CN113801425A - Fluorine-containing functional elastomer material - Google Patents

Fluorine-containing functional elastomer material Download PDF

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Publication number
CN113801425A
CN113801425A CN202010542492.2A CN202010542492A CN113801425A CN 113801425 A CN113801425 A CN 113801425A CN 202010542492 A CN202010542492 A CN 202010542492A CN 113801425 A CN113801425 A CN 113801425A
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fluorine
containing functional
elastomer material
mass
functional elastomer
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Inventor
熊勇
薛晨亮
朱立
高凯
周德越
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Daikin Fluorochemicals China Co Ltd
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Daikin Fluorochemicals China Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a fluorine-containing functional elastomer material which can keep good hand feeling, does not need other additional processing techniques, has excellent antifouling property on various pollutants in daily life, is easy to wipe and can delay the product fouling time. The fluorine-containing functionalityThe elastomer material comprises the following components (A) to (C), (A) a styrene thermoplastic elastomer; (B) a fluorine-containing copolymer obtained by copolymerizing a monomer mixture containing the following monomers (b1) to (b3), (b1) CH2＝C(‑CH3)‑C(＝O)‑O‑(CH2)2‑(CF2)5CF3(b2) cyclohexyl methacrylate, (b3) 2-hydroxyethyl methacrylate; (C) an extender oil, wherein the content of the component (A) is 15-35% by mass, the content of the component (B) is 0.5-10% by mass, and the content of the component (C) is 10-30% by mass, based on 100% by mass of the fluorine-containing functional elastomer material.

Description

Fluorine-containing functional elastomer material
Technical Field
The invention relates to a fluorine-containing functional elastomer material for a mouse surface coating material or a USB cable coating material.
Background
With the rapid development of the 3C electronic industry, people pay attention to the product performance of electronic products such as smart bracelets, watches, mice, keyboards and the like, and also increasingly emphasize individuation.
The soft touch material of the electronic product is mainly composed of materials such as thermoplastic vulcanizate (TPV), thermoplastic elastomer (TPE) or thermoplastic polyurethane elastomer (TPU). Products made of the materials have the advantages of good hand feeling and easy processing, but because the stain resistance is poor, the products are basically in dark tones such as grey and black, and cannot meet the personalized requirements.
In order to meet the consumer demand, light-colored or bright-colored products in which a colorant is further added to the soft touch material have also appeared on the market. However, after a few days of normal use, such products form dirt which is difficult to wipe off, so that the product appearance is affected, bacteria, mildew and the like grow on the product surface, and the service life of the product is finally affected.
On the other hand, there has been proposed a method of forming a coating film by coating a surface of a soft touch material, but this method increases the number of steps and cost, and also generates Volatile Organic Compounds (VOC) during the treatment, which is not favorable for environmental protection. In addition, there has been proposed a method of adding silicone, silicone oil or the like to a soft touch material, which can improve the smoothness of the surface of the product and suppress the adhesion of stains, but since silicone itself is not oil-repellent, domestic stains easily penetrate into the material, and low-molecular silicon is also easily precipitated, which affects the texture of the product after long-term use. Therefore, a soft touch material which does not require any additional processing, has excellent touch feeling, has excellent stain resistance to various contaminants, is easy to wipe, and can suppress the penetration of stains has been sought.
In order to improve antifouling properties, patent document 1 discloses a data line coating material that is resistant to various contaminants and contains a fluorosilicone polymer, a polypropylene resin, a polyphenylene ether resin, a polyolefin elastomer, a polystyrene-based thermoplastic elastomer, or the like. However, the data line coating material disclosed in patent document 1 is still insufficient in terms of satisfying all of good texture, excellent stain resistance, easy-to-wipe property, and the like.
Documents of the prior art
Patent document
Patent document 1: CN106554565A
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a fluorine-containing functional elastomer material for soft touch materials, which can maintain a good touch feeling, does not require any additional processing steps, has excellent stain resistance to various contaminants in daily life, is easy to wipe, and can delay the stain time of products.
The present inventors have made intensive studies to achieve the above object and as a result, have found that the above problems can be solved by using a fluorine-containing functional elastomer material comprising a specific fluorine-containing copolymer and a thermoplastic elastomer.
