CN103937064A - Polyethylene resin foam sheet - Google Patents
Polyethylene resin foam sheet Download PDFInfo
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- CN103937064A CN103937064A CN201410022535.9A CN201410022535A CN103937064A CN 103937064 A CN103937064 A CN 103937064A CN 201410022535 A CN201410022535 A CN 201410022535A CN 103937064 A CN103937064 A CN 103937064A
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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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention provides a polyethylene resin foam sheet capable of easily removing foreign matters attached onto the glass by using the water. The polyethylene resin foam sheet provided by the utility model is characterized by comprising polyethylene-based resin, a polymeric antistatic agent, an anionic-based surfactant, and a non-ionic based surfactant. With the mass of polyethylene-based resin as 100 parts, the polyethylene resin foam sheet comprises 5 to 15 parts of polymeric antistatic agent, 0.1 to 5 parts of anionic-based surfactant, and 0.1 to 0.5 parts of non-ionic based surfactant by mass. The mass ratio of anionic-based surfactant to non-ionic based surfactant is 1 to 10.
Description
Technical field
The present invention relates to polyethylene-based resin foamed.
Background technology
Polyethylene-based resin foamed (below also referred to as " foamed sheet ") softness and resiliency excellence therefore can be used in the lining paper of the wrapping material of electronic unit, household appliances, glass etc.
For example, the glass substrate that the flat-panel monitor of liquid-crystal display, plasma display and so on is used with the state being inserted with to each other foamed polyolefin resin sheet stacked be supplied to display manufacturer by glass manufacturer.
In addition, this glass substrate is owing to having the worry that can make while having adhered to from the teeth outwards foreign matter flat-panel monitor produce various unfavorable conditions, therefore, tentatively use after having carried out the operation that water cleans.
Thus, for foamed sheet, also easily utilize washing to remove even if require to have adhered to the foreign matters such as dust on the surface of glass substrate.
For this demand, for example, propose to contain as nonionic the foamed sheet that the polyoxyalkylene that is tensio-active agent is tensio-active agent (for example, patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-185210 communique
Summary of the invention
the problem that invention will solve
Described foamed sheet is tensio-active agent owing to containing nonionic, even if therefore have advantages of that adhering to foreign matter on the surface of glass substrate also can wash this foreign matter together with being tensio-active agent with nonionic off by the surface of washing glass substrate.
But recently, glass substrate is used to more accurate equipment etc., therefore require further to remove the foreign matter adhering on the surface of glass substrate.
For this demand, in order further to improve the removal effect of foreign matter, can consider to increase the amount that nonionic is tensio-active agent.
But, there is following problem: be the amount of tensio-active agent even if increase nonionic, cleaning performance is also insufficient, on the contrary, nonionic is that tensio-active agent self is attached in a large number as foreign matter on the surface of glass substrate, even if water cleans the surface of glass substrate, nonionic is the surface that tensio-active agent also can residue in glass substrate.
In view of the demand, the polyethylene-based resin foamed of foreign matter that provides easy utilization washing removal to be attached to glass is provided problem of the present invention.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research, and found that, the foreign matter that is attached to glass is made up of higher stearic acid based compound of lipophilicity etc. and sebum in addition, fiber, resin particle etc.Discovery in addition, for described foreign matter, by being that tensio-active agent and nonionic are that tensio-active agent combination is used by negatively charged ion, the foreign matter that utilizes washing removal to be attached to glass becomes easy.And then, expect the present invention by these discoveries.
; the present invention is a kind of polyethylene-based resin foamed; it is characterized in that; containing polyethylene-based resin, Polymer Antistatic Agent, negatively charged ion is that tensio-active agent and nonionic are tensio-active agent; with respect to the aforementioned polyethylene-based resin of 100 mass parts; contain the aforementioned Polymer Antistatic Agent of 5～15 mass parts, the aforementioned negatively charged ion of 0.1～5 mass parts is that tensio-active agent, the aforementioned nonionic of 0.1～0.5 mass parts are tensio-active agent, aforementioned negatively charged ion is that the mass ratio that tensio-active agent is tensio-active agent with respect to aforementioned nonionic is 1～10.
According to described polyethylene-based resin foamed, be that tensio-active agent and nonionic are tensio-active agent by containing negatively charged ion, the foreign matter that utilizes washing removal to be attached to glass becomes easy.Can think, for the higher stearic acid based compound of lipophilicity etc., especially nonionic is tensio-active agent performance cleaning performance, and for sebum in addition, fiber, resin particle etc., especially negatively charged ion is tensio-active agent performance cleaning performance.
the effect of invention
According to the present invention, can provide easy utilization washing to remove to be attached to polyethylene-based resin foamed of foreign matter of glass.
Embodiment
Polyethylene-based resin foamed of present embodiment is that to contain polyethylene-based resin, Polymer Antistatic Agent, negatively charged ion be that tensio-active agent and nonionic are polyethylene-based resin foamed (being designated hereinafter simply as " foamed sheet ") of tensio-active agent.
