CN102585367A - Polypropylene composition supporting laser marking and preparation method and application thereof - Google Patents
Polypropylene composition supporting laser marking and preparation method and application thereof Download PDFInfo
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- CN102585367A CN102585367A CN2012100363913A CN201210036391A CN102585367A CN 102585367 A CN102585367 A CN 102585367A CN 2012100363913 A CN2012100363913 A CN 2012100363913A CN 201210036391 A CN201210036391 A CN 201210036391A CN 102585367 A CN102585367 A CN 102585367A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract
The invention discloses a polypropylene composition supporting laser marking and a preparation method and an application thereof. The polypropylene composition comprises the following components in percentage by mass: 40-80 percent of polypropylene resin, 5-30 percent of an elastomer, 0-40 percent of an inorganic filler, 0.01-5 percent of a marking agent and 0.01-5 percent of a white toner. The preparation method comprises the following steps of: proportionally mixing the components; melting, blending and extruding by using an extruder; performing water cooling and bracing; and pelletizing. Due to the adoption of the marking agent and the prepared polypropylene composition supporting laser marking, a clear deep-color mark can be formed under a light color background under the condition of a small adding amount of the marking agent, the mark is firm and durable and does not disappear due to mechanical, chemical and physical factors, the cost is relatively low, and the use requirements of plastic parts in the industries of automobiles, home appliances, IT (Internet Technology), office equipment, electric tools, packages and the like can be fully met.
Description
Technical field
The present invention relates to a kind of polypropene composition, but a kind of polypropene composition of laser labelling particularly.
Background technology
Vestolen PP 7052 is prone to advantages such as recovery because of it has light weight, anti-solvent, is prone to processing, is widely used in industries such as automobile, household electrical appliances, machinery and packing.In recent years, along with developing rapidly of every profession and trade, polyacrylic consumption also is the trend that increases year by year.Polypropylene articles is in practical application, for the needs that use often require to identify to improve its easy identification and trackability on its surface.Traditional marking method mainly is to adopt the printing ink code spraying technology, but the mark that is to use this method to obtain often fades easily or disappear, and the use of printing ink also can pollute environment.
In recent years, the laser marking technology is obtaining application more and more widely aspect the plastics sign.Compare with conventional art; The laser marking technology has unique advantage, and laser-processing system combines with Computerized digital control system can constitute high-efficient automatic equipment, can get various literal, symbol and pattern fast; Degree of freedom is high, and mark can not erased and faded for a long time.The laser marking technological accumulation and inheritance is friendly in addition, does not use organic reagents such as printing ink.
Though laser marking has above-mentioned various advantage, it is used also has limitation, is exactly a kind of polymkeric substance that is difficult to even can't carries out laser marking such as polyolefine.Even in addition with a kind of polymkeric substance; Because color is different; Its laser marking performance also has very big-difference; Disclose a kind of function of plastic laser marking master batch like Chinese patent CN200910065221.6, be made up of photosensitizers, white pigment, black pigment, organic polymer carrier, it can make at black pp class frosting and produce white clearly pattern or writing; But the Vestolen PP 7052 of light color then is difficult to get dark pattern of ideal and vestige, because it can't absorb the laser of respective wavelength effectively luminous energy is changed into heat energy.In addition, the addition of its mark agent is more, and the performance and the price that influence material are relatively costly.Also do not see research report at present in the domestic and foreign literature patent about light Vestolen PP 7052 laser marking performance.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, but primary and foremost purpose of the present invention is to provide a kind of polypropene composition of laser labelling, and said composition is a kind of polypropene composition that under light background, forms dark mark.
But another object of the present invention is to provide the preparation method of the polypropene composition of above-mentioned laser labelling.
But a purpose more of the present invention is to provide the application of the polypropene composition of above-mentioned laser labelling.
The present invention realizes through following technical scheme:
But a kind of polypropene composition of laser labelling by mass percentage, comprises following component:
Acrylic resin: 40 ~ 80%
Elastomerics: 5 ~ 30%
Mineral filler: 0 ~ 40%
Mark agent: 0.01 ~ 5%
White toner: 0.01 ~ 5%.
