CN1745126A - Dip molded article with low surface resistivity - Google Patents
Dip molded article with low surface resistivity Download PDFInfo
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- CN1745126A CN1745126A CN 200480003410 CN200480003410A CN1745126A CN 1745126 A CN1745126 A CN 1745126A CN 200480003410 CN200480003410 CN 200480003410 CN 200480003410 A CN200480003410 A CN 200480003410A CN 1745126 A CN1745126 A CN 1745126A
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Abstract
The present invention relates to a dip molding having a low surface resistivity, the dip molding having a surface resistivity that is lower than that of a conventional product even after being washed with superpure water. The dip molding of the present invention has a surface resistivity, measured under an atmosphere of 20 DEG C and a relative humidity of 65%, of 10<7> to 10<10> OMEGA /square. Since the dip molding of the present invention has a low surface resistivity, it can suitably be used as a glove for precision electronic component production and semiconductor component production.
Description
Technical field
The present invention relates to dip-molded articles, its preparation method and dip in the plastic cement dairy compositions.
Background technology
By dip in mould comprise natural rubber latex or acrylonitrile butadiene copolymer latex dip in not only softness but also have sufficient mechanical of rubber gloves that the plastic cement dairy compositions forms, therefore be used for every field.
Particularly in the production of the production of precision electronic element and semiconductor element; because contained metal ion can influence work in-process or product in the particulate of rubber gloves surface attachment or the rubber gloves, need before use with pure water or ultrapure water washing rubber gloves.
Yet the polymkeric substance that forms natural rubber latex and acrylonitrile butadiene copolymer latex is the high degree of electrical insulativity, and the surface resistivity of the rubber gloves of being made by these latex surpasses 10
10Ω/square.And by adopting the washing of pure water or ultrapure water, it is higher that the surface resistivity of rubber gloves will become.
When the surface resistivity of rubber gloves surpasses 10
10Ω/square the time, in the working process can the accumulation static, the problem that this static causes is that precision electronic element or semiconductor element are destroyed.
Summary of the invention
Under these conditions, the purpose of this invention is to provide a kind of dip-molded articles, it has low surface resistivity, even and after with the ultrapure water washing, also have the surface resistivity lower than conventional dip-molded articles, and its preparation method is provided.
Realized purpose of the present invention by following measure (1)-(4).
(1) have under 20 ℃ and relative humidity 65% atmosphere, record 10
7-10
10Ω/square the dip-molded articles of surface resistivity,
(2) prepare the method for dip-molded articles, this method is included in to dip in to form on the mold tool to comprise and dips in dipping in of plastic cement dairy compositions and mould layer, and this is dipped in mould layer and contact with cats product,
(3) comprise the rubber latex that is added with cats product dip in the plastic cement dairy compositions and
(4) prepare the method for dip-molded articles, this method is included in to dip in to form on the mold tool and comprises above-mentioned (3) and dip in dipping in of plastic cement dairy compositions and mould layer, vulcanizes this then and dips in and mould layer.
Preferred forms of the present invention
Describe the present invention below in detail.
(dip-molded articles)
The surface resistivity of dip-molded articles of the present invention is measured as 10 under 20 ℃ and 65% relative temperature atmosphere
7-10
10Ω/square.The surface resistivity of described dip-molded articles is preferably 10
8-10
10Ω/square.The dip-molded articles that preparation has than above-mentioned lower surface resistivity is difficult, yet the dip-molded articles of high surface resistance rate can cause accumulation of static electricity in the course of the work, is not suitable for semiconductor element production.
In the present invention, 10
7Refer to 1 * 10
7Principle of identity is applicable to 10
10, 10
11Deng.And, 10
7-10
10Refer at least 1 * 10
7To at the most 1 * 10
10Principle of identity is applicable to 10
8-10
11Deng.
Surface resistivity and volume specific resistance are measured according to ASTM D257-93.The detailed content of measuring method is as be shown in the examples.
Soak in 30 ℃ ultrapure water after 2 hours, dip-molded articles of the present invention preferably has under 20 ℃ and 65% relative humidity atmosphere and is measured as 10
7-10
10Ω/square surface resistivity, more preferably 10
8-10
10Ω/square.Even the dip-molded articles that still has the surface resistivity in this scope in ultrapure water after soaking is more suitable for being used for the production of precision electronic element or semiconductor element.
In the present invention, ultrapure water refers to that 25 ℃ of following resistivity are at least the water of 16M Ω cm.And in the present invention, the temperature of soaking the ultrapure water of dip-molded articles is 30 ℃ ± 10 ℃.