About this foamed sheet, exemplify following foamed sheet this embodiment is described: be that tensio-active agent and nonionic are the polyethylene-based resin composition extrusion foaming of tensio-active agent and be formed as the foamed sheet of sheet by contain Polymer Antistatic Agent, negatively charged ion together with polyethylene-based resin.
First, the material of the foamed sheet that forms present embodiment is described.
As the polyethylene-based resin of foamed sheet that forms present embodiment, preferably using melt mass flow rate (below also referred to as " MFR ") is that 2～6g/10min and resin density are 925kg/m
3above and 935kg/m
3following ldpe resin.
The ldpe resin of preferred MFR as above be because, when MFR is too small, in forcing machine, have problems with the mixing property of Polymer Antistatic Agent, antistatic property reduction, worries that generation is broken bubble etc. and is difficult to obtain good foamed sheet in the time of extrusion foaming.
In addition, the ldpe resin of preferred MFR as above is because when MFR is excessive, melting tension force becomes too low, becomes and is difficult to obtain low-density foamed sheet, becomes the settling that easily produces gum shape at mould front end.
; preferably use MFR ldpe resin above for 2g/10min and below 6g/10min to be because; not only easily make the foamed sheet obtaining become good foamed state; and in the time that it is manufactured, can reduce for removing aforementioned sedimental time/labour, improve the manufacture efficiency of this foamed sheet.
It should be noted that, about this melt mass flow rate, in this manual, in the situation that not illustrating in addition, MFR about aftermentioned Polymer Antistatic Agent is also, mean that method by recording in JIS K7210:1999 " melt mass flow rate (MFR) of plastics-thermoplastics and the test method of melt volume-flow rate (MVR) (プ ラ ス チ ッ Network-Hot plasticity-プ ラ ス チ ッ Network メ Le ト マ ス フ ロ ー レ イ ト (MFR) and び メ Le ト ボ リ ュ ー system フ ロ ー レ イ ト (MVR) Try test method) " B method (wherein, 190 DEG C of test temperatures, load 21.18N) and the value of mensuration.
As the aforementioned polyethylene-based resin of foamed sheet that forms present embodiment, preferably having density as above is because when resin density is too small, the dissipation of the whipping agent of the foamed sheet after certainly extruding is fast, worry the less rigid of resin self, therefore worry cannot suppress to shrink.
In addition, as aforementioned polyethylene-based resin, preferably having density as above is because when resin density adopts excessive value, the rigidity of resin self is excessive, worries that foamed sheet loses the resiliency as wrapping material.
That is, as the aforementioned polyethylene-based resin of foamed sheet that forms present embodiment, preferably there is density as above and be because, favourable to forming the foamed sheet of resiliency excellence.
As the aforementioned Polymer Antistatic Agent that forms foamed sheet together with aforementioned polyethylene-based resin, the Polymer Antistatic Agent that preferably 90 DEG C of crystallization temperature less thaies and MFR are 10～40g/10min.
90 DEG C of the preferred less thaies of crystallization temperature of Polymer Antistatic Agent be because, when crystallization temperature is too high, in forcing machine, crystallization is carried out and is disperseed variation, in addition, in the time of extrusion foaming, in the time that bubble chamber film is stretched, Polymer Antistatic Agent forms piece and indeformable, and it is large that the discrete particles spacing of static inhibitor becomes, and is difficult to show the anti-static function conforming to addition.
, 90 DEG C of preferred less thaies of the crystallization temperature of Polymer Antistatic Agent are because be favourable making foamed sheet bring into play on the anti-static function conforming to addition.
In addition, the MFR of Polymer Antistatic Agent be preferably in foregoing scope be because, when the MFR of Polymer Antistatic Agent is too small, in forcing machine, in mould, become inhomogeneous to the dispersion in polyethylene-based resin, although demonstrate the tendency of surface resistivity excellence electrostatic attenuation rate variation.
In addition, MFR in foregoing scope, be preferably because, while using the excessive Polymer Antistatic Agent of MFR, dispersiveness in polyethylene-based resin reduces, and the melting tension force of polyethylene-based resin composition is reduced, therefore worry can not get low-density foamed sheet or produce the air pocket being communicated with.
, to be preferably in foregoing scope be because be favourable making foamed sheet that foamed state is good bring into play in excellent electrostatic attenuation rate to the MFR of Polymer Antistatic Agent.
It should be noted that, about aforementioned crystallization temperature, in this manual, the in the situation that of explanation not in addition, mean the value of measuring according to the method for recording in JIS K7122:1987 " the transition temperature measuring methods (プ ラ ス チ ッ Network translocation moves temperature-measuring method) of plastics ".
Particularly, (for example use differential scanning calorimeter, " DSC6220 " that SII Nano Technology Inc. manufactures), in mensuration container, fill the sample of about 6.5mg, nitrogen flow is made as to 30ml/min, under the heat-up rate of 10 DEG C/min, be warming up to after 200 DEG C from 30 DEG C, cooling under the speed of cooling of 10 DEG C/min, can measure this exothermic peak temperature when cooling as crystallization temperature.
