 0.01 to 10 parts by weight of the flame-retardant plastic additive composition of claim 1 with respect to 100 parts by weight of the thermoplastic resin.

The thermoplastic resin is selected from the group consisting of polycarbonate resins, acrylic resins, styrene resins, polyester resins, vinyl resins, polyphenylether resins, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins and polyarylate resins. One or more resins or mixtures selected may be used.

In addition, the present invention, the mixing step of preparing a mixture by mixing 10 to 200 parts by weight of the branched acrylic monomer and 10 to 200 parts by weight of the alkyl (meth) acrylate monomers to 100 parts by weight of PTFE latex; And a polymerization step of adding a polymerization initiator to the mixture to polymerize a branched acrylic monomer and an alkyl (meth) acrylate monomer to microencapsulate the outside of PTFE (step 2). It provides a method for producing a flame-retardant plastic additive composition improved transparency comprising a.

Subsequent to the polymerization step, the resulting microcapsules are characterized in that it further comprises a flocculation step of agglomeration to form a flock (flock).

Subsequent to the flocculation step, the floc may further include a grinding step of heating and cooling the floc to a glass transition temperature (Tg) of a resin produced by a polymerization reaction, followed by cooling.

The polymerization reaction is characterized in that the polymerization of any one of emulsion polymerization, suspension polymerization or dispersion polymerization.

The transparent flame retardant plastic additive composition according to the present invention has not only excellent flame retardancy but also excellent transparency and scratch resistance.

In addition, by adding a step of heating to a temperature of Tg or more after the coagulation step to uniformly increase the average particle diameter of the flame retardant plastic additive composition has the advantage that the dispersion can be made very uniform when mixed with the thermoplastic plastic.

1 is a photograph of the specimen of Example 1 and Example 2.
2 is a photograph of a specimen of Examples 3 to 5.

Hereinafter, the present invention will be described in detail.

Hereinafter, the meanings of terms used in the present invention are as follows.

'Flame retardant' refers to a property in which when a polymer molded product comes into contact with a flame, various effects such as a method of making ignition difficult or preventing combustion progress are combined to exhibit a flame retardant effect.

The present invention provides a transparency-enhanced flame retardant plastic additive composition obtained by microencapsulating polytetrafluoroethylene (PTFE) and the outside of the polytetrafluoroethylene with a branched methacrylic copolymer resin having a high refractive index and a high molecular weight.

In the present invention, the branched methacrylic copolymer resin is characterized in that the branched acrylic monomer and the alkyl (meth) acrylate monomer are polymerized to microencapsulate the outside of PTFE.

Preferably, the branched acrylic monomer has a refractive index of 1.555 to 1.595. If the refractive index is less than 1.555, the refractive index is large when added to the transparent thermoplastic resin, resulting in a decrease in transparency.

The branched acrylic monomer may be an aromatic or alicyclic methacrylate, and a compound represented by the following Chemical Formula 2b may be used.

(2b)

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In Formula 2b, Y is oxygen (O) or sulfur (S), and Z is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group , Phenylphenyl group and benzylphenyl group.

The alkyl (meth) acrylate monomers are methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-butyl acrylate (n-butyl acrylate), i-butyl acrylate (i-butyl acrylate), 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-buthyl methacrylate and i-butyl methacrylate Any one or a mixture of two or more selected from the group consisting of (i-buthyl methacrylate) may be used.

Hereinafter, a method for preparing a flame retardant plastic additive composition having improved transparency according to the present invention will be described in detail.

Method for producing a flame-retardant plastic additive composition improved transparency according to the present invention,

A mixing step (step 1) of preparing a mixture by mixing 10 to 200 parts by weight of the branched acrylic monomer and 10 to 200 parts by weight of the alkyl (meth) acrylate monomer to 100 parts by weight of the PTFE latex; And

Adding a polymerization initiator to the mixture to polymerize a branched acrylic monomer and an alkyl (meth) acrylate monomer to microencapsulate the outside of PTFE (step 2); .

Further, the production method is followed by the polymerization step,

The method may further include an aggregating step of aggregating the generated microcapsules to form a flock.

Further, the production method is followed by the aggregation step,

The floc may further include a pulverization step of heating and cooling the floc to a glass transition temperature (Tg) of a resin produced by a polymerization reaction, followed by cooling.

