CN109957202A - Plastic master batch and preparation method thereof, plastics and plastic products - Google Patents
Plastic master batch and preparation method thereof, plastics and plastic products Download PDFInfo
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- CN109957202A CN109957202A CN201910249334.5A CN201910249334A CN109957202A CN 109957202 A CN109957202 A CN 109957202A CN 201910249334 A CN201910249334 A CN 201910249334A CN 109957202 A CN109957202 A CN 109957202A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The present invention provides plastic master batch and preparation method thereof, plastics and plastic products, which includes carrier；Active material, the active material include at least one of antibacterial agent and mould inhibitor；Dispersing agent, the dispersing agent meet at least one of the following conditions: the surface of the dispersing agent can be lower than the surface of carrier energy, and the mobility of the dispersing agent is bigger than the mobility of the carrier；Surface treating agent, the surface treating agent are connected by least one of intermolecular force and chemical bond with the active material and the dispersing agent；And auxiliary agent.In the plastic master batch, active material while so that plastic products realize preferable antibacterial and/or antimold activity, can be improved the utilization rate of active material, cost substantially reduces in the surface enrichment of plastic products.
Description
Technical field
The present invention relates to field of material technology, and in particular to plastic master batch and preparation method thereof, plastics and plastic products.
Background technique
Active material is introduced in plastic raw materials, is the common method of current production antibacterial and mouldproof plastics.In the related technology,
For the stabilization for guaranteeing antibacterial and mouldproof performance, require to consider dispersibility of the active material in plastic resin, generally all as far as possible
It is uniformly distributed it in resin base material, to improve its antibacterial and mouldproof stability and processing stability.Thus, how preferably will
Active material is evenly dispersed to be had been a hot spot of research and difficulties in the plastic.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.
The present invention is following discovery based on inventor and understanding and completes:
Currently used active material much all including noble metal etc. higher costs ingredient, thus realize antibacterial and/
Or while mildew-proof function, the cost of plastic products is significantly improved, and for this problem, inventor, which attempts to find, a kind of to be both able to achieve
Antibacterial and/or anti-mold effect, while cost and lower plastics.Inventor has found in long-term test and practice process, resists
For bacterium mildewproof plastics in the actual application in the fields such as building materials, electric appliance, main function is to inhibit the micro- life of surface of plastic products
The growth and breeding of object, and contacted with surface microorganism and generate antibacterial and mouldproof effect mainly product surface, inventor into
The discovery of one step, common active material in the related technology, the migration rate in solid plastic is extremely low, therefore active material is equal
The processing method of even dispersion in the plastic, causes the effective action of active material insufficient, and most of dispersion is in plastic products
Between active material do not play due effect.For this problem, inventor proposes, if dispersing active material
On the surface of plastic products, then cost can be substantially reduced while guaranteeing preferable antibacterial and/or anti-mold effect.Thus
Inventor has made intensive studies, and active material is connected by discovery by surface treating agent with dispersing agent, can use dispersion
The low-surface-energy and/or large fluidity of agent make active material in the surface enrichment of plastic products, and then can realize preferably
Cost is substantially reduced while antibacterial and/or anti-mold effect.
In view of this, it is an object of the invention to propose that active material can be made in surface of plastic products enrichment, reduce
The plastic master batch of cost, the preparation method of plastic master batch, plastics and plastic products.
In one aspect of the invention, the present invention provides a kind of plastic master batches.According to an embodiment of the invention, the plastics
Master batch includes: carrier；Active material, the active material include at least one of antibacterial agent and mould inhibitor；Dispersing agent, it is described
Dispersing agent meets at least one of the following conditions: the surface of the dispersing agent can be than low, the dispersion of the surface of carrier energy
The mobility of agent is bigger than the mobility of the carrier；Surface treating agent, the surface treating agent pass through intermolecular force and change
At least one of key is learned to be connected with the active material and the dispersing agent；And auxiliary agent.In the plastic master batch, surface treatment
Active material can be connected by agent by intermolecular force or chemical bond with dispersing agent, and dispersing agent has lower surface
Energy or biggish mobility, when preparing plastic products using the plastic master batch, dispersing agent is intended to the table in plastic products
Face enrichment, to drive active material in the surface enrichment of plastic products, so that plastic products are realized preferable antibacterial and/or prevented
It is mould active meanwhile, it is capable to improve the utilization rate of active material, cost substantially reduces.