It should be noted that, exothermic peak occurs when more than two, using having in the more than 5% area peak of total peak area, the temperature on the summit at the peak of highest temperature side is as crystallization temperature.
As aforementioned Polymer Antistatic Agent, can list ethylene series segment and the multipolymer of hydrophilic segment etc. in the quaternary ammonium salt, TOHKEMY 2001-278985 communique of ionomer, the polyethylene glycol methacrylate-styrene polymer based copolymer etc. of polyoxyethylene, polyoxytrimethylene, polyoxyethylene glycol, polyesteramide, polyether ester amides, ethylene-methacrylic acid copolymer etc., recorded.
Wherein, the multipolymer of preferred alkenes tethers section and hydrophilic segment preferably contains polyethers-polyolefin block copolymer (segmented copolymer of polyethers tethers section and polyolefin segment) as aforementioned Polymer Antistatic Agent in polyethylene-based resin composition.
It should be noted that, as Polymer Antistatic Agent, also can be the mixture of two or more materials, in order further to improve antistatic property, can be also the material that mixed polyamide forms in aforementioned segmented copolymer or the material that further copolyamide tethers section forms.
As aforementioned Polymer Antistatic Agent, more preferably the ethylene series segment of more than 70 % by mole propylene and the multipolymer of the polyethers tethers section material as main component will be contained.
Herein, aforementioned multipolymer is that " main component " refers to, polyethers-polyolefin block copolymer shared ratio in Polymer Antistatic Agent is more than 50 quality %.
In addition, aforementioned polyethers-polyolefin block copolymer more than shared ratio is preferably made as 70 quality % in Polymer Antistatic Agent, further be preferably made as 80 quality % more than.
As forming compounding ratio in the polyethylene-based resin composition of polyethylene-based resin foamed of present embodiment, aforementioned polyethylene-based resin and aforementioned Polymer Antistatic Agent, with respect to 100 mass parts polyethylene-based resins, the ratio that aforementioned Polymer Antistatic Agent is made as to 5～15 mass parts is important.
The compounding ratio of the Polymer Antistatic Agent in polyethylene-based resin composition is in aforementioned range to be important, this be because, more than being made as the lower value of aforementioned range, thereby the antistatic property that can prevent foamed sheet is not enough and on glass substrate, adhere to dust, for example, stripping electrification, can suppress to peel off from glass substrate time.
In addition, the compounding ratio of the Polymer Antistatic Agent in polyethylene-based resin composition is in aforementioned range to be important, this be because, by being made as below the higher limit of aforementioned range, thereby the cost that not only can suppress foamed sheet rises, and can prevent that the foaminess of polyethylene-based resin composition from reducing and can not get low-density foamed sheet.
In aforementioned polyethylene-based resin foamed, contained aforementioned negatively charged ion is that tensio-active agent plays a role to antistatic as the low molecule-type static inhibitor of what is called, in the present embodiment, preferably adopt at 20 DEG C as the negatively charged ion of solid is tensio-active agent, wherein, more preferably adopting the HLB value being obtained by Davis's method (Davis method) is that the negatively charged ion of more than 20 (higher limit is generally 50) is tensio-active agent.
It should be noted that, Davis's method refers to, surfactant molecule is divided into atomic group (or functional group), give distinctive radix to each atomic group, obtain HLB value by calculating, for example, can calculate according to the concrete method of recording in the title of being issued by Sanyo Chemical Industries, Ltd. " tensio-active agent introduction " (" interfacial activity AGENT Ru Door ").
It should be noted that, hereinafter, " HLB value " expression " the HLB value being obtained by Davis's method " in the situation that there is no explanation in addition.
Be tensio-active agent as aforementioned negatively charged ion, for example can adopt the sulfonate such as dialkyl sulfosuccinates, alkylsulfonate, alhpa olefin sulfonate, linear alkylbenzene sulfonate, naphthalenesulfonate-formaldehyde condensation products, sulfonated alkyl naphathalene, N-methyl-N-acyl taurine salt is tensio-active agent; The carboxylate salts such as aliphatics unary carboxylation, Voranol EP 2001 carboxylate salt, N-acyl sarcosinate, N-acyl glutamate are tensio-active agent; The sulfuric acids such as alkyl sulfuric ester salt, polyoxyethylene alkyl ether sulfate salt, grease sulfuric acid are tensio-active agent; The phosphate ester salts such as alkylphosphonic, Voranol EP 2001 phosphoric acid salt, polyoxyethylene alkyl phenyl ether phosphoric acid salt are tensio-active agent etc.
It should be noted that, above-mentioned negatively charged ion is that tensio-active agent must not use separately one, also can combine two or more uses.
It should be noted that, aforementioned negatively charged ion in foamed sheet is that the content of tensio-active agent is when very few, be difficult to expect to prevent that this negatively charged ion from being material beyond the tensio-active agent effect in the surface attachment of glass substrate, and become and be difficult to foamed sheet to give fully antistatic effect.
On the other hand, antistatic effect, negatively charged ion are that the raising of the inhibition of the dirt settling beyond tensio-active agent is limited, even if therefore exceeding and contain necessarily aforementioned negatively charged ion in foamed sheet is tensio-active agent, also just there is the worry that is difficult to manufacture foamed sheet.
