CN1243062A - High-anti-static laminated material - Google Patents

Abstract

A highly antistatic laminate containing a substrate and a conductive layer laminated on at least one side of the substrate, the conductive layer containing a conductive polymer and being cured, wherein a surface resistance (RS0) at 25 DEG C, relative humidity 15% of the conductive layer is not more than 10<11> Omega/-, a ratio (RS1/RS0) of surface resistance (RS1) at 25 DEG C, relative humidity 15% of the conductive layer after immersing the highly antistatic laminate in pure water at 40 DEG C for one hour, to RS0 is not more than 10, and a ratio (RS2/RS0) of surface resistance (RS2) at 25 DEG C, relative humidity 15% of the conductive layer after 150% stretching the highly antistatic laminate, to RS0 is preferably not more than 10. The highly antistatic laminate of the present invention provides a highly antistatic laminate having superior transparency, resistance to blocking and antistatic property under low humidity, after immersion in water and after forming, which certainly prevents occurrence of static electricity under any environment.

Description

High-anti-static laminated material

The present invention relates to a kind of high-anti-static laminated material, this laminated material has excellent antistatic property, resistance to water and hot water resistance, and transparent and anti-stick company under low humidity.Particularly, the present invention relates to have the high-antistatic laminated material of electric conductivity, this laminated material will be in storage; protect as IC LSI, silicon chip between transmission and installation period; hard disk, liquid crystal substrate, appliance materials such as electric elements are avoided damaging and because former thereby adhesion dusts such as static; this laminated material is specially adapted to the base band, cover tape, container (as pallet); be used for the dividing plate of clean room etc., also be applicable to OHP, X-ray film; silver salt coating film, printing paper, the base material of synthetic paper etc.

Recent years, more and more need microminiaturized electronic component, as the electronic component of chip class, particularly IC, transistor, diode, crystal oscillator etc.They are encapsulated in the recess (concave surface) of the base band of being made by mould of plastics, and can supply with or transportable the packing so that form one with the coverlay involution.When using, tear coverlay and take out package and then it is installed on the matrix etc.

During this packing is supplied with and is carried, will on the base band, produce static, the result makes it charged, and can produce charged when tearing coverlay on the base band.The charged meeting of base band makes the installation of electronic component become difficult and can produce as problems such as electrostatic breakdowns.

For addressing these problems, by mediating or be coated with the method for carbon black and surfactant, give thermoplastic resin sheet such as polystyrene, polypropylene as base band original material, polyvinyl chloride, PETG and polyacrylonitrile electric conductivity or antistatic property.

, for from containing the base band that the thermoplastic resin sheet of mediating carbon black obtains to have enough electric conductivities, will make the ratio that adds carbon black be approximately 10-30%.Consequently, the base band of molding has not enough tensile strength, tearing strength, percentage elongation etc.In addition, this band has relatively poor transparency, and this will make the electronic component of confirming to be encapsulated in the base band concave surface become difficult, and feasible the location with optical pickocff is difficult to carry out.

For addressing the above problem, the surface of plastic sheet coating one deck thin contain carbon black (this carbon black be dispersed in binding agent etc. in) thus coating form a conductive layer to guarantee transparency.The result of this processing causes the infiltrative slight raising of light, but not enough, and confirm that the electronic component that is encapsulated in the base band concave surface is still very difficult.The different problem of associated another is that carbon black does not expand with sheet material during method moulding concave surfaces such as deep-draw processes, and this can not obtain desirable electric conductivity.

In addition, have excellent transparency with surfactant by the base band that sheet material forms, but electric conductivity is low, its electric conductivity depends on humidity to a great extent, and this will reduce stable antistatic property.

In recent years, the recycling antistatic container that is used for electronic material is increase trend.When washing and brush the aforesaid antistatic container that contains surfactant for repeated use, surfactant is washed off, thereby has hindered repeated use.

For preventing adhesion, when silicon was applied to thermoplastic resin sheet such as polyester sheet surperficial, silicon can make printability and heat sealability degrade.

The present invention solves these shortcomings of the prior art, and a kind of excellent transparency that has is provided, anti-stick company and under low humidity, in immersing water and after the moulding, have high-anti-static laminated material, it will prevent to produce static in any environment.

This purpose will realize by the present invention who sets forth below.

The present invention is provided below.

(1) a kind of high-antistatic laminated material comprises a base material and a conductive layer at least on one side that is laminated in base material, and described conductive layer comprises conducting polymer and is cured.

(2) as (1) described high-antistatic laminated material, wherein conductive layer further comprises a thermoplastic polymer.

(3) as (1) or (2) described high-antistatic laminated material, wherein conductive layer is to use crosslinking agent to be cured by cross-linking reaction.

(4) as (1) described high-antistatic laminated material, wherein conducting polymer is a kind of conducting polymer of a water-soluble or organic solvent.

(5) as (1) described high-antistatic laminated material, wherein conducting polymer is the polyaniline or derivatives thereof.

(6) as (1) described high-antistatic laminated material, wherein conducting polymer is to contain sulfonic polyaniline or derivatives thereof.

(7) as (1) described high-antistatic laminated material, wherein conducting polymer comprises that the aminobenzenesulfonic acid of alkoxyl replacement is as a polymeric component.

(8) as (1) described high-antistatic laminated material, wherein conducting polymer comprises that amino methoxy benzenesulfonic acid is as a polymeric component.

(9) as (2) described high-antistatic laminated material, wherein thermoplastic polymer is one to have the polyester of a hydrophilic radical.

(10) as (2) described high-antistatic laminated material, wherein thermoplastic polymer is a copolymerization polyester, and this copolyester is one to have the glycol that hydrophilic radical (accounting for the 0.5-15mol% of whole dicarboxylic acids components) dicarboxylic acids and/or has a hydrophilic radical (accounting for the 0.5-15mol% of whole glycol components) and obtain by copolymerization.

(11) as (2) described high-antistatic laminated material, wherein thermoplastic polymer is a grafted polyester, and this grafted polyester is to be aggregated on the polyester by the vinyl monomer-grafted that will have a hydrophilic radical to obtain.

(12) as (3) described high-antistatic laminated material, wherein crosslinking agent is to be selected from a multi-group epoxy compound, one multi-functional isocyanate compound, one polyfunctional group De oxazoline compound, a multi-functional vinyl compound, a multi-functional acyclic compound, one multi-functional carboxylic acid compound, one multi-functional amines, a multi-functional hydroxy compounds, at least a in the multi-functional sulfhydryl compound.

(13) as (1) or (2) described high-antistatic laminated material, wherein conductive layer is that self-crosslinking by conducting polymer and/or thermoplastic polymer is cured.

(14) as (1) described high-antistatic laminated material, wherein conductive layer further comprises a surfactant.

(15) as (1) described high-antistatic laminated material, wherein base material is film or the sheet material of being made by organic resin, and this high-antistatic laminated material has and is not more than 5.0 mist degree.

(16) as (1) described high-antistatic laminated material, wherein base material is by being selected from polyester, Merlon, film or sheet material that a kind of material in polyolefin and the polyurethane is made.

(17) a kind of high-antistatic laminated material comprises a base material and a conductive layer at least on one side that is laminated in base material,

Described conductive layer is at 25 ℃, has under the situation of relative humidity 15% to be not more than 10 ¹¹Sheet resistance (the RS of Ω/ ₀) and at 40 ℃ the high-antistatic laminated material was immersed pure water after one hour, at 25 ℃, the situation lower surface resistance (RS of relative humidity 15% ₁) and RS ₀Ratio (RS ₁/ RS ₀) be not more than 10.

(18) as (17) described high-antistatic laminated material, wherein conductive layer further has one at 25 ℃, relative humidity 15%, the sheet resistance (RS behind the stretching high-antistatic laminated material 150% ₂) and RS ₀Ratio (RS ₂/ RS ₀), it is not more than 10.

(19) as (17) or (18) described high-antistatic laminated material, wherein conductive layer comprises a conducting polymer and is cured.

(20) be used for the container of electronic component, this container is to obtain by the high-antistatic laminated material moulding with above-mentioned (1), (17) or (18).

(21) as (20) described container, this container is a pallet.

(22) be used for the base band of electronic component, this base band is to obtain by the high-antistatic laminated material moulding with above-mentioned (1), (17) or (18).

(23) be used for the pallet of electronic component, this pallet is obtained by the moulding of high-antistatic laminated material that comprises a base material and be laminated in a conductive layer at least on one side of base material, and this pallet comprises a concave surface and a flange at its external margin,

Sheet resistance (the RS of the conductive layer of wherein said flange ₃) at 25 ℃, have under the situation of relative humidity 15% and be not more than 10 ¹¹Ω/ immerses pure water after one hour at 40 ℃ with pallet, at 25 ℃, and the situation lower surface resistance (RS of relative humidity 15% ₄) and RS ₃Ratio (RS ₄/ RS ₃) be not more than 10 and have the conductive layer concave surface of the 0.5-0.7 that is equivalent to thickness of flange, at 25 ℃, the sheet resistance (RS under the situation of relative humidity 15% ₅) and RS ₃Ratio (RS ₅/ RS ₃) be not more than 100.

(24) as (23) the described pallet that is used for electronic component, this pallet is by be shaped (1), and (17) or (18) described high-antistatic laminated material obtains.

(25) be used for the base band of electronic component, this band is to comprise that by shaping a base material and the high-antistatic laminated material of a conductive layer at least on one side that is laminated in base material obtain, the base band comprises a plurality of concave surface and the flanges on its excircle that are used for encapsulating electronic components that longitudinally distribute

Sheet resistance (the RS of its flange conductive layer ₆) at 25 ℃, have under the situation of relative humidity 15% and be not more than 10 ¹¹Ω/, the pure water that in the time of 40 ℃ the base band is immersed be after one hour, at 25 ℃, and the sheet resistance (RS of the situation lower flange conductive layer of relative humidity 15% ₇) and RS ₆Ratio (RS ₇/ RS ₆) be not more than 10 and at 25 ℃, have the sheet resistance (RS of the concave part that is equivalent to the thick conductive layer of flange portion thickness 0.5-0.7 under the situation of relative humidity 15% ₈) and RS ₆Ratio (RS ₈/ RS ₆) be not more than 100.

(26) as (25) the described base band that is used for electronic component, by being shaped as (1), (17) or (18) described high-antistatic laminated material acquisition.