According to an embodiment of the invention, the plastic master batch includes: 5~50 parts by weight of carrier；The active material 6~
50 parts by weight；0.2~2 parts by weight of surface treating agent；20~40 parts by weight of dispersing agent；And 0.2~2 weight of auxiliary agent
Measure part.
According to an embodiment of the invention, the dispersing agent includes at least one of siloxanes and fluorine richness siloxanes.
According to an embodiment of the invention, the dispersing agent includes the different sub- dispersing agent of multiple molecular weight.
According to an embodiment of the invention, the gross mass based on the dispersing agent, according to mass percent meter, the dispersing agent
Including 0.1~10% the first dispersing agent, 20~80% the second dispersing agent and 10~80 third dispersing agent, and described first
The weight average molecular weight of third dispersing agent described in the weight average molecular weight < of second dispersing agent described in the weight average molecular weight < of dispersing agent.
According to an embodiment of the invention, the weight average molecular weight of first dispersing agent be 1000~20000, described second point
The weight average molecular weight of powder is 20000~100000, and the weight average molecular weight of the third dispersing agent is greater than 100000.
According to an embodiment of the invention, active material includes 6~25 parts by weight of 6~25 parts by weight of antibacterial agent and mould inhibitor.
According to an embodiment of the invention, the plastic master batch meets at least one of the following conditions: the carrier include ethylene/
Vinyl acetate co-polymer, polyethylene wax, polyethylene, polypropylene, polymethyl methacrylate, thermoplastic elastomer (TPE), poly- carbonic acid
At least one of ester, polyethylene terephthalate, polybutylene terephthalate (PBT), polyformaldehyde and nylon；It is described anti-
Microbial inoculum includes inorganic antiseptic, preferably includes at least one of Ag series antibacterial agent, Zn series antibacterial agent and Cu series antibacterial agent；It is described
Mould inhibitor includes at least one in captan, probenazole, Bravo, triclosan, trichlorine kappa, copper 8-quinolinolate and carbendazim
Kind；The surface treating agent includes at least one of titante coupling agent, aluminate coupling agent and silane coupling agent；Institute
Stating auxiliary agent includes at least one of antioxidant and heat stabilizer.
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above plastic master batch.According to
The embodiment of the present invention, this method comprises: active material, surface treating agent and dispersant are obtained pre-composition；It will be described
Pre-composition, carrier and auxiliary agent mixing, and obtained mixture is granulated, obtain the plastic master batch.Pass through this method
Mentioned-above plastic master batch can be fast and efficiently prepared, and step is simple, it is easy to operate, it is easy to industrialized production.
According to an embodiment of the invention, including: by the active matter by active material, surface treating agent and dispersant
Matter is mixed with surface treating agent, then by obtained mixture and the dispersant, obtains the pre-composition.
In still another aspect of the invention, the present invention provides a kind of plastics.According to an embodiment of the invention, the plastic bag
It includes: mentioned-above plastic master batch；And matrix plastic.The plastics have whole features of mentioned-above plastic master batch and excellent
Point, this is no longer going to repeat them.
According to an embodiment of the invention, the carrier in the plastic master batch meets at least one of the following conditions: the load
The mobility of body is greater than or equal to the mobility of described matrix plastics；The surface of the carrier can be moulded less than or equal to described matrix
The surface energy of material.
According to an embodiment of the invention, the plastics include: 4~8 parts by weight of plastic master batch；Described matrix plastics 92~
96 parts by weight.
According to an embodiment of the invention, described matrix plastics include polyethylene, polypropylene, polyvinyl chloride, polystyrene, benzene
Ethylene/propene lonitrile copolymer, acrylonitrile/butadiene/styrene copolymer, acrylonitrile/styrene, second
Alkene/vinyl acetate co-polymer, polymethyl methacrylate, thermoplastic elastomer (TPE), polycarbonate, polyethylene terephthalate
At least one of ester, polybutylene terephthalate (PBT), polyformaldehyde and nylon.
In another aspect of the invention, the present invention provides a kind of plastic products.According to an embodiment of the invention, the plastics
Product be made of mentioned-above plastics, and the concentration of the active material of the outer surface of the plastic products be greater than the modeling
The concentration of the active material of the inside of material products.The plastic products have preferable antibacterial and/or anti-mold effect as a result,
The dosage of active material is less simultaneously, and cost significantly reduces.