Dip-molded articles of the present invention preferably has under 20 ℃ and 65% relative humidity atmosphere and is measured as 10
8-10
11The volume specific resistance of Ω cm, more preferably 10
9-10
11Ω cm.Dip-molded articles with the volume specific resistance in this scope still is suitable for the production of precision electronic element or semiconductor element.
Soak in 30 ℃ ultrapure water after 2 hours, dip-molded articles of the present invention preferably has under 20 ℃ and 65% relative humidity atmosphere and is measured as 10
9-10
11The volume specific resistance of Ω cm.Even the dip-molded articles that still has the volume specific resistance in this scope in ultrapure water after soaking is more suitable for being used for the production of precision electronic element or semiconductor element.
Dip-molded articles of the present invention is to mould acquisition by dipping in dipping in of plastic cement dairy compositions.
The method for preparing dip-molded articles of the present invention can roughly be divided into two kinds of methods.
First preparation method of dip-molded articles is included in to dip on the mold tool to form to comprise and dips in dipping in of plastic cement dairy compositions and mould layer, this is dipped in mould layer and contact (below be also referred to as ' preparation method 1 ') with cats product.
Second preparation method of dip-molded articles comprises and adopts the plastic cement dairy compositions that dips in comprise rubber latex and cats product to become dipping in to form on the mold tool to comprise this and dip in dipping in of plastic cement dairy compositions and mould layer, vulcanizes this then and dips in and mould layer (below be also referred to as ' preparation method 2 ').
(first preparation method of dip-molded articles)
Describe above-mentioned preparation method 1 now below in detail.
With regard to used the dipping in regard to the plastic cement breast in the plastic cement dairy compositions of dipping in of being adopted among the preparation method 1, the rubber latex that can enumerate is for example natural rubber latex and synthesis of conjugate elastoprene latex.Particularly, preferably adopt synthesis of conjugate elastoprene latex from the angle of the production easness of dip-molded articles with desired characteristic.
Described synthesis of conjugate elastoprene latex is can to obtain with the monomeric polymerization of conjugate diene monomer copolymerization with other by conjugate diene monomer or conjugate diene monomer.
The example of conjugate diene monomer comprises 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2, the divinyl that 3-dimethyl-1,3-butadiene and halogen replace.They can use individually or with the array mode of two or more.Especially preferably adopt 1,3-butadiene.The consumption of conjugate diene monomer is preferably whole monomeric 30-89.5 weight %, more preferably 45-79 weight %.
Describedly can comprise olefinically unsaturated nitriles monomer, aromatic ethenyl monomer, ethylenically unsaturated carboxylic acids monomer, ethylenically unsaturated carboxylic acids ester monomer and ethylenically unsaturated carboxylic acids amide monomer with other monomeric example of conjugate diene monomer copolymerization.Especially preferably adopt olefinically unsaturated nitriles monomer, aromatic ethenyl monomer and ethylenically unsaturated carboxylic acids monomer, more preferably adopt olefinically unsaturated nitriles monomer and ethylenically unsaturated carboxylic acids monomer.
The monomeric example of olefinically unsaturated nitriles comprises vinyl cyanide and methacrylonitrile.Especially preferably adopt vinyl cyanide.
The example of aromatic ethenyl monomer comprises vinylbenzene, alpha-methyl styrene, monochlorostyrene and Vinyl toluene.
The monomeric example of ethylenically unsaturated carboxylic acids comprises olefinic unsaturated monocarboxylic acid such as vinylformic acid, methacrylic acid, Ba Dousuan and styracin; Unsaturated polycarboxylic acid of olefinic such as methylene-succinic acid, fumaric acid, toxilic acid and butylene three acid; Unsaturated polycarboxylic acid of the olefinic of partial esterification such as methylene-succinic acid mono ethyl ester, fumaric acid mono and butyl maleate.Preferred especially olefinic unsaturated monocarboxylic acid more preferably adopts methacrylic acid.
The monomeric example of ethylenically unsaturated carboxylic acids ester comprises methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, Jia Jibingxisuanβ-Qiang Yizhi, glycidyl acrylate, glycidyl methacrylate, (methyl) vinylformic acid N, N-dimethylamino ethyl ester and (methyl) vinylformic acid N, N-diethylamino ethyl ester.
The example of ethylenically unsaturated carboxylic acids amide monomer comprises (methyl) acrylamide and N-methylol (methyl) acrylamide.
Except that above-mentioned monomer, can adopt vinyl acetate, vinyl pyrrolidone, vinyl pyridine etc.
These monomers can be individually or with two or the form of more kinds of combinations use.