In step 1, 100 parts by weight of the PTFE latex is placed in a reactor, 10 to 200 parts by weight of branched acrylic monomers and 200 to 10 parts by weight of alkyl (meth) acrylate monomers are mixed and stirred for 120 to 240 minutes.

 When the amount of the branched acrylic monomer is less than 10 parts by weight based on 100 parts by weight of the PTFE latex, since the alkyl (meth) acrylate monomer is added in excess of 200 parts by weight, there is a problem that the refractive index is lowered and the transparency is lowered. When it is included in excess, the refractive index is increased to improve the transparency, but there is a problem that the polymerization reaction is not made well.

In the step 2, the polymerization initiator may be used alone or redox of a water-soluble initiator, oil-soluble initiator.

Specific examples of the water-soluble initiator include inorganic initiators such as persulfate, and specific examples of oil-soluble initiators include benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxy peroxide, lauroyl peroxide, octanoyl peroxide and methyl. Organic peroxides such as ethyl ketoperoxide, diisopropyl peroxydicarbonate, cyclohexanone peroxide, t-butylhydroperoxide or diisopropylbenzenehydroperoxide; At least one or more of an azo nitrile compound, an azo acyclic amide compound, an azo cyclic amide compound, an azo amide compound, an azo alkyl compound or an azo ester compound can be used.

The polymerization initiator is used in an amount of 0.001 to 10 parts by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total branched acrylic monomers and alkyl (meth) methacryl monomers.

The polymerization reaction of step 2 is preferably any one of emulsion polymerization, suspension polymerization or dispersion polymerization, more preferably emulsion polymerization, the polymerization temperature is preferably 0 ~ 280 ℃, 40 It is more preferable that it is -120 degreeC. In order to perform the emulsion polymerization, in step 1, a suitable known emulsifier and dispersant may be further added, as long as it does not contradict the transparent flame retardant properties of the present invention. The emulsifier that can be used for these polymerizations is not particularly limited, but various conventionally known emulsifiers can be used. Examples include anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl phosphate ester salts and dialkyl sulfoco salts; Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitol fatty acid ester, and glycerin fatty acid ester; Cationic surfactants, such as an alkylamine salt, can be used. These emulsifiers can be used alone or in combination.

The aggregation step of agglomerating the microcapsules formed in the polymerization step will be described in detail.

In the coagulation step, the formed microcapsules may be coagulated using a known method such as filtration, dialysis, or salting. Preferably, the method of salting is used.

In the salting method, a flocculant is added to form a floc. The flocculant is a monovalent to trivalent metal salt or an acid such as sulfuric acid or acetic acid. Specifically, as the metal salt, CaCl ₂ , MgSO ₄ or Al ₂ (SO ₄ ) ₃ is mainly used, and it is preferable to use an acid rather than a metal salt. Microcapsules in which aggregation occurs are obtained by centrifugation. On the other hand, the floc of the microcapsules obtained through the flocculation step is preferably to remove the moisture through drying.

The flocculated floc of the microcapsules from which the coagulant has been removed from water can be commercialized to a desired size through a step of heating and pulverizing.

The heating temperature can be appropriately added or decreased depending on the type of monomer polymerized in the range of 10 to 200 ° C, more preferably 30 to 130 ° C.

The grinding process may use a known grinding process, and may be a method such as knife cutting or milling. The average particle diameter of the flame-retardant plastic additive composition improved transparency obtained in the crushing step is preferably adjusted to 0.05 ~ 4.00mm, more preferably 1.00 ~ 2.00mm.

After the pulverizing step, if necessary, any one of dehydration, drying, or packaging of the flame-retardant plastic additive composition having improved transparency may be added, or the process may be continuously added.

The flame-retardant plastic-added composition having improved transparency obtained by such a manufacturing method may be used in the production of flame-retardant thermoplastic resin having improved transparency by varying the amount thereof as necessary and including it in a thermoplastic resin.

100 parts by weight of the thermoplastic resin according to the present invention, the transparency of the flame-retardant plastic additive composition is improved by mixing 0.01 ~ 10 parts by weight of the transparency improved flame retardant thermoplastic resin composition after mixing the additives for other extrusion process through a known extrusion process A flame retardant thermoplastic resin with improved transparency can be prepared.