(27) comprise the amortizing packaging material that is used to transport packaged goods of a container and a pair of stretched PTFE film, described stretched PTFE film has a pair of relative end that is installed on the container, wherein said stretched PTFE film is selected from by above-mentioned (1), the part that the high-antistatic laminated material of (17) and (18) is formed.

(28) one by above-mentioned (1), and (17) or (18) described high-antistatic laminated material is as the IC-card of the base material acquisition of card.

What Fig. 1 showed is the embodiment of an amortizing packaging material of the present invention, and wherein 1 is a container, the 2nd, and the high-antistatic laminated material, the 3rd, packaged goods, 4 is that a cover and 5 is frameworks.

Describe the present invention below in detail.

High-antistatic laminated material of the present invention comprises that base material and is laminated in the conductive layer of this base material at least on one side.

The present invention does not do special the qualification to the type of base material, and inorganic substrate and/or organic substrate all can use.The example of inorganic substrate comprises by metal material such as steel, aluminium, and the base material that stainless steel etc. are made, by silica, aluminium, inorganic polymer material that titanium etc. obtain the Alkolate hydrolysis or the like.The example of organic substrate comprises single layer of substrate material or the multi-layer substrate that is made by one or more thermoplastic resin materials, this thermoplastic resin such as polyester, nylon (as nylon-6, nylon-66 etc.), polyolefin is (as polypropylene, polyethylene, polymethylpentene etc.), polystyrene, polyvinyl chloride, polyurethane, the base material that Merlon etc. and are made by thermosetting resin etc.In above-mentioned thermoplastic resin material, what preferably use is polyester, Merlon, polyolefin and polyurethane.Also can use the base material of making by the composite material of above-mentioned inorganic material and organic material.

Above-mentioned base material preferably has planar structure such as film, sheet material etc.For example, can use polyester film or sheet material, steel band, aluminium strip, stainless steel band etc.

Concentrate below polyester film or sheet material are described as base material, the base material of high-antistatic laminated material of the present invention is not limited to polyester film or sheet material.The polyester of indication is a polymer herein, is mainly obtained by an aliphatic and/or aromatic dicarboxylic acid component and an aliphatic and/or aromatic diol component.For example, comprising homopolymers such as PET (PET), PEN (PEN), terephthaldehyde's acid constituents obtains dicarboxylic acids component such as phthalic acid, M-phthalic acid among the PET by partially or completely being replaced by one or more dicarboxylic acids components for they, adipic acid, biphenyl carboxylic acids, diphenyl ether dicarboxylate, decanedioic acid, naphthalenedicarboxylic acid etc., the naphthalenedicarboxylic acid component obtains dicarboxylic acids component such as terephthalic acid (TPA) among the PEN by partially or completely being replaced by one or more dicarboxylic acids components for they, phthalic acid, M-phthalic acid, adipic acid, biphenyl carboxylic acids, diphenyl ether dicarboxylate, decanedioic acid, etc., they partially or completely replace with one or more dihydroxylic alcohols components, and the ethylene glycol component obtains among PET and/or the PEN, dihydroxylic alcohols component such as diethylene glycol (DEG), triethylene glycol, 1, the 6-hexylene glycol, propane diols, cyclohexanol, neopentyl glycol, butanediol, 1, ammediol etc.

This polyester sheet or film also can contain just like silica, talcum, calcium carbonate, aluminium oxide, silicated aluminum, titanium dioxide, zeolite, organic or inorganic lubricants such as granules of polystyrene.From the angle of transparency, preferably use a spot of lubricant, its consumption depends on the particle size of lubricant.Usually, the average particle size particle size of preferred lubricant is not more than 5 microns, more preferably is not more than 2 microns, and addition preferably is not more than 5000ppm, more preferably is not more than 3000ppm.In addition, as long as the inherent characteristic of polymer is unaffected, can add additive, UV absorbent, stabilizing agent or pigment.

In the present invention, one is conductive layer-laminated on one side at least of aforesaid base material, and wherein conductive layer comprises a conducting polymer and is cured.Since the effect of the conducting polymer that adds, thereby can produce electric conductivity, and particularly the antistatic property under the low humidity situation can be improved.

Conducting polymer is not done special the qualification in the present invention, but can use conducting polymer with π-electron conjugated structure, as polyaniline, polypyrrole, polythiophene, and derivative, and the conducting polymer that preferably provides can be dissolved or dispersed in a water or the organic solvent, water particularly, conducting polymer is dissolved or dispersed in by means of adulterant in a water or the organic solvent.

The example of such conducting polymer comprises polyaniline and its copolymer, they are by means of adulterant dissolving or dispersion, as inorganic acid (hydrochloric acid, perchloric acid, sulfuric acid etc.), the compound (as benzene sulfonic acid, naphthalene sulfonic acids, polystyrolsulfon acid (polystylenesulfonic acid) etc.) that contains sulfonic acid group; The polyaniline of sulfonation, wherein one or more hydrogen atoms of the part or all of phenyl ring of polyaniline are replaced by sulfonic group; The polypyrrole of chain alkyl keyed jointing or polythiophene; And derivative.In the present invention, the polyaniline of sulfonation and polyaniline and derivative thereof are by adulterant dissolving, and this adulterant is aforesaid acid compound, is particularly preferred.

Below will the polyaniline that be used for sulfonation of the present invention be described in detail.The polyaniline of sulfonation be a polymer wherein in the polyaniline partly or entirely the one or more hydrogen atoms in the phenyl ring replaced by sulfonic group and its structure is not particularly limited.Its example comprises the sulfonated polyaniline that obtained by polyaniline and controlled sulfuric acid sulfonation and by aminobenzenesulfonic acid separately or the polyaniline of the sulfonation that forms with other aniline polymerization.In the present invention, the sulfonated polyaniline of back is preferred, and can be used as aminobenzenesulfonic acid, aminobenzenesulfonic acid and particularly preferred amino methoxy benzenesulfonic acid that alkoxyl replaces.

The example of amino methoxy benzenesulfonic acid comprises 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole-2-sulfonic acid, 4-aminoanisole-3-sulfonic acid, etc.Also can use a compound by the methoxyl group in the alternative above-mentioned amino methoxy benzenesulfonic acid of other alkoxyl (as ethyoxyl, isopropoxy etc.).In the above-mentioned amino methoxy benzenesulfonic acid, the amino methoxybenzene of 2--3-sulfonic acid preferably, the amino methoxybenzene of 2--4-sulfonic acid, the amino methoxybenzene of 2--5-sulfonic acid, the amino methoxybenzene of 2--6-sulfonic acid, the amino methoxybenzene of 3--2-sulfonic acid, the amino methoxybenzene of 3--4-sulfonic acid, the amino methoxybenzene of 3--6-sulfonic acid.

About the polyaniline of the sulfonation used among the present invention, sulfonic content preferably is no less than the 70mol% of phenyl ring amount, and the preferred 80mol% that is no less than is preferably 100mol% especially.It is possible containing sulfonic phenyl ring and not having sulfonic phenyl ring to occur simultaneously or alternately arrange.When sulfonic content is lower than 70mol%, the polyaniline of sulfonation is at water, it is not enough that solvability in ethanol or the mixed solvent and dispersibility can become, and its result causes the electric conductivity of the coating layer of bad coating performance and extension performance on base material and acquisition to reduce sharp.

The number-average molecular weight of the polyaniline of the sulfonation that the present invention uses is preferably 300-500000, and for the intensity of solvability in the solvent and coating layer, it is particularly preferred wherein being not less than 10000 for aforesaid.Have the polyaniline of low-molecular-weight sulfonation and derivative thereof can with a compound polymerization, this compound has groups two or more and amino reaction, as can using diepoxides, diisocyanate cpd, etc.

For the polyaniline of coating sulfonation on base material, coating solution is prepared by predetermined solvent.With respect to the solvent of 100 weight portions, contain the polyaniline of 0.01-10 weight portion sulfonation and more preferably contain the 0.1-2 weight portion in the preferred solution.When the consumption of the polyaniline of sulfonation was less than 0.01 weight portion, the longer-term storage of solution was relatively poor.Consequently, can pin hole on coating layer, occur and make coating layer have extremely low electric conductivity.When its consumption surpasses 10 weight portions, the polyaniline of sulfonation in water or in water/organic solvent solvability and dispersibility and the coating performance of base material trended towards degenerating, and this is worthless.

Above-mentioned solvent can be any, as long as it does not make as the dissolving of base materials such as polyester film or expands.Preferred solvent is Shui Heshui/organic solvent such as ethanol mixed solvent, consider environment for use and the coating performance that therefore causes and the raising of electric conductivity.

Organic solvent is alcohol preferably, as methyl alcohol, and ethanol, propyl alcohol, isopropyl alcohol etc., ketone such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK), cellosolve such as methyl cellosolve, ethyl cellosolve etc., propane diols such as methyl propanediol, ethyl glycol etc., acid amides such as dimethyl formamide, dimethylacetylamide etc., pyrrolidones such as N-methyl pyrrolidone, N-ethyl pyrrolidone etc., they mix use with water with arbitrary proportion.

Typical example comprises water/methyl alcohol, water/ethanol, water/propyl alcohol, water/isopropyl alcohol, water/methyl propanediol, water/ethyl glycol etc.Preferred ratio is water/organic solvent=1/10-10/1.

From with the caking property of base material, ductility and intensity see that conductive layer preferably contains thermoplastic polymer except containing the conducting polymer beyond the region of objective existence.Be used for thermoplastic polymer of the present invention and comprise thermoplastic polymer such as polyester, polyamide (as nylon, aromatic polyamides etc.), polyolefin is (as polyethylene, polypropylene etc.), polyvinyl chloride, polyurethane, polyamide-imides, polyimides etc. are not particularly limited its type.Consider the dispersive property in water, preferred thermoplastic of the present invention has a hydrophilic radical.Hydrophilic radical demonstrates the affinity with water, and this is by as sulfonic group, carboxyl, and the acidic-group of phosphate etc., the alkali metal salt group, the ammonium salt group, amino group and hydroxyl prove.Also can use thermoplastic polymer and this polymer is changed into the thermoplastic polymer with hydrophilic radical with the group that can change into hydrophilic radical.The group that can change into hydrophilic radical is, as ester group, and amide groups, acid anhydrides, glycidyl, cyano group, chloro etc.

