KR20110078211A - Transparent and scratch-resistant thermoplastic resin composition with good flame retardancy - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to ensure excellent scratch resistance and transparency as well as excellent flame retardancy. CONSTITUTION: A thermoplastic resin composition comprises (A) 55-95 weight% of an acrylic resin including a bisphenol-A type oligomer and (B) 5-45 weight% of a flame retardant. The acrylic resin including the bisphenol-A type oligomer comprises 100 parts by weight of a bisphenol-A type oligomer and 55-85 weight% of an alkyl methacrylate monomer, and 0.1-5.0 parts by weight of a vinyl monomer having a functional group. The average molecular weight(Mw) of the bisphenol-A type oligomer is 2,000-100,000.

Description

Transparent and Scratch-Resistant Thermoplastic Resin Composition with Good Flame Retardancy

The present invention relates to a transparent scratch resistant thermoplastic resin composition excellent in flame retardancy. More specifically, the present invention provides a transparent scratch-resistant thermoplastic resin polymer comprising a bisphenol-A type oligomer, an acrylic monomer, and a vinyl monomer including a functional group, and a flame retardant blended therein, thereby simultaneously satisfying transparency, flame retardancy, and scratch resistance. It relates to a resin composition.

Generally, acrylic resins have high transmittance, excellent weather resistance, and good mechanical properties. Due to these characteristics, polymethyl methacrylate (hereinafter referred to as PMMA) resin molded articles are used for various optical lenses, optical discs, light guide plates, optical applications, lighting fixtures, signs, various ornaments, automotive tail lamps, instrument panel covers, outdoor exterior materials, etc. It is applied in various fields. In addition, since the PMMA resin is a thermoplastic resin having both excellent scratch resistance properties, it is very usefully used as an exterior material for electric and electronic products.

However, PMMA resin is very difficult to secure flame retardancy, and no transparent flame retardant PMMA products have been commercialized. Recently, the demand for flame retardant resins is increasing due to tightening environmental regulations, but it is difficult to respond to the current PMMA resin.

An amorphous resin capable of satisfying the transparency of the PMMA resin is a polycarbonate-based (hereinafter referred to as PC) resin. PC resin is widely used in automobile parts, monitors and TV housings, office equipment due to excellent mechanical properties and flame retardancy, as well as transparency, but there is a problem that the scratch resistance is weak.

Therefore, it is possible to consider a method of blending a PC resin having easy flame retardancy and a PMMA resin having excellent scratch resistance to satisfy both flame retardancy and scratch resistance at the same time.

US Patent No. 6,359,069 proposes a method for producing a PMMA copolymer comprising a benzoate-based monomer and blending it with a PC to produce a transparent resin. However, such a PMMA copolymer has a problem in that the manufacturing method is complicated and expensive. US Pat. No. 4,743,654 reports that a transparent PC / PMMA blend can be obtained by dissolving PMMA and PC resin in a solvent under appropriate conditions and then removing the solvent. This method is only applicable in extremely limited conditions. It is not suitable as a method for producing molded articles of various shapes. U.S. Patent No. 4,906,696 proposes a process for preparing PMMA copolymers to which acrylic monomers having cyclohexyl groups are applied and blending them with PC resins. Such copolymers have a problem that the compatibility changes according to the monomer ratio, and the physical properties inherent in PMMA are also lowered. U. S. Patent No. 5,280, 070 prepared a transparent PC / PMMA blend using syndiotactic PMMA resins, but commercially preparing synthiotactic PMMA resins is not easy.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy.

Another object of the present invention is to provide a thermoplastic resin composition which is excellent in scratch resistance and transparency and at the same time excellent in flame retardancy.

Still another object of the present invention is to provide an acrylic thermoplastic resin composition which is excellent in flame retardancy at the same time, while having excellent inherent physical properties of the acrylic thermoplastic resin.

Still another object of the present invention is to provide a molded article molded from an acrylic thermoplastic resin composition which is excellent in all the inherent physical properties of the acrylic thermoplastic resin and at the same time excellent in flame retardancy.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above technical problem, the present invention provides a thermoplastic resin composition comprising 55 to 95% by weight of the acrylic resin containing (A) bisphenol-A oligomer and (B) 5 to 45% by weight of the flame retardant do.

In one embodiment of the present invention, the acrylic resin (A) comprising the bisphenol-A type oligomer is (A-1) 15 to 45% by weight of the bisphenol-A type oligomer, (A-2) alkyl methacryl It contains 0.1-5.0 weight part of vinylic monomers which have a (A-3) functional group with respect to 100 weight part of mixtures containing 55-85 weight% of rate monomers.

In another embodiment of the present invention, the bisphenol-A oligomer is represented by the following formula (1).