According to an embodiment of the invention, in the inside of the plastic products, with the outer surface apart from the plastic products
Distance be gradually increased, the concentration of the active material is gradually reduced.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the present invention provides a kind of plastic master batches.According to an embodiment of the invention, the plastics
Master batch includes: carrier；Active material, the active material include at least one of antibacterial agent and mould inhibitor；Dispersing agent, it is described
Dispersing agent meets at least one of the following conditions: the surface of the dispersing agent can be than low, the dispersion of the surface of carrier energy
The mobility of agent is bigger than the mobility of the carrier；Surface treating agent, the surface treating agent pass through intermolecular force and change
At least one of key is learned to be connected with the active material and the dispersing agent；And auxiliary agent.In the plastic master batch, surface treatment
Active material can be connected by agent by intermolecular force or chemical bond with dispersing agent, and dispersing agent has lower surface
Energy or biggish mobility, when preparing plastic products using the plastic master batch, dispersing agent is intended to the table in plastic products
Face enrichment, to drive active material in the surface enrichment of plastic products, so that plastic products are realized preferable antibacterial and/or prevented
It is mould active meanwhile, it is capable to improve the utilization rate of active material, cost substantially reduces.
According to an embodiment of the invention, the plastic master batch may include: that 5~50 parts by weight of carrier are (specific such as 5 weight
Part, 7 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 weights
Measure part, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight
Deng)；6~50 parts by weight of antibacterial mildew inhibitor active material (such as 6 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 20
Parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight etc.)；The surface treatment
0.2~2 parts by weight of agent (such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight,
1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight etc.)；20~40 parts by weight of dispersing agent (such as 20 parts by weight, 22 parts by weight,
25 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 39 weights
Measure part, 40 parts by weight etc.)；And 0.2~2 parts by weight of auxiliary agent (such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 weights
Measure part, 1.2 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight etc.).In above-mentioned content range, modeling
Expect that each component can be cooperateed with mutually in master batch, mating reaction, makes plastic master batch that there is good service performance, with above-mentioned content model
It encloses and compares, it is relatively blunt to be formed in master batch if vector contg is too low, if vector contg too Gao Zehui relative reduction dispersing agent
Content is unfavorable for active material surface migration；If the content of active material is too low, it is difficult to reach antibacterial and/or anti-mold effect,
The too high then cost relative increase of the content of active material, performance are superfluous；If the content of surface treating agent is too low, it is relatively blunt in
The combination of active material and dispersing agent, the too high levels of surface treating agent then may be excessive and remaining, cause to waste, cost phase
To increase；Relatively blunt to migrate in active material surface if dispersant is too low, dispersant is excessively high then relatively blunt
It is formed in master batch, and increased costs；Auxiliary agent content is too low, the performances relative deficiency such as anti-oxidant of plastic master batch, auxiliary agent content mistake
High then performance relative surplus, increased costs.
According to an embodiment of the invention, the active material may include antibacterial agent and mould inhibitor.Some specific embodiments
In, it may include that 6~25 parts by weight of antibacterial agent are (specific such as 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 weight
Part, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 25 parts by weight etc.), 6~25 parts by weight of mould inhibitor
(it is specific as 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight,
22 parts by weight, 24 parts by weight, 25 parts by weight etc.).Antibacterial agent and mould inhibitor can be with mating reactions, so that plastic products have as a result,
There are ideal antibacterial and anti-mold effect, compared with above range, if content is too low, antibacterial and anti-mold effect are relatively poor, contain
Too high then performance relative surplus is measured, cost is increase accordingly.
According to an embodiment of the invention, the dispersing agent can wrap in order to enable active material surface concentration effect is more preferable
Include at least one of siloxanes and fluorine richness siloxanes.Specifically, siloxanes refers to that key containing Si-O-Si constitutes backbone structure
Polymer is specifically as follows methylsiloxane, methyl phenyl siloxane, ethylsiloxane (predominantly dimethyl silicone polymer
PDMS) etc.；Fluorine richness siloxanes full name Organofluoro Modified Polysiloxane, is the synthetic of special modified silicon and fluorine, is also possible to
Some or all of hydrogen atom on siloxanes replaced by fluorine after product, for example including but be not limited to fluorohydrocarbon based polysiloxane
(such as trifluompropyl methyl polysiloxane, nine fluorine hexyl siloxanes of poly- methyl), perfluoropolyether siloxanes.Dispersing agent has as a result,
There is extremely low surface energy, most active materials can be very good the outer surface for being dispersed in plastic products, surface enrichment effect
It is ideal.
