[1][Mutual cited in the application (s)]
[2]
This application claims the benefit of priority based on the date of December 28, Korea Patent Application No. 10-2016-0181150, 2016, and all information disclosed in the literature of the Korea patent application are included as part of this specification.
[3]
[4]
The invention ABS, including the thermoplastic resin compositions, methods for their preparation and relates to an injection molded article, and more particularly, the conjugated diene ABS system of the type rubber 2 has an average particle diameter of polymer of different species of graft copolymers comprising the same in a specific ratio inherent impact resistance of the resin, the present invention relates to an injection molded article comprising the fusion characteristics of the vibration while the thermoplastic resin composition and that has excellent heat resistance and others advantages it.
BACKGROUND
[5]
Acrylonitrile-butadiene-styrene resin (ABS resin) has been widely used, such as processability, impact resistance and chemical resistance and excellent construction materials, car or motorcycle exterior and interior of the vehicle flow, electrical and electronic equipment. ABS-based resin that is used as interior and exterior of the double car or the like is gradually required to have high heat resistance and a variety of post-processing properties.
[6]
In one example, a method such as automobile rear lamps are heat-sealed, vibration welding, laser welding lamp housing and a polymethyl methacrylate (PMMA) as prepared by bonding the material of the lens using the ABS-based resin for a rear lamp housing when high, the heat resistance as well as a high adhesiveness of the PMMA lens is essentially required.
[7]
On the other hand, although typically used for heat-resistant ABS-based lamp housing and the lens past, hot melting method is low cost device to bond the, in this case without the appearance properties of the final product produced by the poor, had a low productivity problem.
[8]
The trend of the vibration welding in consideration of the appearance characteristics and productivity, preferred or, ABS system used in accordance with the joint surface shape at the time of four Entry to vibration welded to come in can occur cosmetic Jung, and increases the vibration time to improve the unmelted phenomenon the flakes had a problem has occurred that causes a foreign matter defect in the rear lamp assembly to the final case, adds a work for removing the foreign material there is a problem in poor productivity.
[9]
Foreign substance defect problems as described above, but can be solved by a laser welding method, a laser welding device is not desirable from the economic point of view and requires expensive equipment, and therefore a situation the material development for improving the foreign object defect problem urgent.
[10]
[11]
[Prior art document]
[12]
[Patent Document] [Patent Document 1] Korea Patent Registration No. 10-0528768 No.
Detailed Description of the Invention
SUMMARY
[13]
In order to solve the problems of the prior art, an object of the present invention is to provide an ABS-based resin but has excellent mechanical strength such as specific, heat-resistant properties of the improved vibration-sealable thermoplastic resin composition and a production method thereof.
[14]
The invention has for its object to contribute to the like and provides an injection molded article prepared by including the thermoplastic resin composition, a vibration-sealable improvement in reducing the manufacturing cost in manufacturing products, such as rear lamps of the vehicle, failure rate reduction and productivity.
[15]
The above and other objects of the present invention can be achieved by the present invention described below.
Problem solving means
[16]
In order to achieve the above object, the present invention provides A) ABS type graft copolymer comprising 20 to 30% by weight of the conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; a thermoplastic resin composition comprising a molded product is manufactured, including the thermoplastic resin composition is polymethyl formed acid oscillation on a surface fusion methacrylate (PMMA) molded article with vibration welding in the material provides (frequency 230㎐, pressure 480kgf, amplitude 1.2mm conditions) when, to the thermoplastic resin composition, characterized in that the vibration-sealable 6 or less which is calculated by equation (1).
[17]
Equation 1
[18]
Vibration-sealable (second) = T2 - T1
[19]
(Wherein T2 is the time required to vibrate the welding direction and 80 ° direction acid fusion, T1 is a time required when parallel vibration welding and fusing acid direction.)
[20]
In addition, the invention A) ABS type graft copolymer comprising 20 to 30% by weight of the conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; the kneading and provides a method for producing a thermoplastic resin composition characterized by comprising the step of extrusion.
[21]
The invention also provides an injection molded article, characterized in that is manufactured by injection molding the thermoplastic resin composition.