Preferably, but the polypropene composition of above-mentioned laser labelling by mass percentage, comprises following component:
Acrylic resin: 50 ~ 70%
Elastomerics: 10 ~ 20%
Mineral filler: 10 ~ 30%
Mark agent: 0.05 ~ 2%
White toner: 0.1 ~ 1%.
Said acrylic resin is HOPP and/or COPP, can also adopt cationic coordinate polymerization, the coordination polymerization of Ziegler-Natta negative ion or with metallocene catalyst synthetic Vestolen PP 7052.That said COPP can be selected is random, in block or the branch shape multipolymer one or more.
The melt flow rate(MFR) of said HOPP, COPP (MFR) is 1 ~ 60g/10min, preferred 10 ~ 40g/10min.
Said elastomerics is an ethene-alpha-olefin copolymer; Said elastomeric density is 0.850 ~ 0.930g/cm
3, preferred 0.850 ~ 0.870g/cm
3Said elastomeric melt mass flow rate is 0.2 ~ 13g/10min (2.16kg, 190 ℃), preferred 0.5 ~ 5g/10min (2.16kg, 190 ℃); The carbonatoms of alhpa olefin is 2 ~ 10, and the carbonatoms of preferred alhpa olefin is 2 ~ 4.
Said mineral filler be in talcum powder, lime carbonate, whisker or the spun glass one or more, the preferably talc powder.Said talcous median size dimension D 50 is 2 ~ 20 μ m, and D97 is 10 ~ 45 μ m.Preferred median size dimension D 50 is 5 ~ 15 μ m, and D97 is 20 ~ 35 μ m.Talcous particle diameter D50 commonly used and D97 represent.D50 representes that particle diameter accounts for 50% greater than its particle, also accounts for 50% less than its particle, i.e. median size.D97 representes that particle diameter accounts for 97% less than its particle.
Said mark agent is one or more in laser whipping agent or the photosensitive colour-changing agent, the preferential two or more things of joining mutually.Said laser whipping agent or photosensitive colour-changing agent are can produce strong absorption effect laser whipping agent or photosensitive colour-changing agent to the 1064nm wavelength.Said laser whipping agent is the sheet base with silicate such as sheet micas, and the inside has comprised foaming substance, and foaming substance is selected from one or more in white lake, Marinco H and the calcium hydroxide; The photosensitive colour-changing agent with Vilaterm as carrier; The inside has coated which floor MOX or pressed powder; MOX is selected from one or more in White tin oxide, red stone and the weisspiessglanz, and pressed powder is selected from one or more in aluminium, boron, titanium, copper, iron, graphite, silicon and the tin.
Said white toner is any one or a few the mixture in mica, talcum powder, white titanium pigment, zinc sulphide, lime carbonate, zinc white, stibium trioxide, permanent white, the calcined kaolin.
Can also comprise other additives in the compsn of the present invention, like in oxidation inhibitor, antioxygen auxiliary agent, aliphatics lubricant, nucleator, the static inhibitor one or more.Oxidation inhibitor is DBPC 2,6 ditertiary butyl p cresol, 2,4, and 6-tri-butyl-phenol, 4-methylol-2,6 di t butyl phenol, N-cyclohexyl-N '-phenyl are in diamines, tricresyl phosphite (2, the 4 di-tert-butyl-phenyl) ester etc. one or more; The antioxygen auxiliary agent is one or more in thio-2 acid two LAURIC ACID 99 MIN, triphenyl phosphite, thio-2 acid two (18) ester etc.; The aliphatics lubricant is one or more in calcium stearate, the Zinic stearas; Nucleator is 2; 2 '-methylene radical-two (4; 6-di-t-butyl phenoxy) sodium phosphate, two (the 4-tertiary butyl-phenoxy) sodium phosphate, two [2; 2-methylene radical-two (4,6-di-t-butyl phenoxy) phosphoric acid oxyaluminum], in two (2-alkyl, 4-alkyl phenoxy) phosphoric acid salt, diphenyl-methyl sorbyl alcohol one or more; Static inhibitor is one or more in trihydroxyethyl ammonium methyl methyl sulfate salt, Sorbitol Powder mono fatty acid ester, the AEO etc.The quality percentage composition of above-mentioned other additives is 0.01 ~ 5%, preferred 0.1 ~ 3%.