According to an embodiment of the invention, the dispersing agent may include the different sub- dispersing agent of multiple molecular weight.Specifically,
By taking dispersing agent is siloxanes as an example, dispersing agent may include the different siloxanes of various molecular weights, and those skilled in the art can be with
Understand, molecular weight difference described herein can be for specific values for molecular weight, average molecular weight or molecular weight ranges (that is
Molecular weight distribution) it is different.The dispersing agent of multiple not equimolecular quantity ranks as a result, helps to make active material in plastic products
Various concentration gradient distribution is formed, the biggish dispersing agent of molecular weight can keep antibacterial and mouldproof long-term effect, and lesser point of molecular weight
Powder is more likely to be enriched in the outer surface of plastic products to play quick antibacterial and/or mould proof effect, and then can make
Obtaining plastic products has good and stable antibacterial and/or anti-mold effect.
Some specific embodiments according to the present invention, based on the gross mass of the dispersing agent, according to mass percent meter, institute
Stating dispersing agent includes 0.1~10% (specific such as 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%)
The first dispersing agent, 20~80% (specific such as 20%, 30%, 40%, 50%, 60%, 70%, 80%) the second dispersing agent
The third dispersing agent of (specific such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%) with 10~80%, and institute
State dividing equally again for third dispersing agent described in the weight average molecular weight < of the second dispersing agent described in the weight average molecular weight < of the first dispersing agent
Son amount.In the content range, the dispersing agent of three kinds of different molecular weight ranks can cooperate effect, molecular weight it is low first
Dispersing agent is easier the surface enrichment in plastic products, and higher second dispersing agent of molecular weight and third dispersing agent can moulded
Active material forms suitable concentration gradient (internally concentration is gradually smaller from the outer surface of plastic products) in material products, in turn
So that plastic products have both quick and long-acting stable antibacterial and/or anti-mold effect, and the second dispersing agent and third dispersing agent
Content is higher, viscosity in master batch preparation process can be made suitable, it is easier to which the granulation of plastic master batch is processed.
Some specific embodiments according to the present invention, the weight average molecular weight of first dispersing agent are 1000~20000 (tools
Body such as 1000,2000,3000,5000,6000,8000,10000,12000,14000,15000,16000,18000,20000
Deng), the weight average molecular weight of second dispersing agent be 20000~100000 (it is specific such as 20000,30000,40000,50000,
60000,70000,80000,90000,100000 etc.), the weight average molecular weight of the third dispersing agent is greater than 100000 (specifically such as
100001、110000、120000、130000、140000、150000、200000、300000、400000、500000、600000、
650000,700000,800000,850000,900000,1000000 etc.).The dispersing agent of above-mentioned molecular weight ranges can be with as a result,
Mutual cooperation effect makes active material form more suitable concentration gradient distribution in plastic products, so that plastic products
With ideal antibacterial and/or anti-mold effect.
According to an embodiment of the invention, the carrier include ethylene/vinyl acetate copolymer, polyethylene wax, polyethylene,
Polypropylene, polymethyl methacrylate, thermoplastic elastomer (TPE), polycarbonate, polyethylene terephthalate, poly- terephthaldehyde
At least one of sour butanediol ester, polyformaldehyde and nylon.It is possible thereby to be suitable for most of use environment, especially electric appliance is led
Domain.In some embodiments of the invention, when carrier is at least one of ethylene/vinyl acetate copolymer and polyethylene wax
When, preferable with the compatibility of other matrix plastics, which can be used as general master batch and uses；When carrier is other substances
When, it can be used plastic master batch as dedicated master batch, i.e., when the plastic master batch being used to prepare plastic products, base can be kept
Body plastics are consistent with carrier, it is possible thereby to which the plastic products service performance made is more preferably.
