TW201226464A - Thermoplastic resin composition - Google Patents

Abstract

This invention provides a thermoplastic resin composition comprising 5 wt% to 12 wt% of the first grafted-polymer, 16 wt% to 30 wt% of the first polymer, 55 wt% to 70 wt% of the second polymer, and 4 wt% to 8 wt% of the second grafted-polymer. The weight ratio of the second polymer and the first polymer is from 1.8 to 4.1. The species of the polymers, the ratio of the vinyl cryanide based-monomer in the first grafted-polymer, and the ratio of the vinyl cryanide based-monomer in the first polymer are given the definition as set forth in the specification and claim.

Description

201226464 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a resin composition', particularly to a thermoplastic resin composition. [Prior Art] Thermoplastic resin such as vinyl cyanide-styrene resin (abbreviated as AS resin), vinyl cyanide-butadiene-styrene resin (abbreviated as ABS resin) and methyl methacrylate resin (abbreviated as ρ) Μ Μ A) and other resins have been widely used in various fields such as household appliances, mechanical parts, office supplies, electronic components, and A-car industries. However, products made from thermoplastic resins often have disadvantages such as low surface hardness and poor scratch resistance compared to other plastic products, thus limiting the application in some of these fields. Therefore, the prior art uses a method of spraying a protective film on the surface of the thermoplastic resin article or coating the non-woven fabric on the surface thereof to improve the scratch resistance of the surface of the related article, but the surface coating method gives the environment Bringing pollution, without the way of weaving, will increase production costs. In recent years, in order to meet the requirements of the industry for hardness and other properties, the current research of all parties is mainly to mix the aforementioned thermoplastic resin into a composition having specific properties, and then to apply it. The main component of the thermoplastic resin composition used in the coating field is a rubber polymer, a copolymer of a styrene-based monomer and a vinyl cyanide monomer, and an acrylic vinegar monomer and methacrylic acid. a copolymer obtained by polymerizing an ester monomer, wherein a segment derived from a styrene monomer contributes to the processability of the composition and the chain derived from the vinyl cyanide monomer. The segments contribute to the heat resistance and solvent resistance of the composition. The resin composition thus formed is effective in improving the surface hardness thereof, but the components in the resin composition may not be uniformly mixed due to poor phase uniformity, thereby affecting the gloss of the resin composition. Impact resistance. Further, most of the prior art improves the impact resistance of the resin composition by adding a rubber polymer. However, as the amount of the rubber polymer added increases, the transparency of the resin composition deteriorates. Therefore, how to prepare a thermoplastic resin composition which has the advantages of high hardness, good transparency, good impact resistance and solvent resistance has become an urgent research topic in the industry. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a thermoplastic resin composition which has high hardness, good transparency, impact resistance and solvent resistance. The thermoplastic resin composition of the present invention comprises: 5 wt% to 12 wt% of a first-graft polymer, 16 wt% to 3 wt% of a first polymer, and 55 4 wt% of a second polymer' and 4 is a second graft polymer of ~8. The first pure polymer is a butadiene rubber polymer grafted with a styrene monomer unit and a vinyl cyanide monomer unit, and the styrene monomer unit and the cyanide The total weight of the vinyl monomer unit is 27 wt% to 34 w for the single core of the vinyl cyanide monomer. The first polymer comprises at least a styrene monomer unit and at least a cyanide vinyl monomer unit, and based on the total weight of the δ hexene vinyl monomer unit and the vinyl cyanide monomer unit. The vinyl cyanide monomer unit accounts for 16 wt% to 24 wt%. The second 201226464 polymer includes at least one monomer unit selected from the group consisting of an acrylate monomer unit, a methyl acrylate monomer unit, or a combination of the above two units. The second graft polymer comprises at least a butadiene monomer unit, at least one styrene monomer unit, and at least one other copolymerizable monomer unit, and the other copolymerizable monomer unit is selected from the group consisting of An acrylic vine monomer unit, a mercapto acrylate monomer unit or a combination of the above two units. The weight ratio of the second polymer to the first polymer is from 1.8 to 4.1. The effect of the present invention is: the thermoplastic resin composition of the present invention,