But a kind of preparation method of polypropene composition of laser labelling comprises the steps: that the mixing churning time is 0.5 ~ 60min with above-mentioned each component proportional mixing; Then through twin screw extruder or the charging of reciprocating type single screw extrusion machine master spout; In 170 ~ 240 ℃ of following melting mixing 0.1 ~ 5min, screw slenderness ratio is not less than 32, extrudes; The water-cooled tie rod, but pelletizing promptly gets the polypropene composition of laser labelling.
Above-mentioned preparation method can adopt and anyly can the uniform equipment of these mixing of materials be included but not limited to high-speed mixer, low speed mixer, Banbury mixer; On hybrid mode, can adopt single stage method that all components are once dropped into mixes; Also can adopt two step method or multistep processes that two kinds of components are mixed earlier again mixes with other components; Hybrid mode is varied, can adjust according to the practical situation of producing.Preferred 1 ~ the 15min of batch mixing churning time extrudes preferred 190 ~ 210 ℃ of melting mixing temperature, extruding pelletization, water-cooled, air-dry, and particle diameter is of a size of 1 ~ 5mm in any direction, and preferable particle size is of a size of 2 ~ 3mm, and packing gets final product.
But the polypropene composition of laser labelling of the present invention can be used for preparing industries such as automobile, household electrical appliances, IT, office equipment, power tool and packing uses plastic part; Wherein comprise letter, numeral and various sign on various buttons, the keyboard in the main application mode on automobile, household electrical appliances, IT, office equipment, the power tool; Circuit board line patterns etc., the main application mode on packing comprises product bar code, keeping life, identification number, product specification and lot identification mark etc.
The present invention compared with prior art has following beneficial effect:
The mark agent that the present invention adopts has the intense absorption effect to the laser of wavelength 1064nm; Foaming effect, carboniogenesis, Evaporation or chemical reaction can take place at frosting; Form dark writing of contrast intensive or pattern at light acrylic plastering surface energy; And the mark firm and durable, can fully not satisfy the request for utilization of industry plastic parts such as automobile, household electrical appliances, IT, office equipment, power tool and packing because of machinery, chemistry and physical factor effect disappear; Use is joined in the mark agent mutually, under lower addition, just can obtain ideal mark effect, and cost is cheap relatively; Than traditional marking method such as printing ink coding etc., laser marking method environmental friendliness of the present invention.
Embodiment
Further specify the present invention through embodiment below, following examples are preferred implementation of the present invention, but embodiment of the present invention does not receive the restriction of following embodiment.
In following examples shown in the table 1 and the Comparative Examples composite formula: wherein mark agent 1 is laser whipping agent A208, and mark agent 2 is photosensitive colour-changing agent L100407; Mark agent 3 is photosensitive colour-changing agent LS400; White toner 1 is a white titanium pigment; White toner 2 is a zinc sulphide; White toner 3 is a stibium trioxide; Oxidation inhibitor is DBPC 2,6 ditertiary butyl p cresol; Weather resisting agent is 2-hydroxyl-4-methoxy benzophenone; Lubricant is a Zinic stearas.
Embodiment 1
But the polypropene composition of the described laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1:
Wherein the melt flow rate(MFR) of HOPP (MFR) is 10g/10min, and the melt flow rate(MFR) of COPP (MFR) is 30g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.870g/cm
3, its melt mass flow rate is 1.0g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 4; Mineral filler is a talcum powder, and particle diameter is 4.7 μ m.
Its preparation process is following:
Above-mentioned each component is mixed in high-speed mixer in proportion, and the mixing churning time is 0.5min, then through the charging of twin screw extruder master spout; In 200 ℃ of following melting mixing 0.5min, screw slenderness ratio is 32, extrudes; The water-cooled tie rod; Air-dry, pelletizing 2mm, but promptly get the polypropene composition of laser labelling.
Embodiment 2
But the polypropene composition of the said laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 40g/10min, the melt flow rate(MFR) of COPP (MFR) is 60g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.850g/cm
3, its melt mass flow rate is 0.5g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 2; Mineral filler is a talcum powder, and particle diameter is 20 μ m.