[Formula 1]

 (F1 is a reactant of epichlorohydrin or diphenyl carbonate, F2 and F3 are each hydrogen or glycidyl ether)

In another embodiment of the present invention, the bisphenol-A oligomer may have a weight average molecular weight (Mw) of 2,000 to 100,000.

In another embodiment of the invention, the alkyl methacrylate monomer (A-2) is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate and mixtures thereof One or more may be selected from the group consisting of.

In another embodiment of the present invention, the vinyl monomer (A-3) having a functional group may be represented by the following formula (2).

[Formula 2]

(R1 is hydrogen or methyl group, R2 is hydrogen, glycidyl, hydroxyethyl or derivatives thereof)

In another embodiment of the present invention, the acrylic resin (A) including the bisphenol-A type oligomer may further include 0.005 to 0.5 parts by weight of a radical initiator and 0.01 to 0.5 parts by weight of a molecular weight regulator.

In order to solve the other technical problem, the present invention provides a molded article molded from the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention is excellent in scratch resistance, transparency and flame retardancy at the same time.

Hereinafter, the present invention will be described in more detail.

The present invention provides a thermoplastic resin composition comprising 55 to 95% by weight of acrylic resin containing (A) bisphenol-A oligomer and 5 to 45% by weight of (B) flame retardant.

 (A) Acrylic resin containing bisphenol-A type oligomer

Acrylic resin (A) comprising a bisphenol-A type oligomer is a mixture 100 containing (A-1) 15 to 45% by weight of a bisphenol-A type oligomer, and (A-2) 55 to 85% by weight of an alkyl methacrylate monomer. It is characterized by including 0.1-5.0 weight part of vinylic monomers which have a functional group (A-3) with respect to a weight part. If the content of the bisphenol-A oligomer is less than 15% by weight, the effect of improving flame retardancy is less. If the content of the bisphenol-A oligomer exceeds 45% by weight, process problems such as sticking of resin to the reactor may occur.

(A-1) Bisphenol-A type oligomer

In the present invention, the bisphenol-A oligomer is represented by the following Chemical Formula 1, and may be formed by reacting bisphenol-A with epichlorohydrin or diphenyl carbonate.

[Formula 1]

 (F1 is a reactant of epichlorohydrin or diphenyl carbonate, F2 and F3 are each hydrogen or glycidyl ether)

Originally, acrylic resins such as PMMA are very difficult to secure flame retardancy, such as adding 45% by weight or more of flame retardant to secure flame retardant properties of V-0. However, when the bisphenol-A type oligomer of the present invention is mixed with an acrylic resin and a flame retardant is added after the acrylic resin is deformed, a synergistic effect occurs in flame retardancy, and an appropriate amount (5 to 45% by weight) of the flame retardant is produced. Even if added, very excellent flame retardant properties can be secured.

 The bisphenol-A oligomer of the present invention has a weight average molecular weight (Mw) of 2,000 to 100,000, preferably 10,000 to 50,000.

(A-2) Alkyl Methacrylate Monomer

Examples of the alkyl methacrylate monomers of the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, and the like, and mixtures of two or more thereof may also be used. . In this invention, methyl methacrylate is preferable.

(A-3) Vinyl monomer containing a functional group

The vinyl monomer including the functional group of the present invention is a compound containing a carboxyl group, a glycidyl group, a hydroxyl group capable of reacting with an epoxy group or a hydroxyl group present at the end or the middle of a bisphenol-A resin, as shown in Formula 2 desirable.

(2)

(R1 is hydrogen or methyl group, R2 is hydrogen, glycidyl, hydroxyethyl or derivatives thereof)

Examples of the monomer may be acrylic acid, methacrylic acid, maleic anhydride, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and mixtures of two or more thereof. Can be.

The vinyl monomer including the functional group of the present invention serves to allow the bisphenol A oligomer to branch to the acrylic base resin. In the case where the acrylic monomer and the bisphenol A oligomer are mixed and polymerized, the bisphenol A oligomer is an oligomer, not a monomer, and thus does not participate in the reaction and is incorporated into the final resin, resulting in a problem of deterioration of the original physical properties of the acrylic resin. However, when polymerizing the vinyl monomer including the functional group of the present invention together, the functional group of the vinyl monomer reacts with the epoxy group or the hydroxyl group of the bisphenol A oligomer, so that the oligomer can partially branch to the acrylic resin. As a result, the original properties of the acrylic resin can be maintained.

 The vinyl monomer containing a functional group is 0.1 to 15 parts by weight based on 100 parts by weight of a mixture containing 15 to 45% by weight of the bisphenol-A type oligomer (A-1) and 55 to 85% by weight of the alkyl methacrylate monomer (A-2). It is preferably added at 5.0 parts by weight. When added too much, since crosslinking may occur first and resin may become a complete crosslinked body, it is good not to exceed 5.0 weight part, and it is good to add more than 0.1 weight part for proper branching of bisphenol A oligomer.