Thus, aforementioned negatively charged ion is that the mode of tensio-active agent taking the ratio with respect to 100 mass parts polyethylene-based resins as 0.1～5 mass parts contain in foamed sheet is important, preferably contains in foamed sheet with 0.1～3 mass parts.
In aforementioned illustrative material, be tensio-active agent as aforementioned negatively charged ion contained in the foamed sheet in present embodiment, aspect easily removing from glass baseplate surface washing, preferably adopt is the tensio-active agent of solid at 20 DEG C, wherein, more preferably at 20 DEG C, the sulfonate for solid is tensio-active agent.
Be tensio-active agent as sulfonate, preferably use alkylsulfonate.
Wherein, to be particularly preferably alkyl sodium sulfonate be tensio-active agent to alkylsulfonate.
Be tensio-active agent as contained aforementioned nonionic in aforementioned polyethylene-based resin foamed, can adopt polyoxyalkylene is tensio-active agent etc.
It should be noted that, the aforementioned nonionic in foamed sheet is the content of tensio-active agent when very few, becomes and is difficult to expect to prevent that this nonionic from being the lip-deep effect that material beyond tensio-active agent is attached to glass substrate.
On the other hand, nonionic is that the raising of the inhibition of the dirt settling beyond tensio-active agent is limited, therefore, even if exceed, in foamed sheet, to contain necessarily aforementioned nonionic be tensio-active agent, worries that on the contrary nonionic is that tensio-active agent adheres on the surface of glass substrate.
Thus, aforementioned nonionic is that the mode of tensio-active agent taking the ratio with respect to 100 mass parts polyethylene-based resins as 0.1～0.5 mass parts contain in foamed sheet is important, preferably contains in foamed sheet with 0.1～0.4 mass parts.
In aforementioned illustrative material, aforementioned nonionic contained in the foamed sheet as present embodiment is tensio-active agent, can bring into play excellent cleaning performance aspect, preferably adopting polyoxyalkylene is tensio-active agent.
Aforementioned negatively charged ion is tensio-active agent is the mass ratio of tensio-active agent when very few with respect to aforementioned nonionic, and worrying that nonionic is tensio-active agent can be insufficient at residual or cleaning performance on glass.
On the other hand, aforementioned negatively charged ion is tensio-active agent is the mass ratio of tensio-active agent when excessive with respect to aforementioned nonionic, worries that the cleaning performance of the organic metal salts such as stearic acid based compound can be insufficient.
Thus, aforementioned negatively charged ion is that the mass ratio that tensio-active agent is tensio-active agent with respect to aforementioned nonionic is 1～10th, important, is preferably 1～8.
Aforementioned nonionic is that the softening temperature of tensio-active agent is preferably the softening temperature of tensio-active agent lower than aforementioned negatively charged ion.Aforementioned foamed sheet is that the softening temperature of tensio-active agent is the softening temperature of tensio-active agent lower than aforementioned negatively charged ion by aforementioned nonionic, and making nonionic is that tensio-active agent is that tensio-active agent oozes out prior to negatively charged ion.Therefore, nonionic is that the stearic acid based compound that tensio-active agent can be effectively higher with lipophilicity etc. contacts, the cleaning performance of performance to the higher stearic acid based compound of lipophilicity etc.
It should be noted that, softening temperature can be by obtaining according to the mensuration of JIS K5601-2-2:1999.Particularly, use distilled water as thermal medium, measure by ring and ball method.
It should be noted that, manufacture by extrusion foaming for polyethylene-based resin foamed of present embodiment, therefore except mentioned component, also further contain the required composition of foaming.
As the composition for this foaming, can list whipping agent, bubble conditioning agent, except containing as required the additives such as thermo-stabilizer, UV light absorber, antioxidant, tinting material these in foamed sheet.
As aforementioned whipping agent, can list the inorganic gass such as the hydrocarbon such as Trimethylmethane, normal butane, propane, pentane, hexane, tetramethylene, pentamethylene, carbonic acid gas, nitrogen.
Wherein, as aforementioned whipping agent, the preferably mixed butanes of Trimethylmethane and normal butane.
While so using the mixed butanes of Trimethylmethane/normal butane, due to Trimethylmethane, the violent dissipation of the whipping agent in extrusion foaming operation is suppressed, on the other hand, suppress the increase of continuous air bubbles rate with the normal butane of the consistency excellence of polyethylene-based resin, therefore can obtain shrinking less and foamed sheet that continuous air bubbles rate is few, resiliency excellence.
In addition, the amount of the whipping agent using when extrusion foaming also depends on required foaming degree, but with respect to total 100 mass parts of polyethylene-based resin and Polymer Antistatic Agent, is conventionally made as 5 mass parts above and below 25 mass parts.
Conventionally the adding proportion of whipping agent is made as to this scope and is because, whipping agent is 5 mass parts when above, become easily and foamed fully, by being made as below 25 mass parts, the breaking of the bubble chamber film can suppress to foam time.