According to an embodiment of the invention, the plastic master batch needs to carry out forming processes in subsequent use process, therefore adopt
The heat resistance of antibacterial agent and mould inhibitor need to meet the machine-shaping temperature of each plastics, under the hot conditions of the machine-shaping
It does not decompose, as a result, in some embodiments of the invention, the antibacterial agent includes inorganic antiseptic, specifically, can wrap
Include at least one of Ag series antibacterial agent, Zn series antibacterial agent and Cu series antibacterial agent；The mould inhibitor may include captan, thiophene bacterium
At least one of spirit, Bravo, triclosan, trichlorine kappa, copper 8-quinolinolate and carbendazim.As a result, above-mentioned antibacterial agent and
Mould inhibitor has preferable antibacterial and anti-mold effect, and the mobility in solid plastic is extremely low, it is ensured that surface enrichment resists
Microbial inoculum and mould inhibitor can make plastic products have long-term, stable antibacterial and anti-mold effect, and material source is extensive, is easy to get.
It should be noted that above-mentioned inorganic antiseptic is usually the form presence with Metal Supported on antibacterial carrier,
Illustrate by taking Ag series antibacterial agent as an example, Ag (the including but not limited to silver ion for generally including carrier and being supported on antibacterial carrier
Deng), wherein carrier includes but is not limited to zeolite, ceramics and glass etc..
According to an embodiment of the invention, the surface treating agent may include titante coupling agent, aluminate coupling
At least one of agent and silane coupling agent.Surface treating agent can be with the active site on active material and dispersing agent as a result,
In conjunction with allowing active material to be distributed in the outer surface of plastic products under the action of dispersing agent to connect.
According to an embodiment of the invention, can also have the auxiliary agent for restraining or delaying material aging in plastic master batch, it is some
In embodiment, the auxiliary agent may include at least one of antioxidant and heat stabilizer, specifically, antioxidant includes but unlimited
In antioxidant 1010 (i.e. four [β-(3,5- di-tert-butyl-hydroxy phenyl] pentaerythritol esters), (i.e. N, the N '-of antioxidant 1098
1,6- inferior hexyl-bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionamide]), the irgasfos 168 (i.e. (2,4- bis- of phosphorous acid three
Tert-butyl-phenyl) ester), antioxidant 2246 (i.e. 2,2- di-2-ethylhexylphosphine oxide (4- methyl -6- butylphenol)), CA (i.e. three (butyl cresols
At least one of base) butane, DLTP, that is, dilauryl thiodipropionate) and DSTP (i.e. the double octadecyl esters of thio-2 acid), heat
Stabilizer includes but is not limited at least one of barium stearate and barium laurate.Thus, it is possible to which it is preferable to have plastics
Anti-aging and heat resistance.
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above plastic master batch.According to
The embodiment of the present invention, this method comprises: matter active material, surface treating agent and dispersant are obtained pre-composition；By institute
Pre-composition, carrier and auxiliary agent mixing are stated, and obtained mixture is granulated, obtains the plastic master batch.Pass through the party
Method can fast and efficiently prepare mentioned-above plastic master batch, and step is simple, easy to operate, be easy to industrial metaplasia
It produces.
According to an embodiment of the invention, active material, surface treating agent and dispersant can effectively be made in advance
It is connected between three by intermolecular force or chemical bond, and then is conducive to make when being subsequently used for preparing plastic products
Active material is obtained in the surface enrichment of plastic products.Some specific embodiments according to the present invention, can be first by the active matter
Matter is mixed with surface treating agent, then by obtained mixture and the dispersant, obtains the pre-composition.As a result,
It can more fully to contact between three, to connect stronger, sequent surface concentration effect is more preferably.
According to an embodiment of the invention, above-mentioned granulation can be plastics conventional granulation processes, for example including but be not limited to
Extruding pelletization etc..Easy to operate as a result, technical maturity does not have rigors to equipment and technical staff, it is easy to accomplish industrialization
Production.
In still another aspect of the invention, the present invention provides a kind of plastics.According to an embodiment of the invention, the plastic bag
It includes: mentioned-above plastic master batch；And matrix plastic.By introducing mentioned-above plastic master batch, the plastics are for being made modeling
When material products, the active material in plastic master batch can greatly improve the utilization of active material in the surface enrichment of plastic products
Rate avoids the waste of the non-effective active material inside plastic products, while guaranteeing antibacterial and/or anti-mold effect, hence it is evident that
Reduce cost.