[22]
The present invention also provides a car rear lamp module to the injection-molded article being produced by vibration of the lens and PMMA material fusion.
Effects of the Invention
[23]
According to the present invention is effective to provide a heat-resistant ABS resin inherent mechanical strength, while maintaining the heat resistance characteristics are improved vibration welding thermoplastic resin composition and injection-molded article of.
[24]
Moreover, injection molded articles according to the present invention can contribute to the quality, productivity improvements, production cost, production time of manufacture rear lamp module for the automobile to the improvement of vibration welding.
Best Mode for Carrying Out the Invention
[25]
It will be described in detail below the thermoplastic resin composition of the base material.
[26]
The thermoplastic resin composition of the present invention A) average particle size of 0.25 to 0.35㎛ the conjugated diene-based polymer rubber ABS containing the graft copolymer 20 to 30% by weight; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; the sheet produced includes, as the thermoplastic resin composition (length 130mm, vertical 130mm) is polymethyl vibration welding acid is formed on one surface methacrylate (PMMA) material of the sheet (W 130mm, 130mm vertically) and vibration welded (230㎐ frequency, vibration-sealable calculated by the following equation (1) the pressure 480kgf, the amplitude of 1.2mm conditions) is characterized in that not more than 6.
[27]
Equation 1
[28]
Vibration-sealable (second) = T2 - T1
[29]
(Wherein T2 is the time required to vibrate the welding direction and 80 ° direction acid fusion, T1 is a time required when parallel vibration welding and fusing acid direction.)
[30]
In another example, the thermoplastic resin composition of the base material A) average particle size of 0.25 to 0.35㎛ the conjugated diene-based polymer rubber ABS containing the graft copolymer 20 to 30% by weight; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; includes, and is the average particle diameter of 0.6 to 10㎛ the rubber polymer and the average particle size of 0.25 to 0.35㎛ the weight ratio of the conjugated diene polymer rubber 1:15 to 1: 2, or 1:13 to 1: 5 may be characterized in that the.
[31]
Description will now be described in a manner that the thermoplastic resin composition of the base material for each component.
[32]
[33]
A) ABS type graft copolymer containing a conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛
[34]
Wherein A) the graft copolymer is referred to as a conjugated diene-based rubbery polymer (hereinafter referred to as "small-diameter rubber polymer, average particle diameter 0.25 to 0.35㎛.) Copolymer having an aromatic vinyl compound and a vinyl cyanide compound grafted on.
[35]
Conjugated diene-based rubber polymer in the present description refers to a polymer of a conjugated compound structure in which a double bond and single bond array across one.
[36]
In one example, the conjugated diene-based rubber polymer is a butadiene polymer, butadiene-styrene copolymers, butadiene-acrylonitrile copolymer, ethylene-propylene may comprise a copolymer or at least one of the polymers derived from them, preferably butadiene polymer or butadiene-styrene copolymers may be.
[37]
Referred to a polymer derived from the base material means the polymers made with the other monomers of the polymer compound or the polymer or copolymer of a conjugated compound derivative that is not included in the original polymer polymerization.
[38]
In the presently described derivative refers to a compound substituted with a hydrogen atom or atomic group of the original compound by an alkyl group or a halogen atom or an atomic group to another example.
[39]
The small diameter of rubber polymer in the mean particle diameter for example, 0.25 to 0.35㎛, to 0.27 or 0.28 to 0.35㎛ may be 0.32㎛, it is excellent in mechanical properties and appearance characteristics effect, such as impact strength of the final molded product within this range have.
[40]
The average particle diameter in the present description can be measured using a Nicomp 380 Dynamic light equipment to schedule agent ringbeop.
[41]
Wherein A) the graft copolymer as an example, includes the small-diameter rubber polymer of 40 to 70% by weight, 12 to 35% by weight of an aromatic vinyl compound and vinyl cyan compound of 6 to 25% by weight, within the range the mechanical strength, the physical properties such as processability, heat resistance, has excellent effects.