Its preparation process is following:
Above-mentioned each component is mixed at low speed mixer in proportion, and the mixing churning time is 60min, then through the charging of reciprocating type single screw extrusion machine master spout; In 170 ℃ of following melting mixing 5min, screw slenderness ratio is 33, extrudes; The water-cooled tie rod; Air-dry, pelletizing 1mm, but promptly get the polypropene composition of laser labelling.
Embodiment 3
But the polypropene composition of the said laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 60g/10min, the melt flow rate(MFR) of COPP (MFR) is 10g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.930g/cm
3, its melt mass flow rate is 0.2g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 10; Mineral filler is a talcum powder, and particle diameter is 10 μ m.
Its preparation process is following:
Above-mentioned each component is mixed in Banbury mixer in proportion, and the mixing churning time is 15min, then through the charging of reciprocating type single screw extrusion machine master spout; In 240 ℃ of following melting mixing 1min, screw slenderness ratio is 33, extrudes; The water-cooled tie rod; Air-dry, pelletizing 3mm, but promptly get the polypropene composition of laser labelling.
Embodiment 4
But the polypropene composition of the said laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 60g/10min, the melt flow rate(MFR) of COPP (MFR) is 10g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.930g/cm
3, its melt mass flow rate is 5g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 5.
Its preparation process is following:
Above-mentioned each component is mixed in high-speed mixer in proportion, and the mixing churning time is 3min, then through the charging of twin screw extruder master spout; In 190 ℃ of following melting mixing 3min, screw slenderness ratio is 33, extrudes; The water-cooled tie rod; Air-dry, pelletizing 5mm, but promptly get the polypropene composition of laser labelling.
Embodiment 5
But the polypropene composition of the said laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 10g/10min, the melt flow rate(MFR) of COPP (MFR) is 30g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.870g/cm
3, its melt mass flow rate is 1.0g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 4; Mineral filler is a talcum powder, and particle diameter is 30 μ m.
Its preparation process is following:
Above-mentioned each component is mixed in high-speed mixer in proportion, and the mixing churning time is 3min, then through the charging of twin screw extruder master spout; In 190 ℃ of following melting mixing 3min, screw slenderness ratio is 33, extrudes; The water-cooled tie rod; Air-dry, pelletizing 5mm, but promptly get the polypropene composition of laser labelling.
Embodiment 6
But the polypropene composition of the said laser labelling of present embodiment, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 60g/10min, the melt flow rate(MFR) of COPP (MFR) is 30g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.862g/cm
3, its melt mass flow rate is 0.5g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 5; Mineral filler is a talcum powder, and particle diameter is 2 μ m.
Its preparation process is following:
Above-mentioned each component is mixed in high-speed mixer in proportion, and the mixing churning time is 3min, then through the charging of twin screw extruder master spout; In 190 ℃ of following melting mixing 3min, screw slenderness ratio is 28, extrudes; The water-cooled tie rod; Air-dry, pelletizing 5mm, but promptly get the polypropene composition of laser labelling.
Embodiment 7
But the polypropene composition of the said laser labelling of present embodiment; Its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 40g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.864g/cm
3, its melt mass flow rate is 5g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 4; Mineral filler is a talcum powder, and particle diameter is 4.7 μ m.
Its preparation process is following:
Above-mentioned each component is mixed in high-speed mixer in proportion, and the mixing churning time is 5min, then through the charging of twin screw extruder master spout; In 190 ℃ of following melting mixing 3min, screw slenderness ratio is 33, extrudes; The water-cooled tie rod; Air-dry, pelletizing 5mm, but promptly get the polypropene composition of laser labelling.
Comparative Examples 1
But the polypropene composition of the said laser labelling of this Comparative Examples, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of COPP (MFR) is 30g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.870g/cm
3, its melt mass flow rate is 1.0g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 4; Mineral filler is a talcum powder, and particle diameter is 4.7 μ m.
Its preparation process is with embodiment 1.