That is, the present invention provides a fluorine-containing functional elastomer material comprising the following components (A) to (C),
(A) styrenic thermoplastic elastomers;
(B) a fluorocopolymer obtained by copolymerizing a monomer mixture containing the following monomers (b1) to (b3),
(b1)CH2＝C(-CH3)-C(＝O)-O-(CH2)2-(CF2)5CF3(hereinafter, sometimes referred to as "C6 FMA"),
(b2) Cyclohexyl methacrylate (hereinafter, may be referred to as "CHMA"),
(b3) 2-hydroxyethyl methacrylate (hereinafter, sometimes referred to as "HEMA");
(C) the oil is filled in the oil tank,
the content of the component (A) is 15-35% by mass, the content of the component (B) is 0.5-10% by mass, and the content of the component (C) is 10-30% by mass, based on 100% by mass of the fluorine-containing functional elastomer material.
In addition, the fluorine-containing functional elastomer material of the present invention preferably further contains an organic silicone as the component (D).
Further, the fluorine-containing functional elastomer material of the present invention is preferably used for manufacturing a soft touch material such as a mouse surface coating material or a USB cable coating material. When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, the fluorine-containing functional elastomer material of the present invention preferably further contains a thermoplastic polyurethane elastomer as the component (E). When the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the fluorine-containing functional elastomer material of the present invention preferably further contains polyolefin as the component (F).
Detailed Description
Hereinafter, each component contained in the fluorine-containing functional elastomer material of the present invention will be described in detail.
< ingredient (A) >
The component (A) is a styrenic thermoplastic elastomer.
Examples of the styrene-based thermoplastic elastomer include a block copolymer or a random copolymer having an aromatic vinyl polymer segment (hard segment) and a conjugated diene polymer segment (soft segment). Examples of the source compound of the aromatic vinyl polymer segment include α -alkyl substituted styrenes such as styrene, α -methylstyrene, α -ethylstyrene, and α -methyl-p-methylstyrene. Examples of the source compound of the conjugated diene polymer segment include butadiene, isoprene, and methylpentadiene.
Specific examples of the styrene-based thermoplastic elastomer include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-propylene block copolymer (SEPS), and the like, and among them, a styrene-ethylene-butylene-styrene block copolymer (SEBS) is particularly preferable.
The above components (A) may be used singly or in combination of 2 or more.
The component (A) may be a commercially available product. Examples of commercially available products include: 1818/1650/1652 manufactured by Kraton (r) corporation, usa, and the like; YH503 manufactured by Basil petrochemical, etc.; DP014, 029, 027 manufactured by Takara rubber Co., Ltd.
When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, the content of the component (a) is preferably 15 mass% or more and 35 mass% or less, more preferably 15 mass% or more and 30 mass% or less, and further preferably 18 mass% or more and 26 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of good touch.
When the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the content of the component (a) is preferably 15 mass% or more and 35 mass% or less, more preferably 18 mass% or more and 30 mass% or less, and further preferably 25 mass% or more and 30 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of good touch.
< ingredient (B) >
The component (B) is a fluorine-containing copolymer obtained by copolymerizing a monomer mixture containing the following monomers (B1) to (B3),
(b1)CH2＝C(-CH3)-C(＝O)-O-(CH2)2-(CF2)5CF3(C6FMA)、
(b2) cyclohexyl methacrylate (CHMA),
(b3) 2-hydroxyethyl methacrylate (HEMA).
When the fluorocopolymer is used in a fluorinated functional elastomer material, the fluorocopolymer can be easily blended with an elastomer such as the component (a) and molded to form a coating film having low surface energy on the surface of a product, and thus the fluorocopolymer has the effects of preventing stains, delaying the stain-proofing time of the product, and facilitating wiping.
In the fluorocopolymer, the amount of the monomer (b2) is preferably 2 to 500 parts by weight, more preferably 5 to 200 parts by weight, and still more preferably 10 to 150 parts by weight, and the amount of the monomer (b3) is preferably 1 to 500 parts by weight, more preferably 2 to 200 parts by weight, and still more preferably 5 to 150 parts by weight, based on 100 parts by weight of the monomer (b 1).