[42]
As another example, wherein A) the graft copolymer comprises the small-diameter rubber polymer of 45 to 68% by weight of aromatic vinyl compound from 14 to 35% by weight and a vinyl cyanide compound 6 to 20% by weight, in this case, heat resistance, mechanical there is an excellent effect that the physical properties balance of the strength and the like.
[43]
In another example, the A) the graft copolymer is the small diameter of rubber polymer 48 to 65% by weight, and an aromatic vinyl compound of 20 to 35% by weight and a vinyl cyanide compound 7 to 17% by weight, in this case, heat resistance, mechanical it is excellent in physical properties such as strength of the effect.
[44]
Aromatic vinyl compounds in the base material is one example, it may be used styrene, α- methyl styrene, p- methyl styrene, and at least one member selected from vinyl toluene, to preferably comprises styrene.
[45]
A vinyl cyanide compound in the present description is for example, acrylonitrile, and meth be at least one selected from acrylonitrile and ethacrylic in krill, which is preferably acrylonitrile.
[46]
A specific example, the A) the graft copolymer is small diameter butadiene rubber polymer - a styrene-acrylonitrile copolymer may be, in this case there is the advantage of excellent physical properties of the final product.
[47]
Wherein A) the graft copolymer A) graft copolymer, B) graft copolymer and C) a matrix resin of 20 to 30% by weight relative to the total weight, 22 to 30, including by weight%, or 23 to 27% by weight it may be desirable, in which case there is the excellent effect of physical properties such as balance.
[48]
[49]
B) the average particle diameter of 0.6 to 10㎛ of the rubber-modified produced by continuous mass polymerization, including the rubber polymer graft copolymer
[50]
Wherein B) is a graft copolymer has an average particle size of 0.6 to 10㎛ the conjugated diene rubber polymer (hereinafter referred to as "large-diameter rubber polymer") copolymer is an aromatic vinyl compound and a vinyl cyanide compound grafted on.
[51]
The large aperture rubber polymer may be in the average particle diameter for example, 0.6 to 10㎛, 0.6 to 8㎛, 0.65 to 5㎛, 0.65 to 3㎛, to 5 or 6 to 10㎛ 9㎛, the thermoplastic resin within this range but the mechanical strength of the composition excellent in the effect of vibration welding characteristic is improved.
[52]
Wherein B) the graft copolymer is for example, may comprise a large-diameter rubber polymer 5 to 20% by weight of aromatic vinyl compound of 50 to 70% by weight and a vinyl cyanide compound for 10 to 30% by weight, the mechanical strength in this range, while excellent in physical properties such as heat resistance can be improved sealable during vibration welding.
[53]
As another example, the B) graft copolymer may comprise a large-diameter rubber polymer of 8 to 15% by weight, aromatic vinyl compounds, 52 to 75% by weight and a vinyl cyanide compound from 12 to 35% by weight, within the range the mechanical strength , while excellent in physical properties such as heat resistance, vibration-sealable improves the effect of reducing the defect rate during post-processing, and increasing the productivity.
[54]
The aromatic vinyl compound and vinyl cyanide compound may include the same ones as the compounds which can be included in the A) a graft copolymer.
[55]
[56]
A specific example, the B) graft copolymer is large aperture polybutadiene rubber polymer - a styrene-acrylonitrile copolymer may be, in this case, there is an effect that the final product has excellent physical properties, while improving the vibration welding characteristics.
[57]
Wherein B) the graft copolymer A) graft copolymer, B) graft copolymer and C) a matrix resin of 2 to 10 wt% based on the total weight, from 3 to 10 which comprises in weight percent, or 3 to 7% by weight it may be desirable, but in this range the balance between the physical properties of the thermoplastic resin composition excellent in the effect that the sealing properties improve.
[58]
[59]
Wherein the weight ratio of A) a graft copolymer and B) graft copolymer is from 1: may be preferred from 3 to 1:10, more preferably 1: may be 9:05 to 1. This range has the effect in which the physical properties of the final molded article excellent in balance while improving the vibration characteristics in the fusion.