The acrylic resin (A) containing the bisphenol-A oligomer may further contain 0.005 to 0.5 parts by weight of a radical initiator, 0.01 to 0.5 parts by weight of a molecular weight regulator, and the like, in addition to the above composition. Additives such as stabilizers and lubricants may be introduced.

In the present invention, the radical polymerization initiator has a half life of 1 to 40 min at the polymerization temperature, and a content of 0.005 to 0.5 parts by weight is appropriate.

Examples of the initiator include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2-bis (4,4-di-t- Butylperoxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxylaurate , 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzo Ate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, n -Butyl-4,4-bis (t-butyl peroxy) valerate, α, α'-bis (t-butylperoxy) diisopropyl benzene, dicumyl peroxide, 2,5-dimethyl-2,5 -Bis (t-butyl peroxy) hexane, t-butyl cumyl peroxide, di-t-butyl perox Id may select one kind or two or more kinds in the category consisting of use and the like.

As the molecular weight modifier used in the present invention, those represented by n-alkyl mercaptan in the form of CH3 (CH2) nSH are used. For example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and the like are preferable, and n-octyl mercaptan and n-dodecyl mercaptan and the like are suitable.

In the present invention, the molecular weight modifier is used in an amount of about 0.01 to 0.5 parts by weight, more preferably about 0.10 to 0.3 parts by weight, based on 100 parts by weight of the monomer mixture.

(B) flame retardant

The flame retardant used in the present invention mainly uses phosphorus-containing flame retardant and contains 5 to 45% by weight of the resin composition. Phosphorus-containing flame retardants that can be applied refer to conventional flame retardants, for example, phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene ) And metal salts thereof may be applied.

Depending on the application, halogen-based compounds may also be used as flame retardants, and halogen-based compounds generally used may be used. Preferably, halogen-based compounds that can be melted at a normal processing temperature, more specifically, melting points at 250 ° C. or lower, or Preference is given to compounds having a softening point.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the components of the present invention and other additives may be mixed at the same time and then melt extruded in an extruder and prepared in pellet form.

The reaction apparatus used in the present invention is not particularly limited. However, since there is an exothermic phenomenon due to a polymerization reaction in the reactor, it is preferable to control the reaction apparatus by circulating a refrigerant through a jacket or a coil.

In the thermoplastic resin manufacturing method of the present invention, an antidripping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a pigment, a dye, an inorganic additive, or a mixture thereof may be added depending on the end use.

 The present invention also provides a molded article molded from the thermoplastic resin composition. Since the thermoplastic resin composition of the present invention is excellent in scratch resistance, transparency and flame retardancy at the same time, it can be used to produce a plastic molded article having excellent characteristics, it can be preferably used for electrical, electronic components or various transparent products. .

The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Specifications and preparation methods of each component used in the following Examples and Comparative Examples are as follows.

(A) Acrylic resin containing bisphenol-A type oligomer

(A-G1) acrylic resin-1

70% by weight of methyl methacrylate, 30% by weight of bisphenol A (BPA) -containing oligomer resin (YD-019, Kukdo Chemical Co., Ltd.) were prepared, and 0.5 parts by weight of acrylic acid, 0.05 parts by weight of n-octylmercaptan, and 0.03 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane was added as a radical initiator to obtain a uniform state. This was supplied to a reactor and polymerized at 150 ° C., and the physical properties of the polymer are shown in Table 1.

(A-G2) acrylic resin-2

Resin was prepared under the same conditions as (A-G1) except that 0.5 parts by weight of 2-hydroxyethyl acrylate was added instead of acrylic acid. Physical properties of the prepared polymer are shown in [Table 1].

(A-G3) acrylic resin-3

Resin was prepared under polymerization conditions equivalent to (A-G1) except that 0.5 part by weight of glycidyl methacrylate was added instead of acrylic acid. Physical properties of the prepared polymer are shown in Table 1.

PMMA  Suzy

The weight average molecular weight was 90,000, and PM-7200 grade of Cheil Industries was used.

PC  Suzy

 SC-1100 Grade, a PC product of Cheil Industries, Inc., was used.

(B) Flame retardant

Rabitle FP-100 Grade, manufactured by Fushimi, Japan, is a compound having a phenoxyphosphazene oligomer structure.

Example  1-3

The acrylic polymer (A-G1), (A-G2), (A-G3) and the flame retardant indicated above are added to the contents shown in the following [Table 2], and the temperature range of 220 to 260 ° C. in a conventional twin screw extruder is shown. Extruded in the form of pellets. The prepared pellets were dried at 60 ° C. for 3 hours and then injected at 8 ° C. in a molding temperature of 220 ° C. and mold temperature of 60 ° C. to prepare impact, flame retardant, and pencil hardness specimens.