The monomer mixture of the component (B) may contain other monomers in addition to the above-mentioned monomers (B1) to (B3). Examples of the other monomer include a halogenated olefin monomer and an isocyanatoacrylate monomer. Examples of the halogenated olefin monomer include chlorobutene and monochloroacetic acid vinyl ester. Examples of the isocyanate acrylate monomer include 4-isocyanatobutyl (meth) acrylate and 3-isocyanatopropyl (meth) acrylate.
The component (B) may be either a random copolymer or a block copolymer, and is preferably a random copolymer. The component (B) can be obtained by polymerizing the above-mentioned monomers, polymerization initiator, solvent and, if necessary, chain transfer agent by a known polymerization method, for example, the method described in Japanese patent application laid-open No. 2014-223623. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, azobisisobutyronitrile, and the like. Examples of the solvent include acetone, methyl ethyl ketone, ethanol, isopropyl alcohol, and propylene glycol. Examples of the chain transfer agent include lauryl mercaptan, thioglycol, and sodium hypophosphite. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.
The weight average molecular weight of the component (B) can be measured by GPC, for example, and is obtained in terms of polystyrene, and is preferably 1000 to 1000000, more preferably 1000 to 50000, and further preferably 2000 to 20000.
When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, the content of the component (B) is preferably 0.5 mass% or more and 10 mass% or less, more preferably 3 mass% or more and 9 mass% or less, and further preferably 3 mass% or more and 6 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of achieving both antifouling property and cost.
When the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the content of the component (B) is preferably 0.5 mass% or more and 10 mass% or less, more preferably 3 mass% or more and 9 mass% or less, and further preferably 3 mass% or more and 6 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of achieving both antifouling property and cost.
< ingredient (C) >
The component (C) is an extender oil, and an extender oil generally used for soft touch materials such as a mouse surface coating material and a USB cable coating material can be used.
The type of the component (C) is not particularly limited, and examples thereof include naphthenic oils, paraffin oils, aromatic oils, and the like.
When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, the content of the component (C) is preferably 10 mass% or more and 30 mass% or less, more preferably 13 mass% or more and 26 mass% or less, and further preferably 15 mass% or more and 23 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of processability.
When the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the content of the component (C) is preferably 10 mass% or more and 30 mass% or less, more preferably 15 mass% or more and 25 mass% or less, further preferably 17 mass% or more and 25 mass% or less, and further more preferably 13 mass% or more and 18 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of processability.
< ingredient (D) >
From the viewpoint of enhancing the hand, the stain-proofing property against various contaminants, the oil-repellency and the easy-to-wipe property, the fluorine-containing functional elastomer material of the present invention preferably further contains an organic silicone as the component (D).
Examples of the organic silicone include chain polysiloxanes such as polydimethylsiloxane and methylphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; a silicone resin formed with a three-dimensional network structure; modified polysiloxanes such as amino-modified polysiloxanes, alkyl-modified polysiloxanes, and fluorine-modified polysiloxanes. From the viewpoint of imparting a more favorable texture, polydimethylsiloxane represented by the following general formula (2) is preferable.
(C2H6OSi)n (2)
(wherein n represents a number in the range of 1000 to 20000.)
As the polydimethylsiloxane, commercially available products can be used, and examples thereof include silicone oils AK12500 manufactured by wacker chemical corporation; KF96-10000CS and KF96-100000CS, manufactured by shin Etsu chemical industries Co., Ltd; RM4-7081, MB50-017, 31-441, HMB-0221, etc., manufactured by Dow Corning.
When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, the content of the component (D) is preferably 0.5 mass% or more and 10 mass% or less, more preferably 0.5 mass% or more and 5 mass% or less, and further preferably 1 mass% or more and 3 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of enhancing the touch feeling, the stain resistance against various contaminants, the oil repellency, and the easy-wiping property.
When the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the content of the component (D) is preferably 0.5 mass% or more and 10 mass% or less, more preferably 0.5 mass% or more and 5 mass% or less, and further preferably 1 mass% or more and 3 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material, from the viewpoint of enhancing the hand feeling, the stain resistance against various contaminants, the oil repellency, and the easy wiping property.