[60]
Wherein A) the graft content of the copolymer and B) graft copolymer can be preferably 20 to 40% by weight or 25 to 35 wt% based on the total weight of the thermoplastic resin composition of the base material, the physical properties within the range while excellent in balance, and there is an effect that workability is improved vibration-sealable.
[61]
Further, the weight ratio of the large-diameter and small-diameter rubber polymer rubber polymer contained in the thermoplastic resin composition of the substrate is 1:15 to 1: 3 or 1:13 to 1: 6, and it is may be desirable, within this range based ABS has a unique resin in mechanical strength, processability and a high quality molded article is improved even if the vibration welding characteristic is not degraded heat resistance of the can manufacturing.
[62]
[63]
C) a matrix resin
[64]
The matrix resin may be a heat-resistant styrene-based resins known in the art, the alpha example -alkyl styrene-aromatic vinyl compound-vinyl cyan compound copolymer, an alpha-alkylstyrene-vinyl cyan compound copolymer, the maleimide compound-aromatic the vinyl compound may comprise a copolymer, or both. While the mechanical strength of the thermoplastic resin composition is excellent if it contains the heat-resistant styrene-based resin as the matrix resin, the workability and heat resistance, has excellent effects.
[65]
Alkyl styrene-aromatic vinyl compound-alpha in the base material of the aromatic vinyl compound-vinyl cyan compound copolymer is an alpha-aromatic vinyl compound other than the alkyl styrene.
[66]
The heat-resistant styrene-based resin is excellent in processability and heat resistance may be used as an example the glass transition temperature is more than 115 ℃ or 115 to 140 ℃, the final resin composition is within this range effects.
[67]
Glass transition temperature on the substrate can be measured by differential scanning calorimetry (DSC).
[68]
The alpha-alkyl-styrene-aromatic vinyl compound-vinyl cyan compound copolymer is for example, alpha-alkyl styrene of 50 to 80% by weight or 60 to 75% by weight; An aromatic vinyl compound and 0 to 15% by weight or 0-10% by weight; And a vinyl cyanide compound from 20 to 50% by weight or 25 to 40% by weight; may include, and in this case it is excellent in mechanical strength such as excellent heat resistance, while the effect of the resin composition.
[69]
Alpha in the base-alkyl styrene is alpha-to be at least one selected from the group consisting of ethyl styrene, and preferably contains alpha-methyl styrene and alpha methyl styrene.
[70]
A specific example, the alpha-alkyl-styrene-aromatic vinyl compound-vinyl cyan compound copolymer is an alpha-methylstyrene-styrene-may be an acrylonitrile copolymer, wherein the alpha-alkylstyrene-vinyl cyan compound copolymer is an alpha- It specifies that not be the acrylonitrile copolymer, but is not limited thereto-methyl styrene.
[71]
The maleimide compound-aromatic vinyl compound copolymer may include one example, the maleimide compound to 30 to 70% by weight, the aromatic vinyl compound of 30 to 60% by weight and maleic anhydride 0-10% by weight, in which case the resin composition while the excellent physical properties such as mechanical strength, has a heat resistance with a high degree of advantage.
[72]
As another example, the maleimide compound-aromatic vinyl compound copolymer may include a maleimide compound of 40 to 60% by weight of aromatic vinyl compound of 40 to 55% by weight and the maleic anhydride from greater than 0 to 8% by weight, the range It has excellent heat resistance effects within.
[73]
The maleimide compounds are for example, N- phenylmaleimide, N- methyl maleimide, N- ethyl maleimide, N- butyl maleimide and N- cycloalkyl may be at least one selected from the group consisting of cyclohexyl maleimide, preferably it is intended to include N- phenyl maleimide.
[74]
It specifies the may be a maleic anhydride copolymer, but not limited to - as a specific example, the maleimide compound-aromatic vinyl compound copolymer is N- phenylmaleimide-styrene.
[75]
In addition, the matrix resin is an aromatic vinyl compound in order to improve the processability - it may be possible to use in combination with the heat-resistant styrene-based resin, a vinyl cyan compound copolymer.