According to an embodiment of the invention, the carrier in the plastic master batch meets at least one of the following conditions: the load
The mobility of body is greater than or equal to the mobility of described matrix plastics；The surface of the carrier can be moulded less than or equal to described matrix
The surface energy of material.Specifically, can only carrier mobility be greater than matrix plastic, can only carrier surface can lower than matrix mould
Material, surface can be lower than matrix plastic while being greater than matrix plastic with the mobility of carrier.Thereby, it is possible to promote plastic master
Grain in surface enrichment from active material to plastic products.
According to an embodiment of the invention, the plastics may include: that 4~8 parts by weight of plastic master batch are (specific such as 4 weight
Part, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight etc.)；92~96 parts by weight of described matrix plastics are (specific such as 92 weight
Part, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight etc.).It in the range, can be in the use of less active material
Reach better antibacterial and/or anti-mold effect when amount, compared with above range, if the content of plastic master batch is too low, plastics
Antibacterial and/or anti-mold effect it is relatively poor, and if the too high levels of plastic master batch, cost relative increase.
According to an embodiment of the invention, described matrix plastics may include polyethylene, polypropylene, polyvinyl chloride, polyphenyl second
Alkene, styrene/acrylonitrile copolymer, acrylonitrile/butadiene/styrene copolymer, acrylonitrile/phenylethylene ethylene/propenoic acid ester copolymerization
Object, ethylene/vinyl acetate copolymer, polymethyl methacrylate, thermoplastic elastomer (TPE), polycarbonate, poly terephthalic acid
At least one of glycol ester, polybutylene terephthalate (PBT), polyformaldehyde and nylon.Thus, it is possible to which meeting largely makes
With the requirement of environment, especially appliance field, and material source extensively, be easy to get, cost is relatively low.
It should be noted that above-mentioned plastics can by the form of the mixture of plastic master batch and matrix plastic particle exist,
It is also possible to the plastic grain being granulated after mixing plastic master batch and matrix plastic.
In another aspect of the invention, the present invention provides a kind of plastic products.According to an embodiment of the invention, the plastics
Product be made of mentioned-above plastics, and the concentration of the active material of the outer surface of the plastic products be greater than the modeling
The concentration of the active material of the inside of material products.The plastic products have preferable antibacterial and mouldproof effect as a result, living simultaneously
Property substance dosage it is less, cost significantly reduce.
Some specific embodiments according to the present invention, in the inside of the plastic products, with apart from the plastic products
The distance of outer surface be gradually increased, the concentration of the active material is gradually reduced.Most active materials can as a result,
Antibacterial and/or mildew-proof function are effectively played, is avoided and is dispersed in internal active material in the related technology and can not effectively play work
With the not high problem of utilization rate significantly reduces cost while guaranteeing preferable antibacterial and/or anti-mold effect.
It should be noted that describing mode " distance of the outer surface apart from the plastic products " used herein is
Refer to minimum range of some site apart from plastic products outer surface inside plastic products.It will be understood by those skilled in the art that this
Active material tends to be enriched with to the outer surface of plastic products in the plastic products of invention, then certain site and plastics inside plastic products
The distance between article outer surface is bigger, then the concentration of the site active materials is then lower, by taking plastic products are spherical as an example,
From the spherical surfaces of plastic products on the direction of the centre of sphere, the concentration of active material is gradually decreased.
According to an embodiment of the invention, the plastic products can be plastic master batch and matrix plastic granulate mixture is direct
It carries out what forming processes obtained, is also possible to that plastic master batch and matrix plastic are mixed and be granulated, then granulation is obtained
Product carries out what forming processes obtained.Requirements is not particularly limited in specific moulding process, can be common plastics product at
Type technique, for example including but be not limited to injection molding, extrusion molding etc..In forming process, the low-surface-energy of dispersing agent and
Active material is enriched in the outer surface of plastic products under the action of large fluidity, is substantially increased the utilization rate of active material, is kept away
The waste for having exempted to be dispersed in the active material inside plastic products, greatly reduces cost.
According to an embodiment of the invention, the specific structure and shape of the plastic products are not particularly limited, it can be according to reality
Border requirement flexible choice, specifically, the plastic products can be the shell of electric appliance, internal element, feet, handle etc..
The embodiment of the present invention is described below in detail.
Embodiment 1
Material proportion: see Tables 1 and 2.