The resin composition has the advantages of high pencil hardness, good light transmittance, good impact resistance and good solvent resistance by blending different polymers and controlling the specific component content within a specific range. It is more versatile and can achieve the object of the present invention. [Embodiment] The thermoplastic resin composition of the present invention comprises: 5 wt% to 12 wt% of a first-graft polymer, 16 wt% to 30 wt% of a first polymer, and 55 to 7 wt%. The first polymer, and 4 wt% to 8 (d) of the second graft polymer. The eucalyptus polymer is a butyl rubber polymer enthalpy grafted with an m-type monomer unit and a vinyl cyanide monomer unit, and the 'vinyl monomer unit and the vinyl cyanide The ratified vinyl monomer unit accounts for 27% by weight to 3" of the total weight of the monomer unit. «Haidi polymer includes at least one styrene monomer unit and at least one vinyl cyanide monomer. , Ganzi ® 7L, wherein the vinylidene monomer unit accounts for 16% of the total weight of the styrene monomer unit and the vinyl cyanide monomer. Wt% 〜24 wt%. 201226464 The second polymer comprises at least one monomer selected from the group consisting of an acrylate monomer unit, a methacrylic vine monomer unit or a combination of the above two units: The graft polymer comprises at least a butadiene monomer unit, at least one styrene monomer unit and at least one other copolymerizable monomer unit, and the other copolymerizable monomer unit is selected from the group consisting of acrylate units. a bulk unit, a mercapto acrylate monomer unit or a combination of the above two units. The weight ratio of the compound to the first polymer is 18 to 41. Preferably, the first graft polymer is based on the total weight of the styrene monomer unit and the vinyl cyanide monomer unit. The vinyl cyanide monomer unit accounts for 28 wt% to 32 wt%; more preferably, the vinyl cyanide monomer unit accounts for 29 Wt% to 32 Wt%: and more preferably, the vinyl cyanide monomer unit accounts for 29 wt% 〜3 1 wt% 杈佳地' In the first polymer, the vinyl cyanide monomer is based on the total weight of the styrene monomer unit and the vinyl cyanide monomer unit. Single/element accounts for 17Wt%~23 Wt%; more preferably, vinylidene cyanide monomer units account for 18 wt%~22 Wt%; and more preferably 'cyanide vinyl monomer units account for 19 wt%~ 22 Preferably, the weight ratio of the second polymer to the first polymer is 1.9 to 4.0; more preferably, the 'weight ratio is 2 〇 to 4 〇; and more preferably, the weight is 2.0 to 3.9 〇. Preferably, the first graft polymer is a graft polymerization reaction of a styrene-butadiene rubber polyglycan with a styrene monomer and a vinyl cyanide monomer. More preferably, the Ding (four) oak The polymer is poly 201226464; the styrene monomer is cyanide-based ethylene (semi-fine SM), and the cyanide precursor is deuterated ethylene (abbreviated as AN). ;+ 稀 与 氮化 氮化 氮化 该 该 该 该 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 烯 烯 烯 烯 烯 烯 烯 烯 烯 烯The material is a copolymer obtained by reacting a monostyrene monomer with a disordered ethylene precursor, and more preferably, the vinyl monomer is stupid, and cyanide The vinyl monomer is vinyl cyanide. In the specific embodiment of the present invention, the first polymer is a mixture of styrene and melamine. The copolymer of acetonide, styrene-cyanide ethylene copolymer (abbreviated as A S). Preferably, the celestial flute - take people,,. K-one polymer is a copolymer obtained by polymerizing a mono-acrylate monomer with a monomethyl methacrylate monomer, or a self-polymerized homopolymer of propylene 1 SB monomer. Or a homopolymer of a self-polymerized methyl methacrylate monomer. More preferably, the acrylic acetonate monomer is decyl acrylate and the methacrylate monomer is methacrylate. Preferably, the second polymer is a polymethyl methacrylate (abbreviated as PMMA) or a copolymer obtained by polymerizing methyl methacrylate with decyl acrylate. More preferably, the second polymer is a copolymer obtained by polymerizing methacrylate with > methyl acrylate, although the copolymer is still generally referred to as polymethacrylic acid. Preferably, the second graft polymer is a core-shell graft polymer, 201226464 and the core thereof is a butadiene rubber rubber binder composed of a butadiene monomer unit. Or a copolymerized stupid B is composed of a styrene monomer unit and a 'shell'. Preferably, the S/, its copolymerizable monomer unit constitutes 'the second graft polymer unit and the other copolymerizable single system are-grafted with a stupid ethylene series. Rubber polymer. Preferably, the second graft rubber polymer is a polymer obtained by graft-reacting monophenylene by-butadiene, early and other. , ', human ground' the butadiene rubber polymer is obtained by polymerization of butadiene monomer to obtain ^ ^ ^ r ^ „ polybutene, the styrene monomer is ethyl bromide and the other The monomer unit copolymerized is methyl methacrylate. In the specific embodiment of the present invention, the second graft polymer is a methacrylic acid "butadiene·thin ethylene copolymer (abbreviated as deleted). The thermoplastic resin composition is prepared by subjecting the above four copolymers, i.e., the first graft polymer, the first polymer, the second polymer, and the second graft polymer, to -240. Preferably, in the present case, it is exemplified that the first graft polymer and the first polymer are between 18 ° C and 220. Mixing at a temperature to obtain a monobutylene-styrene-cyanide copolymer resin (ie, ABS in the following specific examples), and then the butadiene-styrene-cyanide copolymer resin And the second polymer and the second graft polymer are kneaded at a temperature of 22 〇β (: to 240 C, thereby obtaining the present invention Thermoplastic resin composition 201226464