Comparative Examples 2
But the polypropene composition of the said laser labelling of this Comparative Examples, its component and quality percentage composition are as shown in table 1: wherein the melt flow rate(MFR) of HOPP (MFR) is 10g/10min; The melt flow rate(MFR) of COPP (MFR) is 30g/10min; Elastomerics is the multipolymer of ethene-alpha-olefin, and its density is 0.870g/cm
3, its melt mass flow rate is 1.0g/10min (2.16kg, 190 ℃), the carbonatoms of terminal olefin is 4; Mineral filler is a talcum powder, and particle diameter is 4.7 μ m.
Its preparation process is with embodiment 1.
The laser marking effect of each component and consumption and the finished product in table 1 embodiment and the Comparative Examples
Can find out from mensuration result each embodiment and Comparative Examples; The present invention adopts the mark agent and joins mutually and use the shortcoming that has overcome the light polypropene composition laser marking weak effect for preparing in the prior art or can't carry out laser labelling; And the usage quantity of mark agent still less; The gained Injection moulded part can form dark writing of contrast intensive or pattern through laser on its surface under light background, can fully satisfy the request for utilization of every profession and trade to the laser labelling polypropylene material.
Claims (10)
1. but the polypropene composition of a laser labelling is characterized in that: by mass percentage, comprise following component:
Acrylic resin: 40 ~ 80%
Elastomerics: 5 ~ 30%
Mineral filler: 0 ~ 40%
Mark agent: 0.01 ~ 5%
White toner: 0.01 ~ 5%.
2. but the polypropene composition of laser labelling according to claim 1 is characterized in that: by mass percentage, comprise following component:
Acrylic resin: 50 ~ 70%
Elastomerics: 10 ~ 20%
Mineral filler: 10 ~ 30%
Mark agent: 0.05 ~ 2%
White toner: 0.1 ~ 1%.
3. but the polypropene composition of laser labelling according to claim 1 is characterized in that, said acrylic resin is HOPP and/or COPP, and the melt flow rate(MFR) of said HOPP, COPP is 1 ~ 60g/10min.
4. but the polypropene composition of laser labelling according to claim 1 is characterized in that, said elastomerics is an ethene-alpha-olefin copolymer; Said elastomeric density is 0.850 ~ 0.930g/cm
3, melt mass flow rate is 0.2 ~ 13g/10min; The carbonatoms of said alhpa olefin is 2 ~ 10.
5. but the polypropene composition of laser labelling according to claim 1 is characterized in that, said mineral filler is a talcum powder, one or more in lime carbonate, whisker, the spun glass.
6. but the polypropene composition of laser labelling according to claim 1; It is characterized in that; Said mark agent is one or more in laser whipping agent or the photosensitive colour-changing agent, and said laser whipping agent or photosensitive colour-changing agent are can produce strong absorption effect laser whipping agent or photosensitive colour-changing agent to the 1064nm wavelength.
7. but the polypropene composition of laser labelling according to claim 1; It is characterized in that said white toner is any one or a few the mixture in mica, talcum powder, white titanium pigment, zinc sulphide, lime carbonate, zinc white, stibium trioxide, permanent white, the calcined kaolin.
8. but the polypropene composition of laser labelling according to claim 1 is characterized in that, also comprises in oxidation inhibitor, antioxygen auxiliary agent, weather resisting agent, various ester class or aliphatics lubricant, nucleator, the static inhibitor one or more.
9. but the preparation method of the polypropene composition of each described laser labelling of claim 1 ~ 8 is characterized in that comprising the steps: that the mixing churning time is 0.5 ~ 60min with above-mentioned each component proportional mixing; Then through twin screw extruder or the charging of reciprocating type single screw extrusion machine master spout; In 170 ~ 240 ℃ of following melting mixing 0.1 ~ 5min, screw slenderness ratio is not less than 32, extrudes; The water-cooled tie rod, but pelletizing promptly gets the polypropene composition of laser labelling.
10. but the polypropene composition of each described laser labelling of claim 1 ~ 8 is used in preparation automobile, household electrical appliances, IT, office equipment, power tool or packing product.
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| CN114702758A (en) * | 2022-03-10 | 2022-07-05 | 镇江市元润电子有限公司 | Preparation method of flame-retardant heat-resistant modified polypropylene PP plastic particles |
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Application publication date: 20120718 |