With regard to conjugated diene rubber latex, from the easness of showing effect of the present invention with obtain to have the angle of the dip-molded articles of flexible and excellent oil-proofness and physical strength, preferred adopt from comprise conjugate diene monomer, olefinically unsaturated nitriles monomer and the monomeric monomer mixture of ethylenically unsaturated carboxylic acids polymerization obtained those.In this case, composition ratio is preferably: conjugate diene monomer is 30-89.5 weight %, preferred 45-79 weight %, the olefinically unsaturated nitriles monomer is 10-50 weight %, preferred 20-40 weight %, the ethylenically unsaturated carboxylic acids monomer is 0.5-20 weight %, preferred 1-15 weight %.
Not only the preferred conjugated diene rubber latex with above-mentioned composition that adopts in preparation method 1 also preferably adopts this latex among the preparation method 2 that will describe below.
Described conjugated diene rubber latex can pass through conventional known emulsion polymerization usually, adopts above-mentioned monomer to prepare.
Dip in the plastic cement breast except that above-mentioned, described plastic cement dairy compositions also agent of preferred package Containing Sulfur and the vulcanization accelerator of dipping in, and, also have zinc oxide (if necessary).
With regard to vulcanizing agent, can adopt and dip in commonly used those in moulding, the example comprises sulphur such as Powdered sulphur, flowers of sulfur, precipitated sulfur, colloid sulphur, surface treated sulphur or insoluble sulphur; With polyamines such as hexamethylene-diamine, Triethylenetetramine (TETA) and tetren.Preferred especially sulphur.The consumption of vulcanizing agent is preferably the 0.1-10 weight part, for the latex solid content of 100 weight parts, and more preferably 0.2-4 weight part.
With regard to vulcanization accelerator, can adopt and dip in commonly used those in moulding, the example comprises dithiocarbamic acid such as diethyldithiocar bamic acid, dibutyl dithiocaarbamate, two-2-ethylhexyl dithiocarbamic acid, dicyclohexyl dithiocarbamic acid, phenylbenzene dithiocarbamic acid and dibenzyl aminodithioformic acid and zinc salt thereof; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, bisbenzothiazole base disulfide, 2-(2,4-dinitrophenyl sulphur) benzothiazole, 2-(N, N-diethyl thiocarbamyl sulfenyl) benzothiazole, 2-(2,6-dimethyl-4-morpholino sulfenyl) benzothiazole, 2-(4 '-morpholino disulfide group) benzothiazole, 4-morpholinyl-2-[4-morpholinodithio base disulfide and 1, two (the 2-[4-morpholinodithio base mercapto methyl) ureas of 3-.Preferred especially zinc dibutyl dithiocarbamate, 2-mercaptobenzothiazole and 2-mercaptobenzothiazole zinc.These vulcanization accelerators can be individually or with two or more kinds of array configurations use.
The consumption of vulcanization accelerator is preferably the 0.1-10 weight part, dips in plastic cement milk solids content meter, more preferably 0.2-4 weight part with respect to 100 weight parts.
The consumption of zinc oxide preferably is at most 5 weight parts, with respect to 100 weight parts dip in plastic cement milk solids content meter, more preferably be at most 2 weight parts.
The described plastic cement dairy compositions that dips in can also comprise pH regulator agent, thickening material, antiaging agent, dispersion agent, pigment, filler, tenderizer etc. as required, during they are generally used for dipping in and mould.
The described solids content concn that dips in the plastic cement dairy compositions is generally 20-40 weight %, preferred 25-35 weight %, and the pH that dips in the plastic cement dairy compositions is at least 8 usually, is preferably 9-11.
In preparation method 1 of the present invention, when comprise above-mentioned dip in dipping in of plastic cement dairy compositions mould layer dipping on the mold tool form after, this is dipped in moulds layer and contact with cats product.
Dip in regard to the mold tool with regard to described, it is for example made by porcelain, pottery, metal, glass, plastics etc.When described dip-molded articles was gloves, this molding die had the shape corresponding to the staff profile, and, wait that according to the spy target purposes of making gloves can take different shape, as comprise the shape from the wrist to the finger tip and comprise shape from the ancon to the finger tip.
With regard to above-mentionedly dipping in dipping in of plastic cement dairy compositions and mould with regard to the method for layer dipping on the mold tool to form to comprise, can adopt the conventional known molding process that dips in, the example comprises direct dipping method, anode agglutinant dipping method and Teague agglutinant dipping method.From being easy to obtain the angle of the uniform dip-molded articles of thickness, special preferred anodes agglutinant dipping method.