The thermoplastic resin is selected from the group consisting of polycarbonate resins, acrylic resins, styrene resins, polyester resins, vinyl resins, polyphenylether resins, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins and polyarylate resins. One or more resins or mixtures selected may be used.

Hereinafter, the constitution and effects of the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, but the scope of the present invention is not limited by these examples.

Into a reactor containing 1,000 g of PTFE latex (50 wt% solids), 250 g of o-Phenylphenoxy ethyl acrylate (PPE, refractive index: 1.5760) and 250 g of methyl methacrylate (MMA) were added. Mix. At this time, 20g of alkylbenzenesulfonate as an emulsifier is added to be able to easily emulsify, and stirred and mixed at 300rpm for 1 hour.

5 g of benzoyl peroxide, a polymerization initiator, is added to the reactor and heated to 70 ° C. to initiate a polymerization reaction. By this reaction, the ortho phenylphenoxy ethyl acrylate and methyl methacrylate are polymerized to enclose the outside of PTFE in an emulsion state to form microcapsules.

The flocculant H ₂ SO ₄ was added to the microcapsules emulsion solution to coagulate, and then rotated at 1,000 rpm to aggregate the microcapsules by centrifugation, and then the reaction temperature was increased to 100 to 110 ° C. Form to maintain strength to some extent. Thereafter, the mixture was cooled, washed several times with pure water and dried to obtain a flame-retardant plastic additive composition having improved transparency in the form of microcapsules.

15 g of the flame-retardant plastic additive composition having improved transparency was compounded with 3,000 g of polycarbonate resin to prepare a flame-retardant thermoplastic resin composition having improved transparency. At this time, the extruder used was TEK30 (30 mmφ, L / D = 48) of SM PLATEK Barrel temperature was processed to 280 ~ 300 ℃, screw speed 50rpm conditions.

In Example 1, the transparency was improved in the same manner as in Example 1 except that 400 g of o-Phenylphenoxy ethyl acrylate (PPE, refractive index: 1.5760) and 100 g of methyl methacrylate were added. A flame retardant thermoplastic resin composition was prepared.

In Example 1, except that 250 g of o-Phenylphenoxy ethyl methacrylate (PPM, refractive index: 1.5710) and 250 g of methyl methacrylate were added in place of the ortho phenylphenoxy ethyl acrylate. In the same manner as in Example 1 was prepared a flame-retardant thermoplastic resin composition with improved transparency.

In Example 1, except that 375 g of o-Phenylphenoxy ethyl methacrylate (PPM, refractive index: 1.5710) and 125 g of methyl methacrylate were added instead of the oso phenylphenoxy ethyl acrylate. In the same manner as in Example 1 was prepared a flame-retardant thermoplastic resin composition with improved transparency.

Example 1 was carried out except that 400 g of o-Phenylphenoxy ethyl methacrylate (PPM, refractive index: 1.5710) and 100 g of methyl methacrylate were added instead of the oso phenylphenoxy ethyl acrylate. In the same manner as in Example 1 was prepared a flame-retardant thermoplastic resin composition with improved transparency.

Comparative Example 1

A general flame retardant thermoplastic resin composition was prepared in the same manner as in Example 1, except that 167 g of butyl acrylate (BA) and 333 g of methyl methacrylate were added instead of ortho phenylphenoxy ethyl acrylate. Prepared.

[Experimental Example 1]

Injection molded specimens were prepared from the flame retardant thermoplastic resin compositions obtained in Examples and Comparative Examples, and flame retardancy, light transmittance, turbidity, and drip were measured and shown in Table 1 below. In addition, photographs of the specimens of Example 1 and Example 2 are shown in FIG. 1, and photographs of the specimens of Examples 3 to 5 are shown in FIG. 2.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1

Configuration

PTFE 1000 g 1000 g 1000 g 1000 g 1000 g 1000 g MMA 250g 100 g 250g 125 g 100 g 333 g PPE 250g 400 g PPM 250g 375 g 400 g BA 167 g
Properties

Light transmittance (%) 83 85 88 90 92 75 Haze 15 10 8 5 3 45 Drip none none none none none none UL grade V0 V0 V0 V0 V0 V0

In Table 1, compared to the flame retardant thermoplastic resin of Comparative Example 1 in which the outside of PTFE was microencapsulated with BA (butyl acrylate) and MMA (methyl methacrylate), the outside of PTFE had a high refractive index and a high molecular weight branched methacrylic air. It can be seen that the light transmittance and turbidity of the flame-retardant thermoplastic resin microencapsulated with the copolymer resin (PPE or PPM) and MMA (methyl methacrylate) are remarkably excellent.