The advantages of the hammer hardness and solvent resistance are good. Example

The illustrations are for illustrative purposes only, and are intended to be illustrative and should not be construed as limiting. <Chemical Source> 1. Polybutadiene: obtained by subjecting a butadiene monomer purchased from Formosa to a polymerization reaction. 2. Polymethyl methacrylate (abbreviated as pmma): manufactured by Chi Mei Industrial Co., Ltd.; model CM-207' has a weight average molecular weight (Mw) of 85,000. 3. Methyl methacrylate-butadiene-styrene copolymer (abbreviated as mbs): manufactured by Kaneka; model number M-511 〇<instrument source> 1. Two-axis extruder: Werner &Pfleiderer; For ZSK-25. 2. Injection molding machine: Zhenxiong; model is SM-90. Before the detailed description of the examples, it is to be noted that the polymer aggregating agent used below is prepared by the inventors, which is obtained by adding 85 parts by weight of η-ethyl acrylate and 15 parts by weight of acrylic acid. 0.3 parts by weight of a third-dodecyl mercaptan, 2.0 parts by weight of potassium oleate, 1.0 part by weight of dioctylsulfonate 201226464 sodium succinate, 0.4 parts by weight of cumene hydroperoxide, 0.3 weight A portion of sodium sulfoxide sulfoxylate and 200 parts by weight of distilled water were reacted at a reaction temperature of 75 ° C for 5 hours to obtain a polymer aggregating agent containing a carboxylic acid group. [Preparation of ABS precursor] <Preparation Example 1 > The preparation steps of the preparation example are as follows: (1) 95 parts by weight of 1,3-butadiene, 5 parts by weight of ethylene cyanide, and 15 parts by weight The potassium persulfate solution was '3 parts by weight of pyrophosphoric acid sodium, 1.5 parts by weight of potassium oleate, 14 parts by weight of distilled water, and 0.2 parts by weight of a third-dodecyl mercaptan at 65. The reaction was carried out for 12 hours at a reaction temperature to obtain a rubber latex having a solid content of about 4% by weight and containing rubber particles having an average particle diameter of 〇.1. — (2) Using 3 parts by weight (dry weight) of a polymer aggregating agent to increase the particle size of the rubber particles in 1 part by weight (dry weight) of the rubber latex to 0.3 m to obtain a particle hypertrophy Rubber latex. A rubber latex with 100 parts of dry weight (dry weight) of particles, 23.3 parts by weight of styrene, 1 part by weight of vinyl cyanide, parts by weight of potassium oleate, and 2 parts by weight of 32 parts by weight Alkyl mercaptan, 0.5 parts by weight of cumene hydroperoxide, 0.2% by weight of ferrous sulfate solution, 3 parts by weight of sodium formaldehyde sulfoxylate solution, 2 parts by weight of hydrazine 25% ethylenediaminetetraacetic acid solution and 2 parts by weight of steamed water mixed. 10 201226464 to obtain rubber grafted latex. (4) The rubber grafted latex is coagulated and dehydrated by vaporized calcium, and then dried to a moisture content of 2 wt% or less, thereby producing a plurality of butadiene rubber particles having a surface grafted with AS, that is, an ABS precursor. And the ethylene cyanide monomer unit 3 was set to 30 wt% based on the total weight of AS' as shown in Table 1 below. <Preparation Examples 2 to 8 >