[76]
A specific example, the matrix resin is a maleimide compound-aromatic vinyl compound copolymer of 15 to 35% by weight and an aromatic vinyl compound may include 65 to 85% by weight of a vinyl cyan compound copolymer, in which case both the heat resistance and processability there are excellent advantages.
[77]
As another example, the matrix resin is a maleimide compound-aromatic vinyl compound copolymer of 25 to 33% by weight and an aromatic vinyl compound to vinyl cyan compound copolymer 67 to 75 wt%, and the heat resistance within this range, processability, etc. both have excellent effect.
[78]
The aromatic vinyl compound-vinyl cyan compound is one example, may include an aromatic vinyl compound of 60 to 80% by weight and a vinyl cyanide compound from 20 to 40% by weight, there is the excellent effect processability of the resin composition within the range.
[79]
Specifies a may be an acrylonitrile copolymer, but not limited to - as a specific example, the aromatic vinyl compound-vinyl cyan compound is styrene.
[80]
Further, the aromatic vinyl compound-vinyl cyan compound can be preferably used in that the weight average molecular weight of 60,000 for example to 200,000g / mol, or 80,000 to 180,000g / mol, the heat resistance of the resin composition within the range is not improved lowering the fluidity is excellent in workability effect.
[81]
The weight average molecular weight in the base material is a sample can be measured by a back, a gel permeation chromatography method pretreatment dissolved in a solvent (for example THF).
[82]
[83]
The thermoplastic resin composition according to the present invention the average particle diameter is different from each other conjugated diene to the ABS-based graft copolymer of two kinds including a rubber polymer mixed with the heat-resistant matrix resin, ABS-based resin inherent impact resistance, maintaining the heat resistance and it may be characterized as a vibration welding properties are improved.
[84]
When Specifically, the molded article made of the thermoplastic resin composition is polymethyl acid formed on a surface vibration welding methacrylate (PMMA) and vibration welded molded product of the material (frequency 230㎐, pressure 480kgf, 1.2mm amplitude of the conditions), the equation the vibration-sealable, as calculated by the formula 1 can be characterized as 6 or less, 5.5 or less, 5.0 or less or 4.5 or less.
[85]
Further, the thermoplastic resin composition of the present invention may further comprise optional additives known in the art, if necessary.
[86]
The additive may be at least one selected from In one example, a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, colorant, antistatic agent and the like.
[87]
Other additives that are not expressly described as in the following description of the thermoplastic resin composition of the base material, if the range is being carried out in a conventional in the art are not particularly limited and may be carried out by appropriately selected as needed, .
[88]
[89]
Hereinafter, a manufacturing method of the thermoplastic resin composition of the base material.
[90]
The thermoplastic resin composition production method of the invention A) ABS type graft copolymer and 20 to 30% by weight containing the conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; and the kneading may be characterized in that it comprises the step of extruding.
[91]
During the mixing, it may optionally a lubricant, and further include additives such as an antioxidant, a light stabilizer, a colorant mixing, if necessary.
[92]
The additive A) graft copolymer, B) graft copolymer and C), the matrix resin 100 parts by weight based on 0.1 to 5 parts by weight or 0.5 to 3 may be included in parts by weight, this range in the final product the mechanical strength, heat resistance in If the physical properties such as not decrease up the effect of the additive can be expressed.
[93]
The kneading and extrusion can be carried out in the condition of 100 to 150 to 750rpm and 800rpm or 200 to 300 or 220 to 280 ℃ ℃, there is excellent in processability and moldability advantage in the range.
[94]
[95]
The thermoplastic resin composition of this disclosure may be prepared into injection molded product through a process of injection, the injection-molded article may be characterized as having excellent heat distortion temperature of for example, heat resistance of more than 95 ℃ or 95 to 112 ℃ .
[96]
Heat distortion temperature in the substrate load 18.5kgf / cm and on the basis of ASTM D648 using a specimen having a thickness of 1/4 " 2 can be measured in terms of.