Comparative Examples 1 and 2

PMMA resin and PC resin were added in the amounts as shown in the flame retardant and [Table 2], respectively, to prepare specimens in the same manner as in the above examples.

Property evaluation method

(1) Vicat Softening Temperature (VST): ISO 306, 5kg, 50 ℃ / hr was measured.

(2) IZOD impact strength (kgfcm / cm, 1/8 ", Unnotched): measured with Unnotched specimens, and others were measured by ASTM D256.

(3) Melt index (220 ^° C., 10 kg): measured by ASTM D1238.

(4) Scratch resistance: 10 x 10 cm 2 specimens were measured by pencil hardness according to JIS K 5401 standard. Scratch resistance is evaluated as 3B, 2B, B, HB, F, H, 2H, 3H, etc. according to the result of pencil hardness.The higher the H value, the better the scratch resistance. The higher the B value, the lower the scratch resistance. Tends to be.

(5) Light transmittance: 100 x 100 x 3 mm specimens were produced by injection molding, and measured by a haze meter (? 80, manufactured by Nippon Denshi Kogaku Kogyo Co., Ltd.).

(6) Flame retardant: measured by UL94 standard using a 2.0 mm thick specimen.

According to the composition of the present invention, a methacrylate resin polymer comprising a bisphenol-A oligomer was prepared, and although the bisphenol-A oligomer was included, the physical properties of the polymer were similar to those of general PMMA, and excellent transparency and scratch resistance properties were obtained. The thermoplastic resin polymer having the same content could be prepared.

* BPA resin: YD-019 (Kukdo Chemical Co., Ltd.)

* MMA: Methyl Methacrylate

* AA: acrylic acid

* HEA: hydroxyethyl acrylate

* GMA: glycidyl methacrylate

n-OM n-octyl mercaptan

* Initiator: 1,1-bis (t-butylperoxy) cyclohexane

* PMMA: PM-7200 (Cheil Industries)

* PC: SC-1100 (Cheil Industries)

The composition shown in Table 2 was prepared by adding a flame retardant to Table 1, according to Examples 1 to 3, it was found that the scratch resistance is good through a good H hardness pencil hardness, at the same time V Since -0 was shown, the flame retardant and scratch resistance were simultaneously satisfied. On the other hand, in Comparative Examples 1 and 2, the PMMA resin showed a limit in flame retardancy, while the PC resin showed excellent flame retardancy, but the pencil hardness was relatively poor, making it difficult to expect scratch performance. Seemed. In particular, when comparing Example 1-3 with Comparative Example 1, when the flame retardant is added to the acrylic resin containing the bisphenol-A oligomer according to the composition of the present invention, the flame retardancy compared to the case of adding a flame retardant to the general acrylic resin It can be seen that there is a synergistic effect in terms of improvement.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (9)

(A) 55 to 95% by weight of an acrylic resin comprising a bisphenol-A oligomer; And (B) 5-45 weight percent flame retardant; Thermoplastic resin composition comprising a. The acrylic resin (A) comprising the bisphenol-A oligomer is 15 to 45% by weight of the (A-1) bisphenol-A oligomer and 55 to 85 (A-2) alkyl methacrylate monomers. A thermoplastic resin composition comprising 0.1 to 5.0 parts by weight of a vinyl monomer having a functional group (A-3) based on 100 parts by weight of a mixture containing% by weight. The method of claim 1, wherein the bisphenol-A oligomer is a thermoplastic resin composition, characterized in that represented by the following formula (1): [Formula 1]

(F1 is a reactant of epichlorohydrin or diphenyl carbonate, F2, F3 are each hydrogen or glycidyl ether). The thermoplastic resin composition of claim 1, wherein the bisphenol-A oligomer has a weight average molecular weight (Mw) of 2,000 to 100,000. The thermoplastic resin composition according to claim 1, wherein the flame retardancy measured by UL94 standard using a 2.0 mm thick specimen is V-0. 3. The alkyl methacrylate monomer (A-2) according to claim 2, wherein the alkyl methacrylate monomer (A-2) is from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate and mixtures thereof. Thermoplastic resin composition, characterized in that at least one selected. The thermoplastic resin composition according to claim 2, wherein the vinyl monomer having the functional group (A-3) is represented by the following general formula (2): [Formula 2]

(R1 is hydrogen or methyl group, R2 is hydrogen, glycidyl, hydroxyethyl or derivatives thereof). The thermoplastic resin composition according to claim 2, wherein the acrylic resin (A) containing the bisphenol-A oligomer further comprises 0.005 to 0.5 parts by weight of a radical initiator and 0.01 to 0.5 parts by weight of a molecular weight regulator. A molded article molded from the thermoplastic resin composition according to any one of claims 1 to 8.