Preparation Examples 2 to 8 were prepared in the same manner as in Preparation Example 1, except that the amount of styrene and ethylene cyanide in the step (3) was different, so that the step (4) was The content of the vinyl cyanide monomer unit in the obtained ABS precursor was also different, as shown in Table 1 below. Table 1 Stupid ethylene content)

Ethylene cyanide amount (parts by weight) Content of cyanide ethylene monomer unit in ABS precursor (wt%)tt

[Note] The above---I, __I__ υ υ 笨 乙 乙 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体The total weight of the unit] and the [cyanide vinyl monomer unit] is 100 Wt% for the thermoplastic resin composition of the present invention. First, the following is the use of the styrene-cyanide ethylene copolymer (simplified below). AS) & is an applicant's self-made product, in which Examples 1 to 4 and Comparative Examples 1, 2, 4, 5 and 7 are ASs using the model number PN-106 L150 (201226464) The content of the ethylene monomer unit was 18 wt%); Examples 5 and 6 were AS using the model number PN-107 L125 (wherein the content of the cyanide monomer unit was 20 wt%); Examples 7 and 8 The AS is prepared according to the preparation work in the case of Tw 548308. The only difference is that: 7 〇Wt% of styrene and 30% by weight of vinyl cyanide are used to make the... The vinyl cyanide monomer unit content is 22 wt%. The preparation method of AS in Comparative Examples 3, 6, 8, and 9 is the same as that of the actual -7, except that: Comparative Example 6 is a modified ethylene with 90 wt% of styrene and 1 Å. The vinyl cyanide monomer unit of the obtained AS towel contains (4) 14 -; in comparison with Examples 3, 8 and 9, it is changed to use 72-read styrene and 28% by weight of acetylated ethylene' to make AS The vinyl cyanide monomer unit content is 28%. . <Example 1> In the present example, 25 8 wt% of the ABS precursor of Preparation Example i was first kneaded with 74 to 2 wt% of AS at 220 ° C using a twin-axis extruder to extrude ABS. Then, 'the amount of 24 wt% ABS, 7 〇% of pMMA and 6 wt% of MBS is placed in another biaxial extruder, and it is kneaded at 24 '' to obtain the thermoplasticity of the present invention. Resin composition. <Examples 2 to 8 > Examples 2 to 8 The thermoplastic resin composition of the present invention was prepared in the same manner as in Example 1, except that the types and amounts of the components were not the same. The parameters are as shown in Table 2 below. <Comparative Examples 1 to 9 > Comparative Examples 1 to 9 were prepared in the same manner as in Example 1 except that the types and amounts of the respective components were not the same as 201226464. The parameters are as shown in Table 2 below. [Property test] <Light transmittance-total light transmittance> This test method is to use an injection molding machine first, and the above embodiment! The thermoplastic resin composition of 8 to Comparative Examples 1 to 9 was formed into a test sample having a thickness of 2.5 mm, wherein the molding temperature was set at 2 〇〇 t to 24 〇 C 'the mold temperature was set to 5 〇 ° C, and The test was carried out according to the standard method of Α§τΜ D(10)3, and the results are shown in Table 2 below.