The aqueous dispersion of above-mentioned thermoplastic polymer can be dispersed in the water by dissolving one thermoplastic polymer in a water-soluble organic compound that suits and with solution and obtain.For example, the thermoplastic polymer with hydrophilic radical preferably mixes with water-soluble organic compound under 50 ℃ of-200 ℃ of temperature and dissolves, and adds entry then and stirs so that its dispersion; Or mixture is added to the water and stirs the mixture so that its dispersion; Or under 40-120 ℃ of temperature, in the presence of water-soluble organic compound, in water, stir thermoplastic polymer with hydrophilic radical.

Above-mentioned water-soluble organic compound is in the time of 20 ℃, and the solubility in water is no less than 20g/l, is typically fat or alicyclic ring alcohol, ether, ester, ketone etc.Such example comprises monohydric alcohol such as methyl alcohol, ethanol, isopropyl alcohol, n-butanol etc.; Glycol such as ethylene glycol, propane diols etc.; Diol, derivatives such as methyl cellosolve, ethyl cellosolve, normal-butyl cellosolve etc.; Ether such as diox, oxolane etc.; Ester such as acetate etc.; Ketone such as methyl ethyl ketone etc.These organic compounds can be used alone or as a mixture.Consider in water dispersive property and during to the coating performance of base material, above-mentioned water-soluble organic compound, isopropyl alcohol, normal-butyl cellosolve and ethyl cellosolve are preferred.

In the present invention, consider that from electric conductivity the polyester that preferably will contain hydrophilic radical uses as thermoplastic polymer.Hydrophilic radical is introduced in polyester, by for example, with polyester and controlled sulfuric acid (con.sulfuricacid) thus sulfonic group is introduced in reaction, or with the monomer that hydrophilic radical is arranged as the copolymerization component, for ease of producing the preferred latter's method.

The polyester that the present invention preferably contains hydrophilic radical is a water-insoluble basically copolyester, it is to obtain by the glycol polymerisation that will have and not have the dicarboxylic acids of hydrophilic radical and/or be with or without hydrophilic radical, dicarboxylic acids content with hydrophilic radical part is 0.5-15mol%, the dicarboxylic acids content that does not contain the hydrophilic radical part is 85-99.5mol%, the content of the two all is the total amount of relative dicarboxylic acids, glycol content with hydrophilic radical part is 0.5-15mol%, the glycol content that does not contain hydrophilic radical part is 85-99.5mol%, and the content of the two all is the total amount of relative glycol.When the dicarboxylic acids with hydrophilic radical part and/or glycol content surpass 15mol%, copolyester has low anti-art, yet when it was less than 0.5mol%, copolyester was difficult for disperseing in water, and consequently aqueous dispersion can not be applied on the base material easily.

In the present invention, hydrophilic radical particularly preferably is the metal organic sulfonate group, and in the case, the dicarboxylic acids that contains the metal organic sulfonate group is preferably as the monomer original material.The example that contains the dicarboxylic acids of metal organic sulfonate group comprises the sulfo group terephthalic acid (TPA), the 5-sulfoisophthalic acid, 4-sulfo group phthalic acid, 4-sulfo group naphthalene-2,7 dicarboxylic acids, the slaine of 5-(4-sulfophenoxy) M-phthalic acid etc., what especially preferably provide is 5-sulfoisophthalic acid sodium and sulfo group para-phthalic sodium.These contain the total amount of the dicarboxylic acid component of metal organic sulfonate group for the dicarboxylic acid component, and preferred content is 0.5-15mol%, particularly preferred 2.0-10mol%.

But the copolymerization component is depended in the variation of the dispersibility of above-mentioned polyester in water, as the kind and the mixed proportion of water-soluble organic compound of solvent etc.In order to obtain the purpose of better resistance to water, as long as the dispersibility in water is not weakened, the content of preferred hydrophilic radical is little.

The above-mentioned dicarboxylic acids that does not contain the polyester of hydrophilic radical can be an aromatics, aliphatic series or alicyclic dicarboxylic acid.Terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid etc. can be used as aromatic dicarboxylic acid and uses.The content of preferred aromatic dicarboxylic acids in total dicarboxylic acid component is not less than 40mol%.When being less than 40mol%, polyester has lower mechanical strength and resistance to water.Aliphatic series or alicyclic dicarboxylic acid's example comprises butanedioic acid, adipic acid, decanedioic acid, 1,3-pentamethylene dicarboxylic acids, 1,2-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid etc.

The diol component of above-mentioned polyester mainly is the aliphatic diol with 2-8 carbon atom, for example can make spent glycol, 1, ammediol, propane diols, 1, the 4-butanediol, neopentyl glycol, 1, the 6-hexylene glycol, 1,2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, the paraxylene glycol, diethylene glycol (DEG), triethylene glycol etc.Polyethers such as polyethylene glycol, polypropylene glycol, poly-tetramethylene glycol etc. also can use.In addition, but but copolymerization oxidation carboxyl acid component as to oxidation ethoxybenzoic acid and copolymerization dicarboxylic acids and/or contain a spot of amido link, urethane bonds, ehter bond, the diol component of carbonic acid key etc.

The above-mentioned polyester that contains hydrophilic radical is that above-mentioned dicarboxylic acid component and above-mentioned diol component pass through ester exchange reaction, and polycondensation reaction etc. obtain according to conventional method.The polyester that contains hydrophilic radical that is obtained is heated and with the stirrings such as solvent as the normal-butyl cellosolve, forms the aqueous solution or aqueous dispersion thereby add entry then and stir.

In the present invention, grafted polyester is, by the vinyl monomer (it is the polymeric component of a branched polymer) that will have a hydrophilic radical, glycerol polymerization obtains to the side chain of (being a kind of trunk polymer) polyester, and this polyester also can be used as thermoplastic polymer and uses.Use the result of this polymer to improve transparency, with the cohesive and the durability of base material.

The vinyl monomer with hydrophilic radical that can be grafted on the polyester can be to have carboxyl, sulfonic group, alkali metal alkali, the ammonium salt base, hydroxyl, the vinyl monomer of amide groups etc., and vinyl monomer has the group that can change into hydrophilic radical, as ester group, amide groups, anhydride group, glycidyl, chloro, itrile group etc.Wherein, the vinyl monomer with carboxyl or its alkali metal alkali or its ammonium salt base is most preferred.

Its example comprises the monomer with carboxyl or its alkali, as acrylic acid, and methacrylic acid, its alkali metal salt, its ammonium salt; Alkyl acrylate such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate etc.; Alkyl methacrylate such as methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, metering system tert-butyl acrylate etc.; The monomer such as the 2-hydroxy ethyl methacrylate that contain hydroxyl, 2-hydroxyethyl meth acrylate etc.The monomer such as the acrylamide that contain acid amides, Methacrylamide, N methacrylamide, N-methyl acrylamide, N hydroxymethyl acrylamide, the N-methylol methacrylamide, N-methoxy acrylamide, N-methoxy Methacrylamide, N, N-dihydroxymethyl acrylamide, N phenyl acrylamide etc.; The monomer such as the glycidyl acrylate that contain epoxy, GMA etc.; Or the like.

Other example with hydrophilic radical monomer is to contain the monomer of epoxy such as arylolycidyl ethers etc., contains the monomer of sulfonic group or its alkali, as styrene sulfonic acid, and vinyl sulfonic acid and its salt etc.; The monomer that contains carboxyl or its ester group, as crotonic acid, itaconic acid, maleic acid, fumaric acid and its salt; With monomer that contains acid anhydrides such as anhydrous maleic acid, anhydrous itaconic acid etc.

They can use simultaneously with other monomer.The example of other monomer comprises vinyl isocyanate, aromatic radical isocyanates, styrene, vinyl methyl ether, EVE, acrylonitrile, methacrylonitrile, vinylidene chloride, vinylacetate, vinyl chloride etc.One or more can be by copolymerization in them.Mol ratio with the monomer of hydrophilic radical and other monomer is 30/70-100/0 preferably.When the ratio of the vinyl monomer with hydrophilic radical was less than 30mol%, coating layer can not have enough transparencies.

Polyester (in dicarboxylic acid component) can be an aromatics, aliphatic series or alicyclic dicarboxylic acid.The example of aromatic dicarboxylic acid comprises terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid etc.The content of preferred these aromatic dicarboxylic acids is not less than the 40mol% of total dicarboxylic acids content.When being less than 40mol%, grafted polyester may have low mechanical strength and resistance to water.Aliphatic series and alicyclic dicarboxylic acid can be butanedioic acids, adipic acid, decanedioic acid, 1,3-pentamethylene dicarboxylic acids, 1,2-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid etc.As diol component, the main aliphatic diol with 2-8 carbon atom that uses is meant ethylene glycol, 1 especially, ammediol, propane diols, 1,4-butanediol, neopentyl glycol, 1, the 6-hexylene glycol, 1,2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, terephthalyl alcohol, diethylene glycol (DEG), triethylene glycol etc.In addition, polyethers such as polyethylene glycol, polypropylene glycol, poly-tetramethylene glycol etc. also can use.In addition, the hydroxycarboxylic acid component, but as can copolymerization to the dicarboxylic acids of '-hydroxyethoxy yl benzoic acid and copolymerization and/or contain a spot of amido link, urethane bonds, ehter bond, the diol component of carbonic acid key etc.

Vinyl monomer with a hydrophilic radical can be grafted on the polyester by the method for known glycerol polymerization.Its typical example is as follows.

For example, can use wherein light of radical polymerization, heat, irradiation etc. is used for producing free radical at polyester, and polyester is a kind of trunk polymer, and vinyl monomer is by glycerol polymerization; Cationic polymerization is AlCl wherein ₃, TiCl ₄Deng be as produce that cationic catalyst uses and vinyl monomer by glycerol polymerization; Metal Na is wherein used in anionic polymerisation, and metal Li etc. to be producing anion and vinyl monomer by glycerol polymerization, etc.

In addition, comprise the method that in polyester (it is a kind of trunk polymer), imports polymerisable unsaturated double-bond and react with vinyl monomer.Monomer with polymerisable unsaturated double-bond can be a fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 2,5-norbornene dicarboxylic acids and its acid anhydrides, anhydrous tetrahydrophthalic acid etc.Wherein, fumaric acid most preferably, maleic acid and 2,5-norbornene dicarboxylic acids.