In addition, for adjusting the aforementioned bubble conditioning agent of the bubble being formed by whipping agent, can list mixture, the Cellmic C 121 etc. of the inorganic powder such as talcum, silicon-dioxide, the polycarboxylic acid that also can be used as decomposition-type foaming agent and sodium carbonate or sodium bicarbonate (sodium bicarbonate).
These may be used alone, can also be used in combination multiple.It is below 0.5 mass parts that the addition of this bubble conditioning agent is preferably made as in every 100 mass parts polyethylene-based resins.
The foamed sheet of present embodiment can similarly be manufactured with common extrusion foaming sheet, gives an example, can be by following operation manufacture: extrusion foaming operation, by aforementioned polyethylene-based resin composition extrusion foaming, make extrusion foaming sheet; Coiling process, batches the sheet of extruding with reeling machine, make reel; Curing step, during the reel slaking of batching necessarily; Decorate coiling operation, reel rewinding is become to product volume with rewinding machine etc.
The thickness of aforementioned foamed sheet is preferably 0.3～2mm, 0.3～1mm more preferably.Aforementioned foamed sheet, because thickness is more than 0.3mm, therefore has advantages of that resiliency becomes excellent.In addition, aforementioned foamed sheet, because thickness is below 2mm, therefore has advantages of that stacking efficiency improves in the time of the lining paper as glass substrate.
About the thickness of foamed sheet, use constant voltage thickness measurement machine (Teclock company manufactures, model " SCM-627 "), use counterweight cylindraceous, at the face (area: 60.8cm of the toroidal of radius 4.4cm
2) the upper load (containing deadweight) that foamed sheet is applied to 95g, the thickness of mensuration foamed sheet now.
It should be noted that, on width, measure 50 points every 5cm, using the arithmetical av of its measured value as thickness.In addition, cannot obtain the locating of 50 points time, measure as much as possible, using the arithmetical av of its measured value as thickness.
The basic weight of aforementioned foamed sheet is preferably 15～50g/m
2, 20～40g/m more preferably
2.Aforementioned foamed sheet is because basic weight is 15g/m
2above, therefore have advantages of that stiffness uprises.In addition, aforementioned foamed sheet is because basic weight is 50g/m
2below, therefore have advantages of that resiliency becomes excellent.
It should be noted that, about the basic weight of foamed sheet, to cut foamed sheet along the width of extruding direction 20cm in the direction orthogonal with extruding direction, by weight W (g) and the area S (cm of this section
2) obtain by following formula.In addition,, while being not enough to the size of the level that the width of 20cm cuts in the direction orthogonal with extruding direction, cut as wide as possible orthogonal shape, by weight W (g) and the area S (cm of this section
2) obtain by following formula.
Basic weight (g/m
2)=W/S × 10000
The surface resistivity of aforementioned foamed sheet is preferably 10
6～10
12Ω/, more preferably 10
8～10
12Ω/.Aforementioned foamed sheet is because surface resistivity is 10
6more than Ω/, therefore have advantages of and can fully suppress oozing out of the low molecular weight compositions that caused by Polymer Antistatic Agent.In addition, aforementioned foamed sheet is because surface resistivity is 10
12below Ω/, therefore can be suppressed at the manufacture of foamed sheet time, when the use of foamed sheet, produce static, its result, has advantages of that can suppress dust etc. is attached to foamed sheet.
It should be noted that, the method that the surface resistivity of foamed sheet is recorded by JlS K6911:1995 " Thermocurable plastics universal test method (the general Try test of Hot hardening プ ラ ス チ ッ Network method) " is measured.
Embodiment
Then, list embodiment and comparative example is further specifically described the present invention.
(evaluation)
Illustrate and start the example that the foamed sheet 7 days carries out various evaluations when from extrusion foaming.
First, physical property, the physical property of foamed sheet and the evaluation method of foamed sheet to material is described.
(softening temperature of tensio-active agent)
Measure by aforesaid method.
(thickness of foamed sheet and basic weight)
Measure by aforesaid method.
(surface resistivity of foamed sheet)
The surface resistivity of foamed sheet is measured by the method for recording in JIS K6911:1995 " Thermocurable plastics universal test method " (" the general Try test of Hot hardening プ ラ ス チ ッ Network method ").; use-testing device (digital superelevation resistance/microgalvanometer R8340 and resistivity measurement box R12702A that ADVANTEST CORPORATION manufactures); on test film with the load pressure receiving electrode of about 30N; be determined at the resistance value of charging after 1 minute under 500V, obtain surface resistivity by following formula.
Wherein, test film cuts out width 100mm × length 100mm × reel thickness and makes from the reel of foamed sheet.In addition, under the atmosphere of 20 ± 2 DEG C of temperature, humidity 65 ± 5%, test film was placed after 24 hours, under the atmosphere of 20 ± 2 DEG C of temperature, humidity 65 ± 5%, carried out said determination as testing circumstance.The quantity of test film is made as to 5, measures the tow sides of each test film, using the geometrical mean of the measured value of 10 of totals as surface resistivity.