Under the situation of anode agglutinant dipping method, will dip in the mold tool usually and immerse in the agglutinant solution, agglutinant attached to mould on after, its immersion is dipped in the plastic cement dairy compositions, on this mould, form to dip in thus and mould layer.
Described agglutinant is not particularly limited, as long as it is the metal-salt ionogen, the example comprises metal halide such as bariumchloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; Nitrate such as nitrate of baryta, nitrocalcite and zinc nitrate; Acetate such as barium acetate, calcium acetate and zinc acetate; With vitriol such as calcium sulfate, sal epsom and Tai-Ace S 150.Special preferably calcium chloride and nitrocalcite.
Usually use agglutinant with the form of the aqueous solution, alcoholic solution or its mixture.Agglutinant concentration is generally 5-70 weight %, preferred 20-50 weight %.
In preparation method 1 of the present invention, must make described dip in mould the layer contact with cats product.
With regard to the cats product that is used for the present invention, can adopt routine known, the example comprises primary amine salt, secondary amine salt, tertiary ammonium salt and quaternary ammonium salt.Especially preferably adopt quaternary ammonium salt.
The example of primary amine salt comprises hydrochloride, vitriol, nitrate and the acetate of the primary amine of alkyl with substituting group such as 1-18 carbon atom, alkenyl, aryl or aralkyl.The lower limit of carbon number is 1 for alkyl in the above-mentioned substituting group, is 2 to alkenyl, is 6 to aryl, is 7 to aralkyl.To this restriction of carbon number lower limit applicable among the present invention to other substituent explanation.
The example of secondary amine salt comprises hydrochloride, vitriol, nitrate and the acetate of the secondary amine of alkyl with substituting group such as 1-18 carbon atom, alkenyl, aryl or aralkyl.
The example of tertiary ammonium salt comprises hydrochloride, vitriol, nitrate and the acetate of the tertiary amine of alkyl with substituting group such as 1-18 carbon atom, alkenyl, aryl or aralkyl.
The example of quaternary ammonium salt comprise that following formula (1) characterizes those, pyridinium salt and imidazole salts.
Formula (1)
In the formula, R
1-R
4The group that expression is selected from alkyl, alkenyl, aryl and the aralkyl of 1-18 carbon atom also can be same to each other or different to each other.X represents halogen atom.
The R that is used for the quaternary ammonium salt of preparation method's 1 Chinese style (1) sign
1-R
4The sum (being also referred to as the total number of carbon atoms in the substituting group) of institute's carbon atoms is preferably 5-30 in the substituting group of expression, 8-30 more preferably, more preferably 12-30 then, preferred especially 14-30.
The specific examples of the compound that formula (1) characterizes comprises Trimethyllaurylammonium chloride, bromination lauryl trimethyl ammonium, cetyltrimethylammonium chloride, cetrimonium bromide, chlorination stearyl trimethyl ammonium, bromination stearyl trimethyl ammonium, chlorination lauryl benzyl dimethyl ammonium, chlorination hexadecyl benzyl dimethyl ammonium, chlorination didecyldimethyl ammonium, Varisoft TA 100 and chlorination diallyl dimethyl ammonium.
The example of pyridinium salt comprises those that following formula (2) characterizes.
Formula (2)
In the formula, R
5-R
9Expression is selected from the group and the hydrogen atom of alkyl, alkenyl, aryl and the aralkyl of 1-18 carbon atom, and can be same to each other or different to each other.R
10Expression is selected from the group of alkyl, alkenyl, aryl and the aralkyl of 1-18 carbon atom.X represents halogen atom.
The specific examples of the compound that formula (2) characterizes comprises chloride laurylpyridine, bromination lauryl pyridine, cetylpyridinium chloride and brocide.
The example of imidazole salts comprises those that following formula (3) characterizes.
Formula (3)
In the formula, R
11And R
12The group that expression is selected from alkyl, alkenyl, aryl and the aralkyl of 1-18 carbon atom also can be same to each other or different to each other.R
13Expression is selected from the group of alkyl, alkenyl, aryl and the aralkyl of 12-24 carbon atom.X represents halogen atom.
The specific examples of the compound that formula (3) characterizes comprises chlorination 2-lauryl-N-methyl-N-lauryl imidazoles and chlorination 2-lauryl-N-ethyl-N-lauryl imidazoles.
In above-mentioned quaternary ammonium salt, those that preferred formula (1) characterizes, more preferably adopt cetyltrimethylammonium chloride, Trimethyllaurylammonium chloride, chlorination lauryl benzyl dimethyl ammonium and cetylpyridinium chloride, especially preferably adopt cetyltrimethylammonium chloride.