In addition, can use a kind of method, this method is the polyester (a kind of trunk polymer) and branched polymer reaction that will have functional group on side chain, and this branched polymer has the group that at one end reacts with above-mentioned functional group.For example, on side chain, have the polyester of an active hydrogen, as-OH ,-SH ,-NH ₂,-COOH ,-CONH ₂Deng and have the polyvinyl that a hydrogen is accepted base at the other end, as-N=C=O ,-C=C=O, epoxy radicals, glycidyl, cured ethylene group etc., reaction, or reaction is what to finish under opposite combining form.

In the present invention, employed polyester (a kind of trunk polymer) and be used for the weight ratio 40/60-95/5 preferably of the vinyl monomer of grafting, more preferably 55/45-93/7 particularly preferably is 60/40-90/10.When the weight ratio of polyester less than 40% the time, the vinyl monomer reaction not exclusively and residue can destroy the characteristic that common polyester has, as hear resistance, processability etc.On the contrary, when it surpasses 95%, improved conductance and transparency, this also is a purpose of the present invention, but can not realize fully sometimes.

In order to improve the case hardness of conductive layer, the monomer that contains many carboxyls, as three benzene hexacarboxylic acids, 1,3, the 5-benzenetricarboxylic acid, PMA, anhydrous three benzene hexacarboxylic acids, anhydrous PMA etc., can use, its consumption is not more than the 5mol% as the polymerizable components of above-mentioned polyester that contains hydrophilic radical and grafted polyester.When its content surpasses 5mol%, the polymer that the is obtained thermally labile that may become, gel easily is not preferred as the component of conductive layer of the present invention.

Above-mentioned back a kind of method, when thermoplastic polymer had the ability to carry out self-crosslinking, the cross-linking reaction group was directed in this thermoplastic polymer.The example of crosslinking reactive group comprises, acryloyl group, vinyl, epoxy radicals, NCO ， oxazolinyl, silanol groups, acid chloride, carboxyl, amino, hydroxyl, sulfydryl etc.These cross-linking reaction groups are to be imported into by the polymeric component that polymerization contains the cross-linking reaction group.For example, when thermoplastic polymer is above-mentioned when containing the polyester of hydrophilic radical, have of dicarboxylic acid component and/or the diol component use of the monomer of crosslinking reactive group as polyester, when being above-mentioned grafted polyester when thermoplastic polymer, the monomer with crosslinking reactive group uses as the dicarboxylic acid component of polyester and/or diol component or monomer with crosslinking reactive group uses as vinyl monomer.

The content of above-mentioned thermoplastic polymer is not done special restriction simultaneously, consider the electric conductivity and the mechanical performance of the conductive layer that is obtained, for the conducting polymer of 100 weight portions such as the polyaniline of sulfonation etc., 50-2000 weight portion preferably, more preferably 100-1500 weight portion, most preferably 200-1000 weight portion.

High-antistatic laminated material of the present invention need comprise a conductive layer that solidifies, and this is because three-dimensional cross-linked effect has improved the resistance to water of conductive layer and behind the dipping, suppressed the reduction of antistatic property in water.Crosslinked method comprises the method for using crosslinking agent, by importing the self-crosslinking method of crosslinking reactive group to conducting polymer and/or thermoplastic polymer, and by the method for heating or crosslinking with radiation conducting polymer and/or thermoplastic polymer, etc.

Crosslinking agent used in the present invention can be a compound; this compound has in a molecule; two or more reactive groups are (as acryloyl group; vinyl; epoxy radicals, NCO ， oxazolinyl; silanol groups; acid chloride, carboxyl, amino; hydroxyl; sulfydryls etc.), or the compound that under usual conditions, in solvent, does not react but, after pH regulates and handles etc. by heat treated as water etc.; have; in a molecule, groups such as two or more new lives' above-mentioned reactive group such as NCO, thus this will make intermolecular self-crosslinking have the ability tridimensional network himself is taking place to form; or have the ability and have the organic compound of active hydrogen, have the inorganic compound of active hydrogen or have active hydrogen polymers compositions (can be above-mentioned conducting polymer or thermoplastic polymer) thus reaction formation cross-bond.The example of these compounds comprises, multi-functional vinyl compound, multi-functional acyclic compound, multi-functional epoxide, multi-functional isocyanate compound, polyfunctional group De oxazoline compound, multi-functional carboxylic acid compound, multi-functional amines, multi-functional hydroxy compounds, multi-functional sulfhydryl compound etc.

The example of multi-functional epoxide comprises with the bis phenol-a epoxy resins of bisphenol-A as original material, the sorbierite polyglycidyl ether, the polyglycereol polyglycidyl ether, the pentaerythrite polyglycidyl ether, diglycerol polyglycidyl ether, glycerine polyglycidyl ether, triglycidyl group three (2-ethoxy) isocyanuric acid ester, the trimethylolpropane polyglycidyl ether, resorcinolformaldehyde resin, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, bisphenol-S diglycidyl ether, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, propylene glycol diglycidylether, poly-1, the 4-butanediol diglycidyl ether, fatty acid glycidyl ester, O-phthalic acid glycidyl ester, dibromoneopentyl glycol diglycidyl ether etc.

Except with the conducting polymer of common appearance and/or thermoplastic polymer reaction, above-mentioned multi-functional epoxide can with the compound reaction with active hydrogen.This compound can be, for example, aliphatic series polyaniline such as diethylenetriamines, trien, tetren, polyoxy propylidene polyamine, triethylene glycol diamine, tetraethyl glycol two peaces etc., cyclic polyamines such as dimethylphenylene diamine, spiral acetal diamines, IPD, two (3-methyl-4-aminocyclohexyl) methane etc., aromatic polyamine such as benzidine methane, benzidine sulfone etc., the amine of modification is as having the polyaminoamide of many active aminos in the synthetic molecules by polyamine and dicarboxylic acids polycondensation, the amine adduct curing agent, Manny phase curing agent etc., etc.

Multi-functional isocyanate compound is, as, thermal response water soluble amino Ethyl formate resin, ELASTRON (trade mark is produced by Daiichi Kogyo Seiyaku) etc.This is that the wherein terminal isocyanates of a kind of urethane resin that reacts is protected by inhibitor, so that it carries out stable treated in water.As the inhibitor that is used for ELASTRON, can use to have the sulfonation of being called carbamoyl (NHCOSO ₃-) the compound of strong hydrophilicity group.ELASTRON demonstrates with the dissociation of inhibitor under certain heat-treat condition and makes active isocyanate regeneration.Specifically, it can be not more than under 100 ℃ the situation predrying and carry out the heat treatment of a few minutes at 120 ℃-170 ℃, because the palingenesis of isocyanates makes ELASTRON at himself intermolecular self-crosslinking, thereby produces the polyurethane coated film with tridimensional network.When the different compounds that contains active hydrogen mixes with ELASTRON and heats, compound is owing to crosslinked effect has been enhanced.For example, polyvinyl alcohol mixes with ELASTRON and heat-treats, and therefore has identical resistance to water.

For example, the polyfunctional group vinyl compound comprises polybutadiene and isoprene.

For example, the polyfunctional group acyclic compound comprises ARONIX (trade mark, by TOA GOSEICO., LTD. produce), concrete example is by Bisphenol F EO-modification (4 moles) diacrylates (M-208), bisphenol-A EO-modification (4 moles) diacrylates (M-210), cyamelide EO-modification diacrylate (M-215), tripropylene glycol diacrylate (M-220), polypropyleneglycol diacrylate (n=ca, 7, PFG#400, M-225), pentaerythritol diacrylate monostearate (M-233), polyethyleneglycol diacrylate (n=ca, 4, PPG#200, M-240), polyethyleneglycol diacrylate (n=ca, 9, PPG#400, M-245) polyethyleneglycol diacrylate (n=ca, 13-14, PPG#600, M-260) polypropyleneglycol diacrylate (n=ca, 12, M-270), pentaerythritol triacrylate (M-305), trimethylolpropane triacrylate (M-309), trimethylolpropane PO-modification (3 moles) triacrylates (M-310), cyamelide EO-modification triacrylate (M-315), trimethylolpropane PO-modification (6 moles) triacrylates (M-320), trimethylolpropane EO-modification (3 moles) triacrylates (M-350), trimethylolpropane EO-modification (6 moles) triacrylates (M-360), dipentaerythritol five-and six-acrylate (M-400), two trimethylolpropane tetra-acrylate (M-408), pentaerythritol tetracrylate (M-450), urethanes acrylate (M-1100), and polyester acrylate (M-7000 series, M-8000 series, M-7100, M-8060).

For example, polyfunctional group De oxazoline compound comprises epocross (trade mark, by NIPPONSYOKUBAIKOGYO CO., LTDSH produces).

For example, multi-functional carboxylic acid compound comprises anhydrous benzenetricarboxylic acid, anhydrous PMA, benzenetricarboxylic acid etc.

For example, multi-functional amines comprises VARSAMINE and VARSAMID (trade mark is produced by Henkel Japan Ltd.).

For example, the polyfunctional group hydroxy compounds comprises polyvinyl alcohol, PPG, PEPA, acrylic polyol, PCDL, trimethylolethane, trimethylolpropane, glycerine, pentaerythrite etc.

For example, multi-functional sulfhydryl compound comprises 1 of triethyl group cyclohexane modification, ammediol etc.

Above-mentioned crosslinking agent can be any as long as it is stable and can be dissolved in the solution that is used for the moulding conductive layer.In the middle of these, multi-group epoxy compound and many functional group isocyanates's compound, particularly, can dissolve also in water is that stable moisture many functional group isocyanates's compound is preferred therein.

The above-mentioned compound that contains the polyfunctional group reactive group can comprise the mono-vinyl compound, single acyclic compound, mono-epoxy compounds, monoisocyanates compound ， Dan oxazoline compound, the monocarboxylic acid compound, monoamine compound, single hydroxy compound, single sulfhydryl compound etc.

When conducting polymer and/or the capable self-crosslinking of thermoplastic polymer, these polymer need have crosslinking reactive group.The example of crosslinking reactive group comprises acrylic, vinyl, epoxy radicals, NCO ， oxazolinyl, silanol groups, acid chloride, carboxyl, amino, hydroxyl, sulfydryl etc.

When laminated material of the present invention is used for the container (particularly pallet) that moulding is used for electronic component, pallet is in that to repeat to wash the back with water reusable.By crosslinked, can avoid making the reduction of antistatic property, and be got rid of at an easy rate at the water that is attached to after the washing on the pallet owing to washing.Because the dry time can be effectively shortened in crosslinked caused curing, because conductive layer is attached with a spot of water and does not rise greatly after washing.In addition, make the dust that adheres to reduce and reduce the damage of pallet by washing.