< ingredient (E) >
When the fluorine-containing functional elastomer material of the present invention is used as a mouse surface coating material, it is preferable that the fluorine-containing functional elastomer material of the present invention further contains a thermoplastic polyurethane elastomer (TPU) as the component (E) from the viewpoint of further improving the oil repellency of the fluorine-containing functional elastomer material of the present invention.
As the thermoplastic polyurethane elastomer (TPU), a block copolymer having a hard segment and a soft segment as repeating units is preferable to be (A 'B')mBlock linear polymers.
Wherein A 'is polyester or polyether with molecular weight of 1000-6000, B' is diol with linear alkyl with carbon atom number of 2-12, chemical structure between A 'B' chain segments is diisocyanate, and m is number of 1-200.
The polyester or polyether with the molecular weight of 1000-6000 is derived from polyester polyol or polyether polyol. Examples of the polyester polyol include polycaprolactone polyol. Examples of the polyether polyol include polyoxypropylene ether polyol and polytetrahydrofuran polyol.
Examples of the diol having a linear alkyl group having 2 to 12 carbon atoms include ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 8-octanediol, 1, 9-nonanediol, diethylene glycol, dipropylene glycol, and tripropylene glycol.
Examples of the diisocyanate include 1, 6-Hexamethylene Diisocyanate (HDI), 4' -diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), isophorone diisocyanate (IPDI), Xylene Diisocyanate (XDI), hydrogenated XDI, and Toluene Diisocyanate (TDI).
As the thermoplastic polyurethane elastomer (TPU), commercially available products can be used. For example, HF-S4070A, HF 3085A, HF 75AE, 85AE, manufactured by Zhejiang Huafeng thermoplastic polyurethane Co., Ltd; 5377A, 345, U-85AU10, etc., manufactured by Corcission corporation.
From the viewpoint of achieving both oil repellency and cost, the content of the component (E) is preferably 20% by mass or more and 50% by mass or less, more preferably 25% by mass or more and 45% by mass or less, and still more preferably 35% by mass or more and 45% by mass or less, relative to 100% by mass of the fluorine-containing functional elastomer material.
< ingredient (F) >
In the case where the fluorine-containing functional elastomer material of the present invention is used for a USB cable covering material, the fluorine-containing functional elastomer material preferably further contains polyolefin as the component (F), more preferably polypropylene, polyethylene, and still more preferably polypropylene, from the viewpoint of moderating the hardness of the resultant USB cable covering material.
The polypropylene used as the component (F) may contain a structural unit derived from a monomer other than a propylene monomer. For example, in addition to a structural unit derived from an ethylene monomer, a structural unit derived from an α -olefin monomer such as 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-nonene, 1-decene, or the like, a structural unit derived from a modifier described later, and the like can be mentioned.
Specific examples of the polypropylene include homopolypropylene, propylene-ethylene copolymers, propylene-butene copolymers, propylene-ethylene-butene copolymers, and modified products thereof. Examples of the modified product include a product obtained by graft-copolymerizing a modifier with a polypropylene resin, a product obtained by copolymerizing a modifier in the main chain of a polypropylene resin, and the like. Examples of the modifier include unsaturated dicarboxylic acids such as maleic acid, citraconic acid, and halogenated maleic acid; esters, amides or imides of unsaturated dicarboxylic acids; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride and halogenated maleic anhydride; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; esters (methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc.), amides, imides, or the like of unsaturated monocarboxylic acids. The polypropylene resin is preferably a polypropylene resin which is not modified.
Among them, homopolypropylene and a propylene-ethylene copolymer are more preferable.
As the polypropylene, commercially available products can be used. For example, H920Y, H390F manufactured by SK corporation of korea; ST302 manufactured by Liangrong chemical industry Co., Ltd; j301 cp produced by Xiaoxing chemical Co., Ltd.
Specific examples of the polyethylene include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. Further, as the polyethylene, commercially available products can be used. Examples thereof include MB9500 manufactured by LG chemical, 7144 manufactured by Mount petrochemical company, LL.8446.21 manufactured by Exxon Mobil, 7042 manufactured by China petrochemical Co., Ltd.