[97]
Injection-molded article of the present description is applicable to the family of the variety of applications is excellent in physical properties such as heat resistance, impact resistance, in particular in accordance with the vibration welding characteristic is improved is made, including the bonding step by vibration welding, such as a rear lamp module of the car It can be used as a rear lamp housings.
[98]
In one example, the injection-molded article according to this disclosure may be an automobile rear lamp housing for the rear lamp housing can, including the step of bonding the lens and the vibration welding method of the PMMA material to manufacture the car rear lamp module.
[99]
Specifically the process is the top plate of PMMA material to bond the vibration welding method (upper part) after the formation of the vibration welding acid to a surface, the injection-molded article made of the thermoplastic resin composition of the present invention, one surface and the upper panel of the (lower panel, lower part) the rear surface of the vibration welding acid formed was disposed in contact with each other, it can comprise the step of using the vibration of vibration fusion bonding by melt fusion splicer acid between the upper panel and the lower panel.
[100]
[101]
Hereinafter, one present preferred embodiment to help understanding of the invention, the following examples are apparent according to the intended well as the scope and spirit the scope those skilled in the art will that various changes and modifications within the possible of the present invention to illustrate the invention, it belongs to such variations and modifications are following claims is granted.
[102]
[103]
The materials used in following Examples and Comparative Examples are as follows.
[104]
A) an ABS-based small-caliber graft copolymer comprising a rubber polymer
[105]
A1) a ABS graft copolymer with an average particle diameter include 0.3㎛ butadiene rubber polymer was used DP270 of LG Chemical Co..
[106]
[107]
B) ABS-based graft copolymer comprising a large-diameter rubber polymer
[108]
B1) an average particle size 0.7㎛ butadiene rubber polymer Nippon A & L Inc. AT-08 as ABS resin containing a was used.
[109]
B2) to the ABS resin with an average particle diameter include 1.2㎛ butadiene rubber polymer was used MA201 of LG Chemical Co..
[110]
B3) to the ABS resin with an average particle diameter include 8㎛ butadiene rubber polymer was used MA210 of LG Chemical Co..
[111]
[112]
C) a matrix resin
[113]
C1) (alpha-methylstyrene), styrene-acrylonitrile copolymer were used 98UHM of LG Chemical Co..
[114]
C2) N- phenylmaleimide-styrene-anhydride Denka's MS-NB to the maleic acid copolymer was used.
[115]
C3) a styrene-92HR, LG Chemical Co. of a copolymer of acrylonitrile was used.
[116]
[117]
EXAMPLES
[118]
Examples 1 to 8 and Comparative Examples 1 to 9
[119]
To a mixture of the ingredients and contents shown in Table 1 and Table 2 below using a twin-screw extruder and extruded into a 230 ℃, conditions of 200rpm to prepare a resin composition in pellet form.
[120]
It emits the resin composition of the pellet (230 ℃, 150bar) to the test piece for measuring physical properties were prepared.
[121]
[122]
TABLE 1
division Example
1 2 3 4 5 6 7 8
A1 26 27 22 26 26 26 26 26
B1 4 - - - 4 - - -
B2 3 8 - - 4 - 4
B3 - - - 4 - - 4 -
C1 70 70 70 70 - - - -
C2 - - - - 20 20 20 26
C3 - - - - 50 50 50 44
A/B* 6.5 9.0 2.8 6.5 6.5 6.5 6.5 6.5
The content of each component is A + B + C being a weight percent based on the total 100 weight% A / B *: A graft copolymer and the content ratio of the graft copolymer B

[123]
[124]
TABLE 2
division Comparative Example
1 2 3 4 5 6 7 8 9
A1 26 25 14 26 17 33 25 20 26
B1 - - - - - - - - -
B2 - 1 12 - 4 4 1 12 -
B3 - - - - - - - - -
C1 74 74 74 - - - - - -
C2 - - - 20 20 20 20 20 26
C3 - - - 54 59 43 54 48 48
A/B* - 25.0 1.2 - 4.3 8.3 25.0 1.7 -
The content of each component is A + B + C being a weight percent based on the total 100 weight% A / B *: A graft copolymer and the content ratio of the graft copolymer B

[125]
[126]
[Test Example]
[127]
Examples and comparative examples of how the specimen was determined by the properties to the manufactured, are shown in Table 3 and Table 4 below the results.