Therefore, the flame retardant plastic additive composition according to the present invention has good dispersibility, no drip property (falling phenomenon), and satisfies the flame retardancy standard, and has excellent transparency.

Claims (11)

Polytetrafluoroethylene (PTFE) containing, the outside of the PTFE is microencapsulated with a branched methacrylic copolymer resin,
The branched methacrylic copolymer resin is produced by polymerization of a branched acrylic monomer and an alkyl (meth) acrylate monomer,
The branched acrylic monomer is an aromatic or alicyclic methacrylate having a refractive index of 1.555 to 1.595, and is a compound represented by the following Chemical Formula 2b,
The alkyl (meth) acrylate monomers are methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-butyl acrylate (n-butyl acrylate), i-butyl acrylate (i-butyl acrylate), 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-buthyl methacrylate and i-butyl methacrylate (i-buthyl methacrylate) is a flame retardant plastic additive composition with improved transparency, characterized in that any one or a mixture of two or more selected from the group consisting of.

(2b)

Chemical formula In 2b, Y is oxygen (O) or sulfur (S), Z is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenyl It is either selected from the group consisting of a phenyl group and a benzylphenyl group.
delete delete delete The method of claim 1,
The flame-retardant plastic-added composition with improved transparency is a flame-retardant plastic-added composition with improved transparency, characterized in that obtained as a flock of agglomerated microcapsules.
0.01 to 10 parts by weight of the flame-retardant plastic additive composition improved transparency of claim 1 with respect to 100 parts by weight of thermoplastic resin,
The thermoplastic resin is selected from the group consisting of polycarbonate resins, acrylic resins, styrene resins, polyester resins, vinyl resins, polyphenylether resins, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins and polyarylate resins. A flame retardant thermoplastic resin composition with improved transparency, characterized in that at least one resin or mixture selected.
delete A mixing step (step 1) of preparing a mixture by mixing 10 to 200 parts by weight of the branched acrylic monomer and 10 to 200 parts by weight of the alkyl (meth) acrylate monomer to 100 parts by weight of the PTFE latex; And
Adding a polymerization initiator to the mixture to polymerize a branched acrylic monomer and an alkyl (meth) acrylate monomer to microencapsulate the outside of PTFE (step 2); Including,
The branched acrylic monomer is an aromatic or alicyclic methacrylate having a refractive index of 1.555 to 1.595, and is a compound represented by the following Chemical Formula 2b,
The alkyl (meth) acrylate monomers are methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), n-butyl acrylate (n-butyl acrylate), i-butyl acrylate (i-butyl acrylate), 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-buthyl methacrylate and i-butyl methacrylate (i-buthyl methacrylate) A method for producing a transparency-enhanced flame retardant plastic additive composition, characterized in that any one or a mixture of two or more selected from the group consisting of.

(2b)

In Formula 2b, Y is oxygen (O) or sulfur (S), Z is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group , Phenylphenyl group and benzylphenyl group.
The method of claim 8, wherein following the polymerization step,
A method for producing a flame-retardant plastic additive composition with improved transparency, characterized in that it further comprises a flocculation step of flocculating the resulting microcapsules to form a flock.
The method of claim 9, wherein following the flocculation step,
Method for producing a flame-retardant plastic additive composition with improved transparency, characterized in that it further comprises a pulverizing step of heating the floc above the glass transition temperature (Tg) of the resin produced by the polymerization reaction, followed by cooling and pulverizing. .
The method of claim 8,
The polymerization reaction is a method of producing a flame-retardant plastic additive composition with improved transparency, characterized in that the polymerization of any one of emulsion polymerization, suspension polymerization or dispersion polymerization.

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