The component (F) may be used alone in 1 kind, or in combination of 2 or more kinds.
From the viewpoint of moderating the hardness of the product to be produced, the content of the component (F) is preferably 10 mass% or more and 40 mass% or less, more preferably 13 mass% or more and 30 mass% or less, and still more preferably 13 mass% or more and 25 mass% or less with respect to 100 mass% of the fluorine-containing functional elastomer material.
< other ingredients >
The fluorine-containing functional elastomer material of the present invention may contain other components within a range not impairing the effects of the present invention. The other components may be appropriately selected depending on the intended use, purpose, and the like of the product. Examples of the other components include various auxiliaries such as an antioxidant, a lubricant, a light stabilizer, a colorant, and a flame retardant.
Examples of the flame retardant include halogen-free flame retardants, specifically melamine cyanurate, melamine polyphosphate, hypophosphite, ammonium polyphosphate, and the like.
As the colorant, a toner or a color masterbatch can be cited.
Examples of the light stabilizer include light stabilizer 622, light stabilizer 770, and light stabilizer 944.
Examples of the lubricant include oleamide and erucamide.
Examples of the antioxidant include antioxidant 1010 and antioxidant 1076.
The other components mentioned above may be used singly or in combination of two or more.
< use >
The fluorine-containing functional elastomer material of the present invention can be used as a soft touch material, and specifically, a mouse surface coating material, a USB cable coating material, and the like can be mentioned.
When the mouse surface coating material is produced using the fluorine-containing functional elastomer material of the present invention, it can be produced by a usual method. Specifically, the raw materials for manufacturing the mouse surface coating material are weighed according to the content, the raw materials except the filling oil are mixed in a high-speed mixer at a high speed for 3-5 minutes, then the filling oil is added, the mixture is further fully mixed for 1-2 minutes, then the mixture is added into a double-screw extruder with the length-diameter ratio of 40-55, the mixture is subjected to melt extrusion and granulation at the forming temperature of 150-220 ℃, drying is performed to obtain the mouse surface coating material modified material, and the obtained modified material is subjected to melt plasticization at the temperature of 200-225 ℃ by using an injection molding machine, so that the mouse is prepared.
When the USB cable covering material is manufactured using the fluorine-containing functional elastomer material of the present invention, the USB cable covering material can be manufactured by a general method. Specifically, the raw materials for manufacturing the USB cable coating material are weighed according to the content, the raw materials except the filling oil are mixed in a high-speed mixer at a high speed for 3-5 minutes, then the filling oil is added, the mixture is further fully mixed for 1-2 minutes, then the mixture is added into a double-screw extruder with the length-diameter ratio of 40-55, the mixture is melted and extruded at the forming temperature of 150-220 ℃ for granulation, and the mixture is dried to obtain the USB cable coating material modified material.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, "%" represents "% by mass" unless otherwise specified.
(experiment 1)
Examples 1, 2-1 to 2-7 and comparative examples 1-1 to 1-2, 2-1 to 2-2
The raw materials of the mouse surface coating material were weighed according to the composition and amount shown in table 1, the raw materials except the extender oil were mixed in a high-speed mixer (model: BL-L25-5D V mixer, manufacturer: eastern guan bailong mechanical equipment ltd, the same shall apply hereinafter) at a high speed for 3 to 5 minutes, and then the extender oil was added and further mixed thoroughly for 1 to 2 minutes. Thereafter, the mixture was fed into a twin-screw extruder (model: CTE-35PLUS, manufacturer: Cordou Ke-Longya (Nanjing) machinery Co., Ltd.,
Figure BDA0002539477360000101
L/D44, the same applies hereinafter), melt-extruding at a molding temperature of 150 to 220 ℃, granulating, and drying to obtain the mouse surface coating material modified material. Next, the resulting modified material was molded into a sample plate of 3cm by 10cm and 0.2cm in thickness at a molding temperature of 160 to 230 ℃ by using an injection molding machine (model: E120-SVP12, manufacturer: Guangdong Shade Plastic machinery Co., Ltd., the same applies hereinafter). And then, melting and plasticizing the obtained modified material at 200-225 ℃ by using an injection molding machine to obtain the mouse.