On the other hand, in the case by crosslinked and be cured local stone so that when the high-antistatic laminated material when processes such as processing are stretched, thereby conductive layer not along with stretching in the decline of the antistatic property at stretching position.Therefore, crosslinking curing should reach skin resistance and is no more than 150% o'clock 10 times of stretching.

When conductive layer contains the polyethylene glycol component, make stretch capability become very good.Polyethylene glycol can be contained separately, but or use as the copolyester component of above-mentioned polyester that contains hydrophilic radical or grafted polyester, or be blended in the branched polymer of above-mentioned grafted polyester.

In the present invention, conductive layer can be formed on the base material with any method, as comprise the extrusion by melting that the composition of conductive layer is carried out fusion, said composition contains conducting polymer, thermoplastic polymer can contain crosslinking agent etc. on the ground of needs, through a head extrusion melt material that is fit to, and coating process, thereby being included in, this method disperses in water or the suitable organic solvent and the dissolving above-mentioned composition precasts coating liquid and this coating liquid is applied on the base material.A kind of method in back is preferred, because thin and its thickness that the thickness of coating layer can be done can be controlled, the laminated material that is obtained has good transparency.

When conductive layer is when being formed by coating process, can use the coating liquid that makes by above-mentioned composition to obtain high-antistatic laminated material of the present invention., above-mentioned composition preferably also contains surfactant, because can avoid occurring in the contraction in the coating, inhomogeneous grade also improves the coating ability.

No matter the surfactant that the present invention uses can it be ion or non-ionic, for example, fluorine surfactant such as fluoroalkyl carboxylic acid, perfluorinated substituted carboxylic acids, full-fluorinated benzene sulfonic acid, perfluoro quaternary ammonium compound, perfluoro polyethylene glycol oxide ethanol etc.; With non-ionic surface active agent such as polyoxyethylene octylphenyl ether, polyethylene oxide alkyl ethers, polyethylene glycol oxide fatty acid esters of sorbitan etc. can preferably use.

When conducting polymer be water-soluble or the aqueous dispersion conducting polymer as when being dissolved in or being scattered in the polyaniline in the water, preferably using non-ionic surface active agent by adulterant (as the polyaniline of sulfonation).

The amount of the surfactant that the present invention uses 0.001-10 weight portion preferably for the conducting polymer of per 100 weight portions such as the polyaniline of sulfonation etc.When the consumption of surfactant surpasses 10 weight portions, overlapping or when reeling, conductive layer can contact with the back side of base material when the high-antistatic laminated material, surfactant can be transferred to the back side of base material, this will be easy to carrying out as lamination, the deposition, the printing etc. secondary operations the time have problems.

The sliding capability of the laminated material that obtains in order to improve, the above-mentioned composition that is used for conductive layer may further include fatty acid metal salts and torpescence particulate.

The fatty acid metal salts that the present invention uses comprises montanic acid sodium, montanic acid calcium, melissic acid sodium, enuatrol, odium stearate, sodium palmitate, sodium laurate, Sodium myristate (sodium myristate) etc., what preferably provide is alkali metal salt and alkali salt and particularly preferably is sodium salt.

The torpescence particulate that the present invention uses comprises inorganic particles such as titanium dioxide (TiO ₂), silica (SiO ₂), calcium carbonate (CaCO ₃), aluminium oxide (Al ₂O ₃), barium sulfate (BaSO ₄), zinc oxide (ZnO), talcum, mica, complex compound particulate etc.; Organic fine particles comprises polystyrene, polyacrylate, and their cross-linking compounds, etc.Consider that from the transparency of coating layer the preferred average initial particle size of these particulates is not more than 0.2 micron.In addition, in order to obtain the 1000ppm that its preferred addition of required transparency is not more than the conductive layer combination thing.

In order further to improve the electric conductivity of conductive layer, SnO ₂(tin oxide) or ZnO (zinc oxide) powder, or inorganic particles or organic fine particles are as TiO ₂, BaSO ₄Deng coating in an identical manner; Coating or lamination have conducting polymer such as polyaniline, the polyaniline of sulfonation, and polypyrrole, soluble polypyrrole, the carbonaceous conductive filler of polythiophene etc., as carbon black, graphite, carbon fiber etc.; Or inorganic or organic fine particles all can add.From the angle of transparency, the preferred average initial particle size of particulate is not more than 0.2 micron.The preferred amount that adds such as the conducting polymer of above-mentioned additive 100 weight portions such as the polyaniline of sulfonation is not more than 4000 weight portions.When it surpasses 4000, cause the decline of the even transparency of crawling owing to the viscosity increase of coating liquid.

Under dry weight, the amount that is applied to base material is 0.01-6.0g/m preferably ²When coating weight is lower than 0.01g/m ²The time, the electric conductivity deficiency that is obtained.On the contrary, surpass 6.0g/m when its consumption ²The time, adhesive property reduces.

The grooved roll rubbing method, contrary roller rubbing method, the scraper rubbing method, the dipping method, method of spin coating, spraying process etc. all are used in the base material conductive layer that particularly is shaped on thermoplastic resin sheet and the film.There is no particular limitation to be suitable for the coating process of electrically conductive composition.Have a kind of line painting method be in film forms process, apply coating after film is shaped processing, apply coating with a kind of off-line coating process separately.Method to preferred use is not done special qualification in the choice.

The conducting polymer that the present invention uses, particularly, the polyaniline of sulfonation is unsettled and be stable in about three minutes 200 ℃ of heat treatments when high temperature promptly is not less than 250 ℃.Therefore, in the time of 200 ℃, heat in short-term usually and can not be harmful to electric conductivity, although stood change, the kind of the thermoplastic polymer and the additive of coexistence is depended in this change, but still the antistatic property that has kept transparency to become reconciled has sufficiently high surface strength simultaneously.

When base material is organic substrate, can implement sided corona treatment, sided corona treatment under nitrogen environment or ultraviolet ray irradiation, or before base material, forming a priming coat earlier applying the coating liquid that contains conductive component, coating liquid has better coating characteristics and also can improve adherence with base material like this.

After conductive layer forms, can on conductive layer, apply sided corona treatment or ultraviolet ray irradiation, can improve the coating characteristics and the printing performance of conductive layer surface like this and on conductive layer, form one deck or make printing very smooth.

In addition, can on conductive layer, be shaped a thin protective layer so that electric conductivity is avoided infringement.

High-antistatic laminated material of the present invention has low-down sheet resistance and conductive layer at 25 ℃, the sheet resistance (RS that has during relative humidity 15% ₀) be not more than 10 ¹¹Ω/ preferably is not more than 10 ¹⁰Ω/ more preferably is not more than 10 ⁹Ω/ has shown antistatic property excellent under low humidity like this.Charge decay time preferably was not more than 2.0 seconds, more preferably no more than 0.5 second.At this, sheet resistance shows, and what be that the difficulty that flows on the surface of conductive layer of electric current and charge decay time show is the easy degree that charged particles is escaped.What the two all showed is antistatic property.

High-antistatic laminated material of the present invention has excellent in water resistance, wherein high-antistatic laminated material of the present invention being immersed 40 ℃ pure water after one hour, at 25 ℃, relative humidity 15% lower conductiving layer sheet resistance (RS ₁) and RS ₀Ratio (RS ₁/ RS ₀) be not more than 10, preferably be not more than 8, be more preferably 5.Also be difficult to reduce its antistatic property owing to immerse in the water, laminated material can be used to wash with water the reusable environment in back may become wet environment with water is arranged.

Laminated material of the present invention has excellent forming characteristic, wherein at the high-antistatic laminated material 150% back conductive layer of the invention that stretches at 25 ℃, the sheet resistance (RS under relative humidity 15% situation ₂), with RS ₀Ratio (RS ₂/ RS ₀) preferably be not more than 10, more preferably be not more than 8, most preferably 5.Stretching when moulding can not reduce antistatic property basically.

Laminated material of the present invention has excellent hear resistance, and wherein after 250 ℃ of heating high-antistatic laminated materials of the present invention continue one minute, conductive layer is at 25 ℃, the sheet resistance (RS under relative humidity 15% situation ₀), with RS ₀Ratio (RS ₉/ RS ₀) preferably be not more than 5.0, more preferably be not more than 3.0.The heating that is used for moulding can not reduce antistatic property basically.

High-antistatic laminated material of the present invention preferably has 75% the visible light transmittance rate of being no less than according to JIS7105 metering, more preferably is no less than 80%, most preferably is to be no less than 85%.Be no less than 75% by setting visible light transmittance rate, when the high-antistatic laminated material was used for packaging material, the visual confirmation inclusion was monitored automatically by TV (TV) camera, inclusion was adhered to bar code processing etc. can both be easy to realize.

The conductive layer of high-antistatic laminated material of the present invention preferably has 75% the visible light transmittance rate of being no less than according to JIS7105 metering, more preferably is no less than 80%, and is most preferred for being no less than 85%.Have the conductive layer of high visible light transmittance by use, also can use lower a little base material and the translucent base material of visible light transmittance rate, this has just increased the kind of spendable base material.When the above-mentioned optics supervision to inclusion is finished, need carry out surface dulling processing etc. for preventing fault.The high visible light transmittance can compensate the reduction of handling the visible light transmissive amount that causes owing to delustring.

The visible light transmittance rate of conductive layer (X) can obtain by the visible light transmittance rate (Z) of measurement high-antistatic laminated material and the visible light transmittance rate (Y) of base material, can probably be calculated by formula Z=XY.The visible light transmittance rate of base material can be by with the conductive layer of swelling high-antistatic laminated materials such as solution, by wiping etc. it is removed then to residue measurement and measures.After carrying out delustring and handling, measurement can be carried out after the suitable solution of coating one is to the surface, and this solution has and measurement material refractive index much at one, and does not encroach on material.

And high-antistatic of the present invention is adopted laminated material and is preferably had and be not more than 5.0 mist degree, more preferably be not more than 3.0, and this laminated material has excellent transparency.

The high-antistatic lamination material that contains a conductive layer, this conductive layer have and are not more than 10 ¹¹The RS of Ω/ ₀, be not more than 10 RS ₁/ RS ₀And be not more than 10 RS ₂/ RS ₀, be by use by above-mentioned contain conducting polymer and thermoplastic polymer as the composition of conductive layer component to form coating layer and to solidify this coating layer and by other method acquisition.