The preparation method of plastic products:
1, it is mixed evenly after antibacterial agent, mould inhibitor and surface treating agent being weighed, then adds dispersant
Uniformly, premix is obtained；
2, after mixing premix, auxiliary agent with carrier, surface migration type antibacterial matrices are made in extruding pelletization；
3, surface migration type antibacterial matrices and matrix plastic (high impact polystyrene HIPS) are mixed into laggard machine-shaping
Antibacterial and mouldproof plastic products are made in technique.
Embodiment 2
Material proportion: see Tables 1 and 2.
The preparation method is the same as that of Example 1 for plastic products.
Embodiment 3
Material proportion: see Tables 1 and 2.
The preparation method is the same as that of Example 1 for plastic products.
Comparative example 1
Material proportion: see Tables 1 and 2.
The preparation method is the same as that of Example 1 for plastic products, and obtaining master batch is common antibacterial matrices.
Comparative example 2
Material proportion: see Tables 1 and 2.
The preparation method of plastic products is the same as comparative example 1.
Table 1 (unit: parts by weight)
Table 2 (unit: parts by weight)
Performance test, with reference to the antibacterial removing other fungus and purifying function antibacterial of GB 21551.2-2010 household and similar applications electric appliance
The particular/special requirement of material carries out:
Antibiotic rate test: being carried out by GB 21551.2-2010 appendix A, and test result is shown in Table 2；
Mould proof level estimate: being carried out by GB 21551.2-2010 appendix C, and test result is shown in Table 2.
According to the test result of table 2 it is found that the plastic products of the application can reach when containing less active material
With the comparable antibacterial and mouldproof effect of ordinary plastic articles for containing more active materials.
Embodiment 4
Material proportion, the preparation method of plastic products and method for testing performance are dispersing agent by not with embodiment 2, difference
Dispersing agent with molecular weight grade is constituted, and dispersing agent concrete composition and performance test results are shown in Table 3, wherein the first dispersing agent
Weight average molecular weight is 8000, and the weight average molecular weight of the second dispersing agent is 65000, and the weight average molecular weight of third dispersing agent is
650000, above-mentioned weight average molecular weight passes through gel liquid chromatogram measuring.
Embodiment 5
Material proportion, the preparation method of plastic products and method for testing performance are dispersing agent by not with embodiment 4, difference
Dispersing agent with molecular weight grade is constituted, and dispersing agent concrete composition and performance test results are shown in Table 3.
Embodiment 6
Material proportion, the preparation method of plastic products and method for testing performance are dispersing agent by not with embodiment 4, difference
Dispersing agent with molecular weight grade is constituted, and dispersing agent concrete composition and performance test results are shown in Table 3.
Embodiment 7
Material proportion, the preparation method of plastic products and method for testing performance are dispersing agent by not with embodiment 4, difference
Dispersing agent with molecular weight grade is constituted, and dispersing agent concrete composition and performance test results are shown in Table 3.
Table 3 (unit: wt%)
| Dispersing agent | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| First dispersing agent | 5 | 100 | 0 | 0 |
| Second dispersing agent | 45 | 0 | 100 | 0 |
| Third dispersing agent | 50 | 0 | 0 | 100 |
| Antibiotic rate | > 99.9% | > 99.9% | 98.3% | 96.5% |
| Mould proof grade | 0 grade | 0 grade | 0 grade | 1 grade |
It can be seen that first dispersing agent of the embodiment 5 due to all using low molecular weight according to the performance test results of table 3,
There is preferable antibacterial and mouldproof effect, but compared with Example 4, process is opposite to have some setbacks, and screw rod is easy to skid and relatively difficult
With blanking, and the first dispersing agent is easy to migrate may cause surface of plastic products hair oil.Embodiment 6 and embodiment 7 respectively only with
Second dispersing agent and third dispersing agent, molecular weight is relatively high, and compared with embodiment 4 and embodiment 5, effective mobility amount is slightly not
Foot, antibacterial and mouldproof effect are declined slightly.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (16)
1. a kind of plastic master batch characterized by comprising
Carrier；
Active material, the active material include at least one of antibacterial agent and mould inhibitor；
Dispersing agent；
Surface treating agent, the surface treating agent pass through at least one of intermolecular force and chemical bond and the active matter
Matter is connected with the dispersing agent；And
Auxiliary agent；
Wherein, the dispersing agent meets at least one of the following conditions:
The surface of the dispersing agent can be lower than the surface of carrier energy,
The mobility of the dispersing agent is bigger than the mobility of the carrier.