Each performance was evaluated by the following method using the sample plate and mouse prepared in examples 1 and 2-1 to 2-7 and comparative examples 1-1 to 1-2 and 2-1 to 2-2.
< hand feeling >
The sample plate obtained in comparative example 1-1 was used as a blank, and the hand feeling was evaluated by a professional evaluator with the hand touching each of the test plate and the blank obtained, based on the following evaluation criteria, and the obtained results are shown in table 2 below.
O: compared with the blank sample, the hand feeling is not different
And (delta): the feel was somewhat different than the blank, but was acceptable
X: compared with the blank sample, the hand feeling difference is larger and unacceptable
< contact Angle >
Using a contact angle tester (model: DSA30 contact angle tester, manufacturer: KRUSS, Germany), 2. mu.l of deionized water and 2. mu.l of n-hexadecane were dropped onto the surface of each sample plate, respectively, at room temperature (25 ℃), and the contact angles of deionized water and n-hexadecane on the surface of each sample plate were measured, respectively. The obtained results are shown in table 2 below.
< antifouling Property >
Each of the prepared sample plates was evaluated for stain resistance by the following method using ketchup, yellow mustard, lipstick, and an oil pen, respectively.
Tomato sauce and yellow mustard sauce
The stains were uniformly applied to each sample plate, left to stand for 2 minutes, rinsed with tap water, blotted to dry, left to stand for 30 minutes, and the color difference value Δ E1 was measured for each sample plate using a color difference meter (CR-400 handheld color difference meter manufactured by konica minolta, the same applies hereinafter). Next, 5 panelists visually checked the sample plate obtained by measuring the color difference value Δ E1 with a standard color plate (the standard color plate was the sample plate prepared in comparative example 1-1, and the same applies hereinafter), and determined the degree of difference from the standard color plate based on the following evaluation criteria, and the average value thereof was taken as a final score. The obtained results are shown in table 2 below.
Then, a clean paper towel was soaked in 75% alcohol and wiped 10 times with the paper towel, and after leaving for 30 minutes, the color difference Δ E2 of each sample plate was measured using a color difference meter. Next, 5 panelists visually checked the sample plate obtained by measuring the color difference value Δ E2 with the standard color plate, determined the degree of difference from the standard color plate based on the following evaluation criteria, and averaged the value to obtain a final score. The obtained results are shown in table 2 below.
In this case, a higher Δ E indicates that the stain is more likely to remain on the sample and the stain-proofing ability is poorer. Preferably, Δ E < 5, and most preferably Δ E ≦ 3.
1. about.1: no difference from the standard color plate
Δ 2: a little difference, and the difference is less than 10 percent
Δ 3: has a little difference, and the difference is more than 10 percent and less than 30 percent
Δ × 4: has obvious difference, and the difference is more than 30 percent and less than 80 percent
X 5: has very obvious difference which is more than 80 percent
② lipstick
Each sample plate was drawn with lipstick (TSTTIN' SECRET 009# color), left to stand for 2 minutes and then rinsed with water, wiped 10 times with a medium force using a clean paper towel, and left to stand for 30 minutes, and then the color difference value Δ E of each sample plate was measured using a color difference meter. The obtained results are shown in table 2 below.
Then, 5 panelists visually collate the measured sample plate with the standard color plate, determine the degree of difference from the standard color plate based on the same evaluation criteria as those of the above-mentioned first step, and take the average value thereof as a final score. The obtained results are shown in table 2 below.
③ oil pen
Each sample plate was drawn with a ZEBRA black oil pen, left to stand for 2 minutes, and then wiped 10 times with a medium power with a clean paper towel, and 5 professional evaluators visually observed the oil pen residue and scratches, and evaluated based on the following evaluation criteria, and the average value was taken as a final score. The obtained results are shown in table 2 below.