ρs=π(D+d)/(D-d)×Rs
ρ s: surface resistivity (Ω/)
D: the internal diameter (cm) of the ring electrode on surface (in resistivity measurement box R12702A, is 7cm.)
D: the external diameter (cm) of the inner circle of surface electrode (in resistivity measurement box R12702A, is 5cm.)
Rs: surface resistivity (Ω)
(contact angle of sheet glass)
Judge the adaptability as the lining paper of glass substrate with contact angle as described below.
First, foamed sheet is cut into the size of 5cm × 10cm, be positioned on the sheet glass (Nippon Electric Glass Co., Ltd manufactures non-alkali glass OA-10G) after washing/drying, and then the mode of aforementioned foamed sheet entirety applied load is loaded to the counterweight of 1kg, at the constant temperature and humidity cabinet of temperature 60 C, relative humidity 80%, (ISUZU makes manufacturing, trade(brand)name " HPAV-120-40 ") interior placement after 24 hours, in 30 DEG C of temperature, relative humidity 0% time dry 24 hours.By the home-use alkaline cleaner that contains 0.4 quality % for sheet glass that carried out this processing, (Kao Corp manufactures, trade(brand)name " Attack ") rinse water clean, implement after rinsing with distilled water, be dried 24 hours 0% time in 30 DEG C of temperature, relative humidity.
Measure the contact angle of the purified water in the glass pane surface contacting with foamed sheet with the solid-liquid interface analytical equipment (trade(brand)name " DROPMASTER300 ") that consonance interfacial chemistry Co., Ltd. manufactures, as the contact angle after cleaning.
It should be noted that, the contact angle after cleaning carries out respectively the mensuration of 20, utilizes its mean value to calculate.
(adhesion amount of stearic acid based compound)
Measure the surface of the glass after the contact angle after cleaning with microscopic examination, the all substances of adhering on the 2cm × 2cm of each glass are implemented to infrared microscopy IR to be measured, measure the number containing the aggregation of stearic acid based compound, obtain arithmetical av (n=3) by measured value.
Measuring method is as follows.
Measure and use Fourier transform infrared spectrophotometer Spectrum One (manufacture of Perkin Elmer company) and quick IR imaging system Spectrum Spotlight300.
Mode determination: spot/ATR method
< condition determination >
Resolving power: 4cm
-1
Scanning times: 256 times
Aperture: 100 × 100 μ m
As pre-treating process, dirt is transferred on atr crystal, by ATR method mensuration.
(cleaning of glass)
By the cleaning of the evaluation of result glass of " contact angle after cleaning " and " adhesion amount of stearic acid based compound ".
Zero: the contact angle after cleaning is that 10 ° of adhesion amounts following and stearic acid based compound are 1/4cm
2following situation
×: the situation beyond zero
(embodiment 1)
Ldpe resin (the trade(brand)name: " LF580 ", density: 929kg/m of manufacturing with respect to Japan Polyethylene Corp.
3mFR=4.0g/10min) 100 mass parts, Polymer Antistatic Agent (polyethers-polypropylene block copolymer that Sanyo Chemical Industries Co., Ltd. is manufactured, trade(brand)name: " PELESTAT300 ", crystallization temperature: 85.4 DEG C, MFR=30g/10min) (alkyl sodium sulfonate that contains carbon numbers 12～16 more than 90 quality % is tensio-active agent as negatively charged ion for the trade(brand)name " CHEMISTAT3033 " manufactured using 6 mass parts, Sanyo Chemical Industries Co., Ltd..70 DEG C of softening temperatures) change into the bubble conditioning agent masterbatch that Co., Ltd. manufactures (containing the masterbatch of Cellmic C 121: trade(brand)name " CELLMIC MB1023 ") with 0.5 mass parts and three associations and carry out compounding with the ratio of 0.3 mass parts, by the formulation obtaining be supplied in series connection forcing machine the first forcing machine (barrel diameter:
), carry out melting mixing taking the temperature that is up in this forcing machine as the mode of 210 DEG C.Wherein, the softening temperature of " alkyl sodium sulfonate of carbon number 12～16 " is identical with the softening temperature of " CHEMISTAT3033 ".
In addition, from the way of this first forcing machine, be pressed into the mixed butanes (Trimethylmethane/normal butane=50/50 (mol ratio)) as whipping agent using the ratio with respect to the aforementioned ldpe resin of 100 mass parts as the mode of 15 mass parts, and then from the way of this first forcing machine, be pressed into using the ratio with respect to the aforementioned ldpe resin of 100 mass parts as the mode of 0.4 mass parts as nonionic be tensio-active agent polyoxyethylene glycol (Sanyo Chemical Industries Co., Ltd. manufacture, trade(brand)name: " PEG600 "), implement aforementioned melting mixing.
After melting mixing in this first forcing machine, the second forcing machine being connected with this first forcing machine (barrel diameter:
) in be cooled to the temperature range (111 DEG C) that is suitable for foaming, be that ring mould (circular die) extrusion foaming of 222mm (slit 0.04mm) is to atmosphere from exit diameter.Resin temperature is now 114 DEG C.