2. plastic master batch according to claim 1 characterized by comprising
5~50 parts by weight of carrier；
6~50 parts by weight of active material；
0.2~2 parts by weight of surface treating agent；
20~40 parts by weight of dispersing agent；And
0.2~2 parts by weight of auxiliary agent.
3. plastic master batch according to claim 1, which is characterized in that the dispersing agent includes siloxanes and fluorine richness silicon oxygen
At least one of alkane.
4. plastic master batch according to claim 3, which is characterized in that the dispersing agent includes the different son of multiple molecular weight
Dispersing agent.
5. plastic master batch according to claim 4, which is characterized in that the gross mass based on the dispersing agent, according to quality
Percentages, the dispersing agent include 0.1~10% the first dispersing agent, 20~80% the second dispersing agent and 10~80%
Third dispersing agent, and third described in the weight average molecular weight < of the second dispersing agent described in the weight average molecular weight < of first dispersing agent
The weight average molecular weight of dispersing agent.
6. plastic master batch according to claim 5, which is characterized in that the weight average molecular weight of first dispersing agent is 1000
~20000, the weight average molecular weight of second dispersing agent is 20000~100000, the weight average molecular weight of the third dispersing agent
Greater than 100000.
7. plastic master batch according to claim 1, which is characterized in that the active material includes: the antibacterial agent 6~25
6~25 parts by weight of parts by weight and the mould inhibitor.
8. plastic master batch according to claim 1, which is characterized in that meet at least one of the following conditions:
The carrier includes ethylene/vinyl acetate copolymer, polyethylene wax, polyethylene, polypropylene, poly-methyl methacrylate
Ester, thermoplastic elastomer (TPE), polycarbonate, polyethylene terephthalate, polybutylene terephthalate (PBT), polyformaldehyde and Buddhist nun
At least one of dragon；
The antibacterial agent includes inorganic antiseptic, is preferably included in Ag series antibacterial agent, Zn series antibacterial agent and Cu series antibacterial agent extremely
Few one kind；
The mould inhibitor includes in captan, probenazole, Bravo, triclosan, trichlorine kappa, copper 8-quinolinolate and carbendazim
At least one；
The surface treating agent includes at least one of titante coupling agent, aluminate coupling agent and silane coupling agent；
The auxiliary agent includes at least one of antioxidant and heat stabilizer.
9. a kind of method for preparing plastic master batch according to any one of claims 1 to 8 characterized by comprising
By active material, surface treating agent and dispersant, pre-composition is obtained；
The pre-composition, carrier and auxiliary agent are mixed, and obtained mixture is granulated, obtains the plastic master batch.
10. according to the method described in claim 9, it is characterized in that, by active material, surface treating agent and dispersant packet
It includes:
The active material is mixed with surface treating agent, then by obtained mixture and the dispersant, is obtained
The pre-composition.
11. a kind of plastics characterized by comprising
Plastic master batch according to any one of claims 1 to 8；And
Matrix plastic.
12. plastics according to claim 11, which is characterized in that the carrier in the plastic master batch meets the following conditions
At least one: the mobility of the carrier is greater than or equal to the mobility of described matrix plastics；The surface of the carrier can be lower than
Or the surface energy equal to described matrix plastics.
13. plastics according to claim 11 characterized by comprising
4~8 parts by weight of plastic master batch；
92~96 parts by weight of described matrix plastics.
14. plastics according to claim 11, which is characterized in that described matrix plastics include polyethylene, polypropylene, polychlorostyrene
Ethylene, polystyrene, styrene/acrylonitrile copolymer, acrylonitrile/butadiene/styrene copolymer, acrylonitrile/styrene/the third
Olefin(e) acid ester copolymer, polymethyl methacrylate, thermoplastic elastomer (TPE), polycarbonate, gathers at ethylene/vinyl acetate copolymer
At least one of ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyformaldehyde and nylon.
15. a kind of plastic products, which is characterized in that be made of the plastics described in any one of claim 11~14, and
The concentration of the active material of the outer surface of the plastic products is greater than the dense of the active material of the inside of the plastic products
Degree.
16. plastic products according to claim 15, which is characterized in that in the inside of the plastic products, with distance
The distance of the outer surface of the plastic products is gradually increased, and the concentration of the active material is gradually reduced.
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