1. about.1: remove 100% of the stain by wiping and have no scratch
Δ 2: wiping removes 100% of the stain but there are scratches
Δ 3: 80% of the stain was removed by wiping and there was a scratch
Δ × 4: wiping off 40-50% of stains and having scratches
X 5: most of the stain remained and could not be removed by wiping
< evaluation of actual use >
Quick experience evaluation
An artificial fat was prepared according to ASTM D4265-14, and the obtained fat and dust were uniformly applied to each sample plate, left to stand for 2 minutes, wiped 10 times with 75% alcohol, left to stand for 30 minutes, and then the color difference value of each sample plate was measured using a color difference meter (among them, the color difference value is preferably < 7). The obtained results are shown in table 2 below.
(evaluation of Long-term use)
And if the performance is obviously improved relative to a blank sample (the mouse is mainly based on quick experience data, and the USB line is based on the condition of wiping by an oil pen), further carrying out long-term use evaluation. Each of the prepared mice was distributed to at least 30 evaluators (50% of evaluators were office workers and laboratory workers, respectively), and each of the evaluators was allowed to normally use for 1 month before testing. After 1 month, the product obtained as a result of comparing the apparent color of the mouse with the standard color plate by visual observation was judged to be "OK" when the value of the degree of difference from the standard color plate was not more than 60% (among them, 80% or more and not more than 3, and more preferably 90% or more and not more than 3), and the other cases were judged to be "NG". The obtained results are shown in table 2 below.
[ Table 1]
Figure BDA0002539477360000121
*1: the commodity name is as follows: YH503, manufacturer: linglin chemical
*2: a fluorocopolymer of C6FMA, CHMA and HEMA, which was obtained by the method of Synthesis example 3 described in Japanese patent application laid-open No. 2014-223623
*3: the commodity name is as follows: paraffin oil KP 6030, manufacturer: kehua (Kehua)
*4: the commodity name is as follows: KF96-10000CS, manufacturer: shin-Etsu chemical industry Co
*5: the commodity name is as follows: HF 75AE, manufacturer: zhejiang Huafeng thermoplastic polyurethane Co., Ltd
*6: the auxiliary agent comprises antioxidant and color masterbatch, wherein the antioxidant is 1010 made by BASF corporation, and the color masterbatch is RT878 made by Zhongming New Material science and technology Limited in Dongguan city
Figure BDA0002539477360000141
As is clear from table 2 above, when the fluorine-containing functional elastomer material of the present invention contains components (a) to (C) (particularly preferably further contains component (D) and component (E)), the resulting mouse surface coating material has a good texture, has excellent antifouling properties against various contaminants, is easy to wipe, and can delay the time for staining the product.
(experiment 2)
Examples 3-1 to 3-2, 4-1 to 4-5 and comparative examples 3-1 to 3-2, 4
Weighing the raw materials of the USB cable coating material according to the composition and the amount shown in Table 3, mixing the raw materials except the filling oil in a high-speed mixer at a high speed for 3-5 minutes, adding the filling oil, and further fully mixing for 1-2 minutes. And then adding the mixture into a double-screw extruder, carrying out melt extrusion and granulation at the forming temperature of 150-220 ℃, and drying to obtain the modified material of the USB cable coating material. Then, the obtained modified material is prepared into a sample plate with the thickness of 3cm multiplied by 10cm and the thickness of 0.2cm by using an injection molding machine at the molding temperature of 160-230 ℃.
Using the sample plates obtained in examples 3-1 to 3-2 and 4-1 to 4-5 and comparative examples 3-1 to 3-2 and 4, respectively, evaluations of the properties were made in the same manner as in experiment 1, and the results are shown in Table 4.
[ Table 3]
Figure BDA0002539477360000151
The values of 1 to 4 and 6 are the same as those of 1 to 4 and 6 in table 1.
*7: the commodity name is as follows: H920Y, manufacturer: korea SK Co Ltd
*8: the commodity name is as follows: PX-200, manufacturer: daba chemical industries, Japan Co., Ltd
Figure BDA0002539477360000161
As is clear from table 4 above, when the fluorine-containing functional elastomer material of the present invention contains components (a) to (C) (particularly preferably further contains component (D) and component (F)), the obtained USB cable-covering material has good hand feeling, excellent antifouling property against various contaminants, is easy to wipe, and can delay the time for staining the product.