Tubular foam after extrusion foaming blow air cooling rear be cooling on the cooling plug of 770mm, length 650mm along diameter, tubular foam is cut off along extruding direction with the cutter of the rear side that is arranged at this cooling plug, obtain the foamed sheet of bar-shape, this foamed sheet is batched with coiling speed 35m/min, make foamed sheet become web-like.
(embodiment 2)
The quantitative change of the trade(brand)name " CHEMISTAT3033 " that Sanyo Chemical Industries Co., Ltd. is manufactured is is 0.8 mass parts with respect to 100 mass parts ldpe resins, be that tensio-active agent uses (Sanyo Chemical Industries Co., Ltd.'s manufacture of the different polyoxyethylene glycol of softening temperature as nonionic, trade(brand)name: " PEG1000 "), and the quantitative change that is tensio-active agent by nonionic is to be 0.1 mass parts with respect to 100 mass parts ldpe resins, in addition, operate similarly to Example 1, obtain the foamed sheet of web-like.
(embodiment 3)
Be that tensio-active agent uses polyoxyethylene lauryl ether (Kao Corp's manufacture as nonionic, trade(brand)name: " EMULGEN109P ") replace polyoxyethylene glycol, and the quantitative change that is tensio-active agent by nonionic is to be 0.2 mass parts with respect to 100 mass parts ldpe resins, in addition, operate similarly to Example 1, obtain the foamed sheet of web-like.
(comparative example 1)
Not using negatively charged ion is tensio-active agent, and be that tensio-active agent uses the different polyoxyethylene glycol of softening temperature (Sanyo Chemical Industries Co., Ltd. manufactures, trade(brand)name: " PEG1000 ") as nonionic, in addition, operate similarly to Example 1, obtain the foamed sheet of web-like.
(comparative example 2)
Be that tensio-active agent uses (Sanyo Chemical Industries Co., Ltd.'s manufacture of the different polyoxyethylene glycol of softening temperature as nonionic, trade(brand)name: " PEG1000 "), and the quantitative change that is tensio-active agent by nonionic is to be 2.0 mass parts with respect to 100 mass parts ldpe resins, in addition, operate similarly to Example 1, obtain the foamed sheet of web-like.
(comparative example 3)
Be that tensio-active agent uses (Sanyo Chemical Industries Co., Ltd.'s manufacture of the different polyoxyethylene glycol of softening temperature as nonionic, trade(brand)name: " PEG1000 "), and the quantitative change that is tensio-active agent by nonionic is to be 0.02 mass parts with respect to 100 mass parts ldpe resins, in addition, operate similarly to Example 1, obtain the foamed sheet of web-like.
Test-results is shown in to table 1.
[table 1]
As shown in table 1, the foamed sheet of embodiment 1～3 within the scope of the invention with not containing negatively charged ion be tensio-active agent comparative example 1 foamed sheet be that quantity not sufficient 0.1 mass parts of tensio-active agent and aforementioned negatively charged ion are that the foamed sheet that mass ratio that tensio-active agent is tensio-active agent with respect to aforementioned nonionic exceedes 10 comparative example 3 is compared with respect to the nonionic of 100 mass parts polyethylene-based resins, the adhesion amount of the stearic acid based compound on glass after cleaning is few.Hence one can see that, and compared with the foamed sheet of the foamed sheet of embodiment 1～3 and comparative example 1,3, the stearic acid based compound that lipophilicity is higher etc. is difficult on glass surface residual.
In addition, as shown in table 1, the foamed sheet of embodiment 1～3 within the scope of the invention exceedes 0.5 mass parts with the foamed sheet that is not the comparative example 1 of tensio-active agent containing negatively charged ion with the amount that is tensio-active agent with respect to the nonionic of 100 mass parts polyethylene-based resins and aforementioned negatively charged ion is that the foamed sheet that tensio-active agent is the comparative example 2 of the mass ratio less than 1 of tensio-active agent with respect to aforementioned nonionic is compared, and the contact angle after cleaning is low.Hence one can see that, and compared with the foamed sheet of the foamed sheet of embodiment 1～3 and comparative example 1,2, sebum, fiber, resin particle etc. are difficult on glass surface residual.
Therefore,, according to the present invention, can provide more in the past than polyethylene-based resin foamed of foreign matter who easily utilized washing to remove to be attached to glass.
Claims (4)
1. one kind polyethylene-based resin foamed, it is characterized in that, containing polyethylene-based resin, Polymer Antistatic Agent, negatively charged ion is that tensio-active agent and nonionic are tensio-active agent,
With respect to polyethylene-based resin described in 100 mass parts, the described Polymer Antistatic Agent that contains 5～15 mass parts, the described negatively charged ion of 0.1～5 mass parts are that the described nonionic of tensio-active agent, 0.1～0.5 mass parts is tensio-active agent,
Described negatively charged ion is that the mass ratio that tensio-active agent is tensio-active agent with respect to described nonionic is 1～10.
2. polyethylene-based resin foamed according to claim 1, wherein, described negatively charged ion is that tensio-active agent is that alkylsulfonate is tensio-active agent, and described nonionic is that tensio-active agent is that polyoxyalkylene is tensio-active agent.