High-antistatic laminated material of the present invention has excellent antistatic property, transparency and anti-stick company after immersing water and after being shaped under low humidity.Therefore, the high-antistatic laminated material is suitable to the base band, container (particularly pallet); magazine; packaging material, IC-card etc., it can protect electronic material such as IC; LSI; silicon chip, hard disk, liquid crystal substrate; electronic components etc. are avoided between transmission and installation period damaging and because former thereby adhesion dusts such as static in storage.

At it is to be used for will making ester moulding form conductive layer then thereon earlier under the situation of the pallet of electrical equipment or base band.The compacting (as 250 ℃ of heating one minute) that preferably will comprise the high-antistatic laminated material of thermoplastic film is base material.High-antistatic laminated material of the present invention can be owing to not stretching and heat when being shaped reduces antistatic property, or produce peeling off of conductive layer, so pallet or base band can obtain by the method for press forming.

When being used for the pallet of electronic component, high-antistatic laminated material of the present invention is pressed into a concave surface (part of processing) and a flange at circumferential periphery.When being used for the pallet of electronic component, the sheet resistance (RS of the flange of conductive layer ₃) at 25 ℃, be not more than 10 under the situation of relative humidity 15% ¹¹Ω/ preferably is not more than 10 ¹⁰Ω/ is more preferably 10 ⁹Ω/.Like this, under the low humidity condition, it just demonstrates excellent antistatic property.

At 40 ℃ pallet was immersed pure water after one hour,, have the sheet resistance (RS of the conductive layer of flange under the situation of relative humidity 15% at 25 ℃ ₄) and RS ₃Ratio (RS ₄/ RS ₃) be not more than 10, preferably be not more than 8, more preferably no more than 5.Antistatic property also seldom reduces in the water owing to immerse, so it can be used for after washing reusable environment and owing to have water to make it become the environment that wets.

Conductive layer concave surface with the 0.5-0.7 thickness that is equivalent to thickness of flange, at 25 ℃, the sheet resistance (RS under the situation of relative humidity 15% ₅) and RS ₃Ratio (RS ₅/ RS ₃) be not more than 100, preferably be not more than 80, more preferably no more than 50.It is very little that heat during like this, owing to stretching or press forming makes the reduction of antistatic property.

When high-antistatic laminated material of the present invention is used for the base band of electronic component, high-antistatic laminated material of the present invention be pressed into longitudinally with its excircle on a plurality of concave surfaces (processing part) that are used to encapsulate electric elements of distributing of flange.Under the situation of the base band that is used for electronic component, the sheet resistance (RS of conductive layer flange portion ₆) at 25 ℃, be not more than 10 under the situation of relative humidity 15% ¹¹Ω/ preferably is not more than 10 ¹⁰Ω/, more preferably 10 ⁹Ω/.Like this, it demonstrates excellent antistatic property under the low humidity situation.

In the time of 40 ℃, the base band was immersed pure water after one hour, at 25 ℃, the sheet resistance (RS of the flange portion of the situation lower conductiving layer of relative humidity 15% ₇) and RS ₆Ratio (RS ₇/ RS ₆) be not more than 10, preferably be not more than 8, more preferably be not more than 5.Because it also is rare immersing the reduction of the antistatic property that is caused in the water, so it can be used for after washing reusable environment and owing to have water to make it become the environment that wets.

At 25 ℃, has the sheet resistance (RS of concave part of the conductive layer of the thickness that is equivalent to flange portion thickness 0.5-0.7 under the situation of relative humidity 15% ₈) and RS ₆Ratio (RS ₈/ RS ₆) be not more than 100, preferably be not more than 80, preferredly be not more than 50.It is very little that heat during like this, owing to stretching or press forming makes the reduction of antistatic property.

When high-antistatic laminated material of the present invention is used for packaging material, particularly as shown in Figure 1 during amortizing packaging material, for example, a pair of stretched PTFE film 2 is clamped the goods 3 as electrical equipment etc., the relative end of a pair of stretched PTFE film 2 is fixed on (as Fig. 1, these ends are fixing by framework 5) on the container 1.High-antistatic laminated material of the present invention can be used as stretched PTFE film 2.

When high-antistatic laminated material of the present invention is used for the base band, pallet, magazine, when packaging material, the base material of IC-card etc., it is at low humidity, after immersing water and after being shaped, have excellent antistatic property, and allow after washing, to reuse, because the antistatic property of concave surface does not almost reduce after shaping.

Explain the present invention in detail below by embodiment, but these embodiment are not construed as limiting to the present invention.The evaluation method that the present invention uses shows below.

1. mist degree

According to JISK7105, mist degree is to be determined by the mist degree instrument 1001DP that NIPPON DENSHOKU produces.

2. sheet resistance (RS ₀, RS ₃, RS ₆)

The conductive layer of high-antistatic laminated material (at the situation lower flange conductive layer partly of pallet and base band) is under 500V voltage, and at 25 ℃, relative humidity 15% time is determined with the sheet resistance instrument that TAKEDA RIKEN produces.

About pallet and base band, have and be equivalent to the sheet resistance (RS of concave part of conductive layer that flange portion thickness is the thickness of 1 0.5-0.7 ₅, RS ₈) be at 25 ℃, relative humidity 15% time is definite, and determines and (RS ₃, RS ₆) ratio (RS ₅/ RS ₃, RS ₈/ RS ₆).

About pallet and base band, the thickness of flange and concave surface be determine by digital thickness gauge with measure its sheet resistance.Send out average thickness value with 5 points and come calculated thickness and sheet resistance.

3. the resistance to water of conductive layer (difference on the sheet resistance)

High-antistatic laminated material, pallet or base band are dipped in 40 ℃ the pure water one hour, the sheet resistance (RS of conductive layer (at the conductive layer of the situation lower flange of pallet and base band) ₁, RS ₄, RS ₇) be 25 ℃, measure during relative humidity 15%.By with the sheet resistance (RS of conductive layer before immersing ₀, RS ₃, RS ₆) ratio (RS ₁/ RS ₀, RS ₄/ RS ₃, RS ₇/ RS ₆) estimate its resistance to water.

4. the difference of the sheet resistance after extending

The biaxial tension equipment that use is made by TOYO SEIKI, (by unidirectional stretching 150%, 15 seconds preheating time, draw speed was 5m/min to the high-antistatic laminated material under nitrogen environment for 92mm * 92mm).This moment base material I, II, III, the temperature of IV and V is respectively 110 ℃, 130 ℃, 110 ℃, 100 ℃ and 150 ℃.

At 25 ℃, measure the sheet resistance (RS of the back conductive layer that stretches during relative humidity 15% ₂) and with stretch before the sheet resistance (RS of conductive layer ₀) ratio (RS ₂/ RS ₀).

5. resistance to blocking

The back side (one side that does not have conductive layer) of the conductive layer of high-antistatic laminated material and other high-antistatic laminate substrate is at 40 ℃, 80%RH and apply 100g/cm ²Overlap under the load.Laminated material was parked 24 hours and two samples are torn.Pass judgment on by following standard.

There is not resistance when tearing: zero

Some resistances: △ is arranged when tearing

Suitable resistance is arranged when tearing: *

Synthetic embodiment 1: the polyaniline of synthetic sulfonation and prefabricated water/alcoholic solution (Paq).

2-aminoanisole-4-sulfonic acid (100mmol) at 23 ℃ by stirring and dissolving (4mol/L) and splash into the aqueous solution of ammonium peroxodisulfate (100mmol) in water-soluble ammonium salt solution.Splash into finish after, stirred the mixture 10 hours at 23 ℃.Product is filtered, thus washing and the dry polymer (13g) that obtains powder type.When room temperature with above-mentioned polymer (3 weight portion) by stirring and dissolving at water-soluble sulfuric acid solution (0.3mol/L, 100 weight portions) thus in obtain the polyaniline of sulfonation.At this moment, the sulfonic group in the polyaniline of sulfonation is 100%.The polyaniline of above-mentioned sulfonation (2 weight portion) is dissolved in the mixture of water/alcoholic solution (Paq) of water (50 weight portion) and isopropyl alcohol (50 weight portion).

Synthetic embodiment 2: synthetic copolyester (A) and the prefabricated water/pure disperse system (Aaq) that contains sulfonate group.

The copolyester that contains sulphonate-base is synthetic as follows, its disperse system prefabricated as follows.Use dimethyl terephthalate (DMT) (48mol%), DMIP (48mol%) and 5-sulfoisophthalic acid sodium (4mol%) are as the dicarboxylic acid component and make spent glycol (80mol%), diethylene glycol (DEG) (20mol%) carries out ester exchange reaction and polycondensation reaction as diol component with usual way.It is 61 ℃ that the copolyester that contains sulphonate-base that obtains has glass transition temperature.Contain the copolyester (300 parts) of sulfonate group and butyl-cellosolve (150 parts) thus stir and heating obtains viscosity solution.Progressively add entry (550 parts) thereby also stir and obtain the even pale aqueous dispersion that solids content is 30wt%.Thereby the water and the isopropyl alcohol that add equal quantities to disperse system obtain having the aqueous dispersion that solids content is the copolyester that contains sulphonate-base of 8wt%.

Synthetic embodiment 3: synthetic grafted polyester (B) and prefabricated aqueous dispersion

(Baq)。

Be equipped with agitator, in the stainless autoclave of thermometer and partial reflux condenser, add dimethyl terephthalate (DMT) (5mol), DMIP (4.5mol), ethylene glycol (6.5mol), 1, ammediol (3.5mol) and tetrabutyl titanate salt (0.002mol) and the ester exchange reaction that surpasses 4 hours from 160 ℃ to 220 ℃.Then, adding fumaric acid (0.5mol) mixture heats more than 1 hour from 200 ℃ to 220 ℃.Thereby reaction system progressively is depressurized and obtained polyester (Bo) in decompression in 1.5 hours for mixture is reacted.