[128]
To ASTM D648 on the basis of using a specimen having a thickness of 1/4 "rate of temperature increase 120 ℃ / hour, load 18.5kgf / cm: 1) Heat distortion temperature (HDT, g / 10min) 2 was measured under the following conditions.
[129]
2) Vibration-sealable evaluation: For the vibration welding evaluation by injection of a resin composition comprising the component and the content of the above Table 1 to prepare a lower plate (lower part) of the flat type horizontal 130mm, vertical 130mm, through injection molding vibration welding the top plate acid formed (upper part) of the PMMA material was produced in the same size and shape and the lower panel.
[130]
The surface of one side of the upper panel and the lower panel formed acid oscillation fusion bonded to ship oscillation fusion splicer (730e, British ultrasound) and then, the direction parallel to the fusing acid 230㎐ frequency, pressure 480kgf, amplitude 1.2mm, a depth of 1mm mode condition attached to the measuring a time (T1, in seconds) it takes to vibration fusion, and to measure the time (T2, sec) required when vibration welding under the same conditions as in the welding direction and the acid in a 80 ° direction. The difference of T2 and T1 less is excellent in vibration welding characteristics.
[131]
3) Izod Impact Strength (IMP, kgcm / cm): was measured using a thickness 1/4 "specimens in accordance with the ASTM D256.
[132]
[133]
4) Appearance evaluation: To visually assess the state of the sample surface. (O: Excellent, Δ: Good, X: poor)
[134]
[135]
TABLE 3
division Example
1 2 3 4 5 6 7 8
HDT 97 98 96 97 101 102 101 105
T2-T1 4.9 4.6 4.3 4.4 5.2 5.0 5.0 4.9
IMP 21 23 22 22 14 15 16 12
Appearance rating ○ ○ ○ ○ ○ ○ ○ ○

[136]
[137]
TABLE 4
division Comparative Example
1 2 3 4 5 6 7 8 9
HDT 100 100 98 101 102 100 101 98 106
T2-T1 7.1 7.0 4.7 7.7 5.1 5.6 7.3 4.8 8.1
IMP 20 20 11 13 7 19 13 12 11
Appearance rating ○ ○ △ ○ ○ △ ○ △ ○

[138]
[139]
As shown in Table 3 and 4, the specimen made of the thermoplastic resin composition of the substrate was confirmed to have excellent impact strength, thermal deformation temperature is equal to or superior over the comparative example, while the vibration welding properties and appearance properties.
[140]
In particular, N- phenyl maleimide in a matrix resin-styrene-case comprising a maleic anhydride copolymer heat resistance was able to be confirmed that further improvement, in this case, vibration welding characteristics were confirmed to somewhat less.

WE CLAIM

[Claim 1]
A) ABS type graft copolymer comprising 20 to 30% by weight of the conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; a thermoplastic resin composition comprising, a sheet (length 130mm, vertical 130mm) is polymethyl vibration welding acid is formed on one surface methacrylate (PMMA) material made of the thermoplastic resin composition a sheet (length 130mm, 130mm vertically) and vibration welded (frequency 230㎐, pressure 480kgf, amplitude 1.2mm conditions) when, to the thermoplastic resin composition, characterized in that the vibration-sealable 6 or less which is calculated by equation (1). Equation 1 vibration-sealable (second) = T2 - T1 (and wherein T2 is the time required to vibrate the welding acid direction and 80 ° direction fusion, T1 is time when parallel vibration welding and fusing acid Direction to be.)
[Claim 2]
The method of claim 1, wherein the average particle size of 0.6 to 10㎛ the conjugated diene-based rubber polymer and the average weight ratio of the rubbery polymer particle size of 0.25 to 0.35㎛ is 1:15 to 1: The thermoplastic resin composition according to claim 2.