3. polyethylene-based resin foamed according to claim 1 and 2, wherein, described nonionic is that the softening temperature of tensio-active agent is the softening temperature of tensio-active agent lower than described negatively charged ion.
4. polyethylene-based resin foamed according to claim 1 and 2, wherein, thickness is 0.3～2mm, and basic weight is 15～50g/m
2, surface resistivity is 10
6～10
12Ω/.
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| JP2013006386A JP5899129B2 (en) | 2013-01-17 | 2013-01-17 | Polyethylene resin foam sheet |
| JP2013-006386 | 2013-01-17 |
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| JP (1) | JP5899129B2 (en) |
| KR (1) | KR102143661B1 (en) |
| CN (1) | CN103937064B (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968486A (en) * | 2015-03-13 | 2016-09-28 | 积水化成品工业株式会社 | Polyethylene based resin foamed sheet |
| CN110078988A (en) * | 2018-01-25 | 2019-08-02 | 积水化成品工业株式会社 | The manufacturing method of sheet material and sheet material |
| CN111518328A (en) * | 2020-04-24 | 2020-08-11 | 浙江润阳新材料科技股份有限公司 | One-step formed antistatic IXPE and preparation method thereof |
| CN111732752A (en) * | 2019-03-25 | 2020-10-02 | 积水化成品工业株式会社 | Packaging sheet |
| CN112123905A (en) * | 2019-06-24 | 2020-12-25 | 株式会社Jsp | Antistatic laminated foam sheet and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101645610B1 (en) * | 2014-11-19 | 2016-08-05 | 롯데케미칼 주식회사 | Resin composition for preparing polyolefin resin foam and polyolefin resin foam formed therefrom |
| JP7271407B2 (en) * | 2019-11-28 | 2023-05-11 | 株式会社ジェイエスピー | Polyolefin resin multi-layer foamed sheet and interleaving paper for glass plate |
| JP7473166B2 (en) | 2020-03-27 | 2024-04-23 | 酒井化学工業株式会社 | Foam Resin Sheet |
| KR20230078955A (en) * | 2020-09-28 | 2023-06-05 | 세키스이가세이힝코교가부시키가이샤 | resin foam sheet |
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| CN102850617A (en) * | 2011-06-30 | 2013-01-02 | 积水化成品工业株式会社 | Polyolefin resin foaming sheet |
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| JP3488163B2 (en) * | 1999-02-10 | 2004-01-19 | 三洋化成工業株式会社 | Block polymer and antistatic agent comprising the same |
| JP4901589B2 (en) * | 2007-06-07 | 2012-03-21 | 株式会社ジェイエスピー | POLYOLEFIN RESIN EXTRUSION FOAM SHEET, GLASS SUBSTRATE COMPOSITION COMPRISING THE FOAM SHEET AND PACKAGING MATERIAL |
| JP5301845B2 (en) * | 2008-02-07 | 2013-09-25 | 株式会社ジェイエスピー | Polyolefin resin extruded foam sheet |
| KR101474029B1 (en) * | 2008-02-07 | 2014-12-17 | 가부시키가이샤 제이에스피 | Extruded foamed body of polyolefin resin |
| JP5638251B2 (en) * | 2009-01-30 | 2014-12-10 | 三洋化成工業株式会社 | Antistatic agent |
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| CN102850617A (en) * | 2011-06-30 | 2013-01-02 | 积水化成品工业株式会社 | Polyolefin resin foaming sheet |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968486A (en) * | 2015-03-13 | 2016-09-28 | 积水化成品工业株式会社 | Polyethylene based resin foamed sheet |
| CN105968486B (en) * | 2015-03-13 | 2020-01-14 | 积水化成品工业株式会社 | Polyethylene resin foamed sheet |
| CN110078988A (en) * | 2018-01-25 | 2019-08-02 | 积水化成品工业株式会社 | The manufacturing method of sheet material and sheet material |
| CN110078988B (en) * | 2018-01-25 | 2021-11-23 | 积水化成品工业株式会社 | Sheet and method for producing sheet |
| CN111732752A (en) * | 2019-03-25 | 2020-10-02 | 积水化成品工业株式会社 | Packaging sheet |
| CN112123905A (en) * | 2019-06-24 | 2020-12-25 | 株式会社Jsp | Antistatic laminated foam sheet and method for producing same |
| CN112123905B (en) * | 2019-06-24 | 2024-02-09 | 株式会社Jsp | Antistatic laminated foam sheet and method for producing the same |
| CN111518328A (en) * | 2020-04-24 | 2020-08-11 | 浙江润阳新材料科技股份有限公司 | One-step formed antistatic IXPE and preparation method thereof |
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| TWI631164B (en) | 2018-08-01 |
| KR102143661B1 (en) | 2020-08-11 |
| CN103937064B (en) | 2018-02-27 |
| JP2014136755A (en) | 2014-07-28 |
| KR20140093179A (en) | 2014-07-25 |
| TW201434909A (en) | 2014-09-16 |
| JP5899129B2 (en) | 2016-04-06 |
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