Then, be equipped with agitator, thermometer, reflux and quantitatively add above-mentioned polyester (Bo) (300 parts) in the reactor of filter, methyl ethyl ketone (360 parts) and isopropyl alcohol (120 parts) and in heating with stirring the mixture so as when backflow dissolving resin.When resin is dissolved fully, maleic acid (25 parts), the mixture of ethyl acrylate (65 parts) and octyl group alkane (1.5 parts) and azodiisobutyronitrile (6 parts) solution that is dissolved in the mixture of methyl ethyl ketone (90 parts) and isopropyl alcohol (30 parts) were splashed into polyester liquid respectively above 1.5 hours, react three hours then, thereby obtain graft polymers (B) solution.This graft polymers solution is cooled to room temperature and adds the triethylamine (59 parts) that is used for neutralization.Then, add ion exchange water (800 parts) and mixture stirred 30 minutes.Thereby add the unnecessary solvent of hot mixt removal and draw aqueous dispersion.This disperse system is added into the water of equal quantities and the mixture of isopropyl alcohol, thereby obtains having alcohol/aqueous dispersion that solids content is 8wt% (Baq).

Synthetic embodiment 4: the prefabricated aqueous dispersion (Caq) that contains polyvinyl alcohol/moisture polyisocyanate crosslinking agent

The aqueous solution of prefabricated one 10% polyvinyl alcohol (saponification percentage is 98%) and in the polyvinyl alcohol of per 100 weight portion solids contents, add the ELASTRON BN69 (10 weight portion) that produces by Daiichi Kogyo Seiyaku, thus obtain containing the aqueous dispersion (Caq) of polyvinyl alcohol/crosslinking agent.

Synthetic embodiment 5: prefabricated base material

Base material and production method thereof that embodiment uses are as follows.

[base material I]

PET (PET) thereby be melted in the time of 290 ℃ extrudes and is that cooling obtains the thick non-oriented sheet material of 500 μ m on 30 ℃ the chill roll in temperature.This sheet material is used for base material I.Visible light transmittance rate is 95%.

[base material I I]

PEN (PEN) thereby be melted in the time of 300 ℃ extrudes and is that cooling obtains the thick non-oriented sheet material of 500 μ m on 30 ℃ the chill roll in temperature.This sheet material is used for base material I I.Visible light transmittance rate is 94%.

[base material I II]

One copolymer wherein in the PET ethylene glycol component of 30mol% replaced by cyclohexanedimethanol, extrude and be that cooling obtains the thick non-oriented sheet material of 500 μ m on 30 ℃ the chill roll in temperature thereby this copolymer is melted in the time of 290 ℃.This sheet material is used for base material I II.Visible light transmittance rate is 95%.

[base material I V]

One copolymer wherein in the PET ethylene glycol component of 30mol% replaced by neopentyl glycol, extrude and be that cooling obtains the thick non-oriented sheet material of 500 μ m on 30 ℃ the chill roll in temperature thereby this copolymer is melted in the time of 290 ℃.This sheet material is used for base material I V.Visible light transmittance rate is 95%.

[base material V]

Extrude and be that cooling obtains the thick non-oriented sheet material of 500 μ m on 30 ℃ the chill roll in temperature thereby Merlon is melted in the time of 290 ℃.This sheet material is used for base material V.Visible light transmittance rate is 95%.

Embodiment 1-1 is to 1-5

The polyaniline solutions (Paq) of the sulfonation that is obtained by synthetic embodiment 1 and the copolyester disperse system (Aaq) that contains sulphonate-base that obtained by synthetic embodiment 2 mix than (weight ratio) with 20/80 solid, and be that 8/100 ratio adds non-ionic surface active agent Emulgen 80 (being made by Kao Corporation) in polyaniline solutions (Paq) weight ratio with sulfonation, the aqueous dispersion of polyvinyl alcohol/moisture polyisocyanate crosslinking agent (Caq) with the solid of disperse system (Aaq) be that 20/100 ratio is added into than (weight ratio), thereby draw the coating liquid of present embodiment.

Above-mentioned coating liquid is applied to base material I, II, and III on IV and the V, reaches 0.5g/m ²Solid concentration and with 70 ℃ hot-air drying.Evaluation result to these sheet materials is presented in the table 1.

Embodiment 2-1 is to 2-5

Except using the disperse system (Aaq) that the grafted polyester disperse system (Baq) that is obtained by synthetic embodiment 3 replaces being obtained by synthetic embodiment 2, with the mode identical, prefabricated coating liquid with embodiment 1.

Above-mentioned coating liquid is applied to base material I, II, and III on IV and the V, reaches 0.5g/m ²Solid concentration and with 70 ℃ hot-air drying.Evaluation result to these sheet materials is presented in the table 1.

Embodiment 3-1 is to 3-5

Except the aqueous dispersion (Caq) that replaces with the glycerine polyglycidyl ether obtaining and this glycerine polyglycidyl ether by synthetic embodiment 4 be 2/100 ratio is added into by the solid of the disperse system (Aaq) of synthetic embodiment 2 acquisitions than (weight ratio), with the mode identical, prefabricated coating liquid with embodiment 1.

Above-mentioned coating liquid is applied to base material I, II, and III on IV and the V, reaches 0.5g/m ²Solid concentration and with 70 ℃ hot-air drying.Evaluation result to these sheet materials is presented in the table 1.

Embodiment 4-1 is to 4-5

Polyaniline solutions (Paq) by the sulfonation of synthesizing embodiment 1 acquisition, copolyester disperse system (Aaq) that contains sulphonate-base and SUMIMAL M-30W (methylated melmac by synthetic embodiment 2 acquisitions, by Sumitomo Chemical Industries, Ltd. make) be that 10/85/5 ratio mixes with solid than (weight ratio), and add mixed solution (water/isopropyl alcohol-50/50 (weight ratio)) thus obtaining one in advance has the solution that solid concentration is 2-5%.Add Megafac F-142D (fluorine surfactant, by DAINIPPON INK AND CHEMICALS, INC. makes) for this solution with the ratio of 0.08wt% thus obtain coating liquid.

Above-mentioned coating liquid is applied to base material I, II, and III on IV and the V, reaches 0.3g/m ²Solid concentration and with 70 ℃ hot-air drying.Evaluation result to these sheet materials is presented in the table 1.

Comparative Examples 1,2

Except not adding the aqueous dispersion (Caq) that obtains by synthetic embodiment 4, with embodiment 1 and 2 identical modes, prefabricated coating liquid uses the mode identical with embodiment 1,2 to obtain sheet material.

Comparative Examples 3

Except not adding the glycerine polyglycidyl ether, in the mode identical with embodiment 3, prefabricated coating liquid uses the mode identical with embodiment 1,2 to obtain sheet material.The evaluation result of these sheet materials is presented in the table 1.

Table 1

	Base material	????RS 0	????RS 1	??RS 1/RS 0	????RS 2	??RS 2/RS 0	???V.L.T.	Mist degree	Caking property
										??1-1	??I	??3.7×10 8	??9.3×10 8	????2.5	??9.6×10 8	????2.6	????88％	????2.8	????○
??1-2	??II	??2.6×10 8	??4.2×10 8	????1.6	??5.7×10 8	????2.2	????87％	????2.5	????○
										??1-3	??III	??4.5×10 8	??1.1×10 8	????2.5	??1.5×10 9	????3.4	????87％	????2	????○
??1-4	??IV	??3.8×10 8	??1.1×10 9	????3	??1×10 8	????2.7	????88％	????2.3	????○
										??1-5	??V	??3.5×10 8	??9.5×10 8	????2.7	??9.1×10 8	????2.6	????88％	????2.2	????○
??2-1	??I	??1×10 8	??1.8×10 8	????1.8	??2.1×10 8	????2.1	????89％	????2.8	????○
										??2-2	??II	??1.1×10 8	??1.7×10 8	????1.5	??2.9×10 8	????2.6	????89％	????2.9	????○
??2-3	??III	??1×10 8	??1.3×10 8	????1.3	??3.4×10 8	????3.4	????89％	????3	????○
										??2-4	??IV	??1.2×10 8	??1.4×10 8	????1.2	??3.8×10 8	????3.2	????89％	????2.5	????○
??2-5	??V	??1.2×10 8	??1.3×10 8	????1.1	??3.6×10 8	????3	????90％	????2.1	????○
										??3-1	??I	??7.2×10 8	??7.9×10 8	????1.1	??2.9×10 9	????4	????89％	????2.5	????○
??3-2	??II	??6.3×10 8	??8.2×10 8	????1.3	??2×10 9	????3.2	????88％	????2.3	????○
										??3-3	??III	??7.6×10 8	??9.1×10 8	????1.2	??2.1×10 9	????2.7	????90％	????2	????○
??3-4	??IV	??7.6×10 8	??7.6×10 8	????1	??1.9×10 9	????2.5	????88％	????2.1	????○
										??3-5	??V	??7.5×10 8	??9×10 8	????1.2	??1.9×10 9	????2.5	????90％	????2.4	????○
??4-1	??I	??4.2×10 8	??5.5×10 8	????1.3	??1×10 9	????2.4	????88％	????2.1	????○
										??4-2	??II	??3×10 8	??4.5×10 8	????1.5	??7.8×10 8	????2.6	????88％	????2.3	????○
??4-3	??III	??3.4×10 8	??4.1×10 8	????1.2	??1×10 9	????3	????89％	????2.1	????○
										??4-4	??IV	??2.9×10 8	??3.2×10 8	????1.1	??6.1×10 8	????2.1	????89％	????2.1	????○
??4-5	??V	??2.8×10 8	??3.6×10 8	????1.3	??6.2×10 8	????2.2	????88％	????2.2	????○
										Comparative Examples 1	??I	??2×10 8	???＞10 15	??＞10000	??4.4×10 8	????2.2	????89％	????2.2	????△
Comparative Examples 2	??I	??7.8×10 8	???＞10 15	??＞10000	??2×10 9	????2.5	????89％	????1.9	????×
										Comparative Examples 3	??I	??8×10 8	???＞10 15	??＞10000	??2×10 9	????2.5	????85％	????1.8	????△

^*V.L.T: the visible light transmittance rate of high-antistatic laminated material

Embodiment 5: pallet

Use the vacuum forming machine of producing by Sanwa Kogyo Kabushiki Kaisha (PLAVAC) at 110 ℃, 55 ℃ of preheat temperatures, 13 seconds preheating time, molding time 15 seconds, the pallet of preparation has the concave surface (9cm * 6cm, dark 4cm) and the wide flange of 3cm of 3 row * 4 row.The sheet material that uses is by embodiment 1-1,1-3, and 2-1,3-1,4-1, the method for 4-3 and 4-5 obtains.