<Impact Strength - Simple Support Beam> This test method first prepares a test sample having a size of 8 〇 x H) mm and a thickness of 4 faces under the same molding conditions as in the light transmittance test method (no flaw on the test piece) IS〇179, < LharPy Impact test method to measure the punching strength of the test sample prepared, u + balance strength, the span is adjusted to 40mm during the test. The results are shown in Table 2 below. <Hardness test - Shao pen> ... τ 砑逖 forming strip 1 , by polishing 10000 mesh high well 锫 and lifting 2, ~ 尤 Mirror mirror molding to produce high gloss and size. Small for 18〇mmxl5〇_ The flat plate is tested according to ASTM D3363; the hardness of the prepared flat plate is measured, wherein the weight of the six-bar is 1.0 kg, and the contact angle of the refill j-plate is 45 degrees. The results are shown in Table 2 below: 2H And F, respectively, when used with a hardness of 2h, will not leave a fortune. (4) Passing through the test ^ < Solvent resistance - A stupidity> This test method is to first determine the forming cloth as described in the method of light transmittance 13 201226464

The test preparation sample 'but different in size, the test sample has a length of 230 mm, a width of 30 mm, a thickness of 2 mm, and a test sample prepared by fixing a 1/4 inch semi-elliptical jig, and then a gauze containing toluene (ie, The gauze soaked in toluene for a period of time was placed on the test panel, and the test sample was completely wetted and placed in a confined space for 24 hours, and the cracking condition was observed to judge its solvent resistance' and classified into AE. Grade, Class A has the worst solvent resistance and Class E has the best resistance. In general, A means that it cannot be used in contact with chemicals; B means that it is not recommended for use in contact with chemicals; c stands for special conditions and treatments to make (10) and chemical '^ joints; D No, no flaw; E means that unless there is a great stress application, the results are shown in Table 2 below.

14 201226464 Table 2

Composition and dosage of resin composition test results ABS PMMA dosage (wt%) MBS dosage (wt%) PMMA /AS (weight ratio) transmittance (%) impact strength (KJ/m2) pencil hardness solvent-resistant ABS precursor Type ABS precursor/AS (different amount) Amount (wt%) Example 1 Preparation Example 1 6.19/ 17.81 24 70 6 3.93 58.7 33.15 2H D Example 2 Preparation Example 1 7.48/ 21.52 29 65 6 3.02 77.5 39.12 Η D Example 3 Preparation Example 1 8.77/ 25.23 34 60 6 2.38 84.5 41.85 Η D Example 4 Preparation Example 1 10.06/ 28.94 39 55 6 1.90 89.2 44.86 Η D Example 5 Preparation Example 2 6.19/ 17.81 24 70 6 3.93 68.1 34.10 2Η D Example 6 Preparation Example 2 10.06/ 28.94 39 55 6 1.90 89.9 45.90 Η D Example 7 Preparation Example 3 10.06/ 28.94 39 55 6 1.90 86.7 46.30 Η D Example 8 Preparation Example 3 7.48/ 21.52 29 65 6 3.02 72.8 40.01 Η D Comparative Example 1 Preparation Example 5 7.48/ 21.52 29 65 6 3.02 61.0 32.75 Η D Comparative Example 2 Preparation Example 5 8.77/ 25.23 34 60 6 2.38 68.1 34.93 Η C Comparative Example 3 Preparation Example 7 7.48/ 21.52 29 65 6 3.02 14.1 41.10 Η C Comparative Example 4 Example 1 11.35/ 32.65 44 50 6 1.53 89.3 49.77 FC Comparative Example 5 Preparation Example 1 4.90/ 14.10 19 75 6 5.32 35.2 27.15 2Η D Comparative Example 6 Preparation Example 6 10.06/ 28.94 39 55 6 1.90 44.6 40.05 Η B Comparative Example 7 Preparation Example 4 10.06/ 28.94 39 55 6 1.90 75.1 45.01 Η C Comparative Example 8 Preparation Example 8 11.35/ 32.65 44 50 6 1.53 49.3 49.91 FC Comparative Example 9 Preparation Example 8 6.19/ 17.81 24 70 6 3.93 18.8 35.21 Η D [Note: ABS The components are composed of ABS precursors and AS. In Table 2, comparing Example 1 and Example 5 with Comparative Example 9, 15 201226464, it was found that the light transmittance of the embodiment of the present invention was significantly improved; Example 2 and the actual palladium Example 8 and Comparative Example Compared with Comparative Example 3, it can be found that the light transmittance and the solvent resistance of the embodiment of the present invention are significantly improved. Compared with Comparative Example 2, the light transmittance, impact strength and resistance of the embodiment of the present invention are compared. Solvent properties were better. Comparing Example 4, Example 6 and Example 7 with Comparative Example 6 and Comparative Example 7, the light transmittance and solvent resistance of the examples of the present invention were significantly improved. Moreover, on the whole, each of the properties of the examples in this case is in line with industry standards and even higher than the standards expected by the industry. Further, from the data of Table 2, it was also found that the pencil hardness and the solvent resistance of Comparative Example 4 were both poor, and Comparative Example 5 and Comparative Example 8 had poor transmittance and solvent resistance. In summary, by blending different copolymers and controlling the composition content within a specific range, the resin composition can have good impact resistance, high light transmittance, high pen hardness and solvent resistance. It is indeed advantageous to achieve the object of the present invention. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent change between the scope of the invention and the description of the invention is Modifications are still within the scope of the invention. White [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 16