[Claim 3]
2. The method of claim 1, wherein A) the graft copolymer has the average particle size of 0.25 to 0.35㎛ the conjugated diene-based rubber polymer of 40 to 70% by weight, 12 to 35% by weight of an aromatic vinyl compound and vinyl cyan compound of 6 to 25% by weight the thermoplastic resin composition characterized in that comprises a.
[Claim 4]
2. The method of claim 1, wherein B) is a graft copolymer including the average particle diameter of 0.6 to 10㎛ rubber polymer 5 to 20% by weight of aromatic vinyl compound of 50 to 70% by weight and 10 to 30% by weight of a vinyl cyanide compound the thermoplastic resin composition according to claim.
[Claim 5]
2. The method of claim 1, wherein C) the matrix resin is an alpha-alkyl-styrene-aromatic vinyl compound-vinyl cyan compound copolymer or an alpha-alkyl-styrene-vinyl cyan compound copolymer; And maleimide compound-aromatic vinyl compound copolymer; 1 including, at least one of said alpha-alkyl-styrene-aromatic vinyl compound-vinyl cyan compound in the aromatic vinyl compound copolymer is an alpha-thermoplastic resin composition, characterized in that the alkyl except styrene.
[Claim 6]
The method of claim 5, wherein C) the matrix resin is a maleimide compound-thermoplastic resin, comprising 70 to 85% by weight of a vinyl cyan compound copolymer - 15 to 30% by weight of aromatic vinyl compound copolymer and the aromatic vinyl compound composition.
[Claim 7]
The method of claim 5, wherein the alpha-alkylstyrene-aromatic vinyl compound-alkyl styrene of 50 to 80% by weight, aromatic vinyl compound and 0 to 15% by weight and a vinyl cyanide compound from 20 to 50% by weight of vinyl cyan compound copolymer is an alpha the thermoplastic resin composition characterized in that it comprises.
[Claim 8]
The method of claim 5, wherein the maleimide compound-aromatic vinyl compound copolymer is characterized in that it comprises a maleimide compound of 30 to 70% by weight, the aromatic vinyl compound of 30 to 60% by weight and maleic anhydride 0-10% by weight The thermoplastic resin composition.
[Claim 9]
The method of claim 8, wherein the maleimide compound is at least one member selected from N- phenylmaleimide, N- methyl maleimide, N- ethyl maleimide, N- butyl maleimide and N- cycloalkyl group consisting of cyclohexyl maleimide the thermoplastic resin composition according to claim.
[Claim 10]
A) ABS type graft copolymer comprising 20 to 30% by weight of the conjugated diene-based rubbery polymer average particle size of 0.25 to 0.35㎛; B) the average particle diameter of 0.6 to 10㎛ the rubber-modified polymer rubber prepared by continuous mass polymerization, including the graft copolymer of 2 to 10% by weight; And C) a matrix resin of 60 to 80% by weight; poly (methyl methacrylate) prepared in the kneading and the thermoplastic resin composition including the step of extrusion molded product is manufactured, including the thermoplastic resin composition is formed acid oscillation on a surface fusing ( PMMA) molded article with vibration welding of the material (frequency 230㎐, pressure 480kgf, amplitude 1.2mm conditions) when, to process for producing a thermoplastic resin composition, characterized in that the vibration-sealable 6 or less which is calculated by equation (1). Equation 1 vibration-sealable (second) = T2 - T1 (and wherein T2 is the time required to vibrate the welding acid direction and 80 ° direction fusion, T1 is time when parallel vibration welding and fusing acid Direction to be.)
[Claim 11]
Any one of claims 1 to 9, characterized in that injection molded articles made by injection of a thermoplastic resin composition according to any one of items.
[Claim 12]
12. The method of claim 11, wherein the molded article has a heat deflection temperature (temperature increase rate 120 ℃ / hour, load 18.5kgf / cm 2 injection-molded article, characterized in that a) at least 95 ℃.
[Claim 13]
12. The method of claim 11, wherein the molded article is an injection molded article, characterized in that the rear lamp housing for automobiles.
[Claim 14]
Car rear lamp module to the injection-molded article according to claim 13 characterized in that the lenses produced by the vibration of the PMMA material fusion.