Evaluation result to these sheet materials is presented in the table 2.

Embodiment 6: the base band

With the process conditions identical, be prefabricated into a 50cm * 50cm sheet material with delegation's concave surface (8mm * 8mm, dark 5mm) with the moulding pallet.Delegation's concave surface is cut into the band of 20mm, and they connect to obtain molding base band with different band.The sheet material that uses is by embodiment 1-1,1-3, and 2-1,3-1,4-1, the method for 4-3 and 4-5 obtains.Evaluation result to these sheet materials is presented in the table 3.

Table 2

Pallet

Base material	?????RS 3	?????RS 5	??RS 5/RS 3	The thickness ratio	????RS 4	??RS 4/RS 3
							???1-1	??6.00×10 8	??4.98×10 9	????8.3	????0.64	?9.60×10 8	????1.6
???1-3	??4.70×10 8	??2.44×10 9	????5.2	????0.61	?9.40×10 8	????2
							???2-1	??3.20×10 8	??1.34×10 9	????4.2	????0.58	?3.84×10 8	????1.2
???3-1	??1.10×10 9	??6.27×10 9	????5.7	????0.6	?1.54×10 9	????1.4
							???4-1	??5.80×10 8	??2.61×10 9	????4.5	????0.55	?6.96×10 8	????1?2
???4-3	??4.60×10 8	??2.58×10 9	????5.6	????0.58	?5.06×10 8	????1.1
							???4-5	??5.40×10 8	??2.97×10 9	????5.5	????0.58	?9.18×10 8	????1.7

Table 3

Band

Base material	????RS 6	????RS 8	??RS 8/RS 6	The thickness ratio	????RS 7	??RS 7/RS 6
							???1-1	?5.20×10 8	?5.93×10 9	????11.4	???0.52	?6.76×10 8	????1.3
???1-3	?5.00×10 8	?3.95×10 9	????7.9	???0.6	?9.00×10 8	????1.8
							???2-1	?3.40×10 8	?1.97×10 9	????5.8	???0.55	?3.74×10 8	????1.1
???3-1	?1.10×10 8	?9.13×10 8	????8.3	???0.52	?1.32×10 8	????1.2
							???4-1	?5.50×10 8	?3.74×10 9	????6.8	???0.55	?6.05×10 8	????1.1
???4-3	?4.80×10 8	?3.46×10 9	????7.2	???0.52	?7.20×10 8	????1.5
							???4-5	?5.20×10 8	?4.63×10 9	????8.9	???0.55	?8.32×10 8	????1.6

Embodiment 7: packaging material

Polyethylene and polyurethane are extruded by multilayer and with blowfilm shaping machine molding of polyethylene polyurethane (every layer thickness 100 μ m, 80 μ m) duplicature, are used as base material VI.

The coating liquid of embodiment 2 is applied to the surface of polyurethane base material VI.Behind finish-drying, polyethylene layer is stripped from and is exposed the conductive polyurethane film.The conductive layer of this film, at 25 ℃, sheet resistance is 2 * 10 during relative humidity 15%RH ⁹Ω/.At 25 ℃, relative humidity 15%RH, after the stretching 150%, sheet resistance is not more than 10 ¹⁰Ω/.

As shown in Figure 1, this film 2 is attached on the corrugated paper framework 5 (25cm * 30cm has the opening of a 15cm * 20cm) with two sides band.Circuit substrate 3 is sandwiched between these two the corrugated paper frameworks 5 with film 2, and places cardboard box 1 in such a way, and promptly by means of the effect of these films, circuit substrate 3 is maintained in the space of chest 1.

High-antistatic laminated material of the present invention has excellent antistatic property, transparency, and resistance to water and resistance to blocking energy, because conductive layer is by conducting polymer, thermoplastic polymer and crosslinking agent reaction are solidified.

Itself please be based on the patent application No.174748/1998 of Japan, its content is cited as a reference at this.

Claims (28)

1. a high-antistatic laminated material comprises a base material and a conductive layer at least on one side that is laminated in this base material, and described conductive layer comprises conducting polymer and is cured.

2. the high-antistatic laminated material of claim 1, wherein said conductive layer further comprises a thermoplastic polymer.

3. claim 1 or 2 high-antistatic laminated material, wherein said conductive layer is to use crosslinking agent to be cured by cross-linking reaction.

4. the high-antistatic laminated material of claim 1, wherein said conducting polymer are a kind of conducting polymers of water-soluble or organic solvent.

5. the high-antistatic laminated material of claim 1, wherein said conducting polymer is the polyaniline or derivatives thereof.

6. the high-antistatic laminated material of claim 1, wherein said conducting polymer is to contain sulfonic polyaniline or derivatives thereof.

7. the high-antistatic laminated material of claim 1, wherein said conducting polymer comprise aminobenzenesulfonic acid that an alkoxyl replaces as polymerizable components.

8. the high-antistatic laminated material of claim 1, wherein said conducting polymer comprises that aminobenzene methoxy base sulfonic acid is as polymerizable components.

9. the high-antistatic laminated material of claim 2, wherein said thermoplastic polymer is a kind of polyester with hydrophilic radical.

10. the high-antistatic laminated material of claim 2, wherein said this thermoplastic polymer is a kind of copolyester, and this copolyester is one to have dicarboxylic acids or that hydrophilic radical accounts for the 0.5-15mol% of whole dicarboxylic acids components and have the glycol that hydrophilic radical accounts for the 0.5-15mol% of whole glycol components or these two kinds of components and obtain by copolymerization.

11. the high-antistatic laminated material of claim 2, wherein said thermoplastic polymer are a kind of grafted polyesters, this grafted polyester is to be aggregated on the polyester by the vinyl monomer-grafted that will have hydrophilic radical to obtain.

12. the high-antistatic laminated material of claim 3, wherein said crosslinking agent are to be selected from least a in one group of compound being made up of multi-group epoxy compound, multi-functional isocyanate compound, polyfunctional group De oxazoline compound, multi-functional vinyl compound, multi-functional acyclic compound, multi-functional carboxylic acid compound, multi-functional amines, multi-functional hydroxyl based compound and multi-functional sulfhydryl compound.

13. being the self-crosslinkings by conducting polymer or thermoplastic polymer or conducting polymer and thermoplastic polymer, the high-antistatic laminated material of claim 1 or 2, wherein said conductive layer be cured.

14. the high-antistatic laminated material of claim 1, wherein said conductive layer further comprises a kind of surfactant.

15. the high-antistatic laminated material of claim 1, wherein said base material are film or the sheet materials of being made by organic resin, and this high-antistatic laminated material has and is not more than 5.0 mist degree.

16. the high-antistatic laminated material of claim 1, wherein said base material are by being selected from polyester, Merlon, film or sheet material that a kind of material in polyolefin and the polyurethane is made.

17. a high-antistatic laminated material comprises an a kind of base material and a conductive layer at least on one side that is laminated in this base material,

Described conductive layer is at 25 ℃, has under the situation of relative humidity 15% to be not more than 10 ¹¹Sheet resistance (the RS of Ω/ ₀), and this high-antistatic laminated material was immersed pure water after one hour at 40 ℃, and at 25 ℃, the situation lower surface resistance (RS of relative humidity 15% ₁) and RS ₀Ratio (PS ₁/ RS ₀) be not more than 10.

18. the high-antistatic laminated material of claim 17, wherein said conductive layer behind this high-antistatic laminated material 150% that stretches, at 25 ℃, during relative humidity 15%, its sheet resistance (RS ₂) and RS ₀Ratio (RS ₂/ RS ₀) be not more than 10.

19. the high-antistatic laminated material of claim 17 or 18, wherein said conductive layer comprise a kind of conducting polymer and have been cured.

20. a container that is used for electronic component, this container are to obtain by claim 1,17 or 18 high-antistatic laminated material are shaped.

21. the container of claim 20, this container is a pallet.

22. a base band that is used for electric elements, this base band are to obtain by claim 1,17 or 18 high-antistatic laminated material are shaped.

23. a pallet that is used for electronic component, this pallet is obtained by the high-antistatic laminated material shaping that comprises an a kind of base material and a conductive layer at least on one side that is laminated in this base material, and this pallet comprises a concave surface and a flange at its circumferential periphery,

Sheet resistance (the RS of the flange of wherein said conductive layer ₃) under 25 ℃, the situation of relative humidity 15%, be not more than 10 ¹¹Ω/ immerses pure water after one hour at 40 ℃ with pallet, its sheet resistance (RS under 25 ℃, the situation of relative humidity 15% ₄) and RS ₃Ratio (RS ₄/ RS ₃) be not more than 10, and have the conductive layer concave surface that is equivalent to thickness of flange 0.5-0.7 thickness, its sheet resistance (RS under 25 ℃, the situation of relative humidity 15% ₅) and RS ₃Ratio (RS ₅/ RS ₃) be not more than 100.

24. the pallet that is used for electronic component of claim 23, this pallet are to obtain by shaping claim 1,17 or 18 high-antistatic laminated material.

25. base band that is used for electronic component, this band comprises a base material by shaping and is laminated in that the high-antistatic laminated material of a conductive layer at least on one side of this base material obtains, the base band comprises a plurality of concave surface of encapsulating electronic components and the flanges on excircle of being used for that longitudinally distribute

Sheet resistance (the RS of flange portion wherein ₆) under 25 ℃, the situation of relative humidity 15%, be not more than 10 ¹¹Ω/, the pure water that in the time of 40 ℃ the base band is immersed be after one hour, its sheet resistance (RS under 25 ℃, the situation of relative humidity 15% ₇) and RS ₆Ratio (RS ₇/ RS ₆) be not more than 10, and under 25 ℃, the situation of relative humidity 15%, have the sheet resistance (RS of concave part of the conductive layer of the thickness that is equivalent to flange portion thickness 0.5-0.7 ₈) and RS ₆Ratio (RS ₈/ RS ₆) be not more than 100.

26. the base band that is used for electronic component of claim 25 is to obtain by shaping claim 1,17 or 18 high-antistatic laminated material.

27. amortizing packaging material that is used to transport packaged goods that comprises a container and a pair of stretched PTFE film, described stretched PTFE film has a pair of relative end that is installed on the container, and wherein said stretched PTFE film is selected from by claim 1,17 or 18 high-antistatic laminated material.

28. an IC-card, it is by obtaining as the base material of card with claim 1,17 or 18 high-antistatic laminated material.

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