Claims (24)

1. A fluorine-containing functional elastomer material, wherein,
comprises the following components (A) to (C),
(A) styrenic thermoplastic elastomers;
(B) a fluorocopolymer obtained by copolymerizing a monomer mixture containing the following monomers (b1) to (b3),
(b1)CH2＝C(-CH3)-C(＝O)-O-(CH2)2-(CF2)5CF3、
(b2) cyclohexyl methacrylate,
(b3) 2-hydroxyethyl methacrylate;
(C) the oil is filled in the oil tank,
the content of the component (A) is 15-35% by mass, the content of the component (B) is 0.5-10% by mass, and the content of the component (C) is 10-30% by mass, based on 100% by mass of the fluorine-containing functional elastomer material.
2. The fluorine-containing functional elastomer material according to claim 1,
the component (A) is a styrene-ethylene-butylene-styrene block copolymer.
3. The fluorine-containing functional elastomer material according to claim 1 or 2,
the content of the component (B) is 3-9% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
4. The fluorine-containing functional elastomer material according to any one of claims 1 to 3,
the content of the component (B) is 3-6% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
5. The fluorine-containing functional elastomer material according to any one of claims 1 to 4,
further contains an organic silicone as the component (D).
6. The fluorine-containing functional elastomer material according to claim 5,
the component (D) is polydimethylsiloxane represented by the following general formula (2),
(C2H6OSi)n (2)
wherein n represents a number in the range of 1000 to 20000.
7. The fluorine-containing functional elastomer material according to claim 5 or 6,
the content of the component (D) is 0.5-10% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
8. The fluorine-containing functional elastomer material according to any one of claims 5 to 7,
the content of the component (D) is 0.5-5% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
9. The fluorine-containing functional elastomer material according to any one of claims 1 to 8,
further comprising component (E) a thermoplastic polyurethane elastomer.
10. The fluorine-containing functional elastomer material according to claim 9,
the component (E) is (A 'B')mA block-type linear polymer having a linear structure,
wherein A 'is polyester or polyether with molecular weight of 1000-6000, B' is diol with linear alkyl with carbon atom number of 2-12, chemical structure between A 'B' chain segments is diisocyanate, and m is number of 1-200.
11. The fluorine-containing functional elastomer material according to any one of claims 1 to 10,
the fluorine-containing functional elastomer material is used as a mouse surface coating material.
12. The fluorine-containing functional elastomer material according to claim 11,
the content of the component (A) is 15-30% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
13. The fluorine-containing functional elastomer material according to claim 11 or 12,
the content of the component (A) is 18-26% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
14. The fluorine-containing functional elastomer material according to any one of claims 11 to 13,
the content of the component (E) is 20-50% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
15. The fluorine-containing functional elastomer material according to any one of claims 11 to 14,
the content of the component (E) is 25 to 45% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
16. The fluorine-containing functional elastomer material according to any one of claims 1 to 8,
further comprising a component (F) of a polyolefin.
17. The fluorine-containing functional elastomeric material according to claim 16,
the component (F) is polypropylene.
18. The fluorine-containing functional elastomer material according to claim 16 or 17,
the fluorine-containing functional elastomer material is used for a USB cable coating material.
19. The fluorine-containing functional elastomeric material according to claim 18,
the content of the component (A) is 18-30% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
20. The fluorine-containing functional elastomer material according to claim 18 or 19,
the content of the component (A) is 25-30% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
21. The fluorine-containing functional elastomer material according to any one of claims 18 to 20,
the content of the component (F) is 10-40% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
22. The fluorine-containing functional elastomer material according to any one of claims 18 to 21,
the content of the component (F) is 13-30% by mass relative to 100% by mass of the fluorine-containing functional elastomer material.
23. A coating material for the surface of mouse is composed of a base,
made of the fluorine-containing functional elastomer material according to any one of claims 1 to 15.
24. A USB cable covering material, wherein,
made of a fluorine-containing functional elastomer material according to any one of claims 16 to 22.
CN202010542492.2A 2020-06-15 2020-06-15 Fluorine-containing functional elastomer material Pending CN113801425A (en)

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Publication Number Publication Date
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