Claims (1)

201226464 VII. Patent application scope: 1 · A thermoplastic resin composition comprising: 2 wt% to 2 wt% of a first graft polymer, the first graft polymer is grafted with styrene a butadiene rubber polymer of a monomer unit and a vinyl cyanide monomer unit, wherein the cyanide is based on the total weight of the stupid monomer and the vinyl cyanide monomer unit The secondary polymer unit comprises 27 wt% to 34 wt%; 16 wt% to 30 wt% of the first polymer 'the first polymer comprises: a small-styrene monomer unit and at least one cyanide In the vinyl monomer unit, the vinyl cyanide monomer unit accounts for 16 _ , (4) 丨 55 Wt% of the total weight of the styrene monomer unit and the cyanoquinone monomer unit. 70 wt% of the second polymer, the second polymer comprising =, a monomer unit selected from the group consisting of an acrylic acid I monomer unit, a methyl acetonic acid acetonide, or a combination of the above two units And 4 Wt% to the second graft polymer, the second graft polymer comprising at least one set of a fine early soap I, at least one vinyl monomer to a further copolymerizable monomer unit, the other copolymerizable:: unit is selected from the group consisting of an acrylic monomer unit, a methacrylic dragon body unit, or a combination of the above two units; The weight ratio of the first polymer is 18 to 41. According to the thermoplastic resin composition described in the first paragraph of the patent application, in the first graft polymer, the styrene monomer unit and the arylated vinyl monomer are 17 2, 201226464. The vinyl cyanide monomer unit accounts for 28 wt% to 32 wt% based on the total weight of the unit. 3. The thermoplastic resin composition according to claim 1, wherein 'in the first polymer, based on the total weight of the styrene monomer unit and the vinyl cyanide monomer unit, The vinyl cyanide monomer unit accounts for 17% by weight to 23% by weight. 4) The thermoplastic resin composition according to claim 1, wherein the weight ratio of the second polymer to the first polymer is 1 9 to 4 〇〇 5. According to the scope of the patent application The thermoplastic resin composition according to the invention, wherein the first graft polymer is a butadiene rubber polymer grafted with styrene-ethyl cyanide. The thermoplastic resin composition according to claim i, wherein: the first polymer is a copolymer obtained by polymerizing styrene and vinyl cyanide. 7·= According to the patent scope! The thermoplastic resin composition according to the invention, wherein the second polymer is a polymethyl methacrylate or a copolymer obtained by polymerizing methyl ketone with decyl acrylate. The thermoplastic resin composition according to item 1 of the patent application, wherein the first graft polymer is a grafted stupid vinyl monomer unit and another silky (four) monolithic rubber polymer. 18 201226464 IV. Designated representative map: (none) (1) The representative representative of the case is: map (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none)