Owing to can realize dipping in and mould layer and contact, preferably with the form of the aqueous solution, alcoholic solution or its mixture use cats product with cats product is more uniform.Its concentration is not had specific limited, but be generally 0.1-10 weight %, preferred 0.1-5 weight %, more preferably 0.5-3 weight %.Cross when low when this concentration, the surface resistivity of the dip-molded articles that is obtained can uprise, and when it was too high, the effect that reduces surface resistivity arrived a platform, and will be difficult to remove dipping in and mould the excessive cats product that adheres on the layer.
Mould the method that contacts with cats product of layer and do not have special restriction for making to dip in, for example, adopt brush or spraying machine to apply to dip in one approach and mould layer, perhaps can adopt and to dip in the method for moulding in the layer immersion cats product solution with cats product solution.From realizing dipping in the more angle of uniform contact, a kind of method in preferred back of moulding between layer and the cats product.
When dipping in when moulding layer and immersing cats product solution, the temperature of this cats product solution is generally 0 ℃-80 ℃, and preferred 20 ℃-60 ℃, soak time was generally 1 second-10 minutes, preferred 30 seconds-5 minutes.
There is not specific limited layer opportunity that contacts with cats product of moulding for making to dip in, get final product after moulding layer so long as on dipping in the mold tool, form to dip in, but preferably carry out before moulding layer sulfuration dipping in, this is owing to can make dip-molded articles have lower surface resistivity like this.
Usually to make dipping in of being obtained mould layer by thermal treatment sulfuration (crosslinked).
Usually dipped in the sulfuration of moulding layer in 10-120 minute by heating under 80 ℃-150 ℃ temperature.With regard to heating means, can adopt infrared rays or warm air outside heating method or high frequency waves inside heating method.Especially preferably use warm air beating.
Can before sulfuration, make dip in mould the layer leach.Usually mould layer and in 20 ℃-60 ℃ hot water, soak and leached in about 1-30 minute by dipping in dipping on the mold tool.This leaches operation can remove to dip in and mould water-soluble impurity contained in the layer (for example excessive emulsifying agent or agglutinant etc.), gives the physical strength of dip-molded articles excellence thus.
Can carry out this after moulding layer sulfuration and leach operation dipping in, but, preferably before dipping in the sulfuration of moulding layer, carry out from more effectively removing the viewpoint of water-soluble impurity.
Dip in mould layer sulfuration after, make the vulcanizate that obtained from dipping on the mold tool demoulding so that dip-molded articles to be provided.This release method can adopt such method: it comprises and utilizes hand to peel off or peel off with hydraulic pressure or compressed air pressure from mould.After the demoulding, can make it under 60 ℃-120 ℃ temperature, stand 10-120 minute thermal treatment.
(second preparation method of dip-molded articles)
In preparation method 2 of the present invention, adopt by what add in rubber latex that cats product forms and dip in the plastic cement dairy compositions.
With regard to described rubber latex, can adopt those that in preparation method 1, enumerate as an example, preferred adopt those with preparation method 1 in identical.
Do not have specific limited for the cats product that in rubber latex, adds, can adopt cited as an example those among the preparation method 1.Preferred especially quaternary ammonium salt.With regard to quaternary ammonium salt, those that formula (1) is characterized, the imidazole salts that pyridinium salt that formula (2) is characterized and formula (3) are characterized can adopt equally, but preferred formula (1) characterize those.
In preparation method (2), the R in formula (1)
1-R
4The total number of carbon atoms (the total number of carbon atoms in the substituting group) contained in the represented substituting group is preferably 5-30, more preferably 8-30.
Especially preferably adopt cetyltrimethylammonium chloride and chlorination diallyl dimethyl ammonium.
The consumption of cats product is preferably the 0.01-5 weight part, with respect to 100 parts by weight of rubber latex polymer meters, and more preferably 0.05-3 weight part, preferred especially 0.1-2 weight part.Cross when low when the cats product consumption, may not can obtain desirable low surface resistivity, measure when excessive, may destroy the stability of dipping in the plastic cement dairy compositions when this.
With regard to regard to the method that adds cats product in the rubber latex, preferably the form with the aqueous solution adds cats product.The concentration of aqueous solution of cationic surfactant active is preferably 0.1-20 weight %, more preferably 0.1-15 weight %.When employing has the aqueous solution of cationic surfactant active of above-mentioned scope concentration, can suppress the formation of thick aggregate in the interpolation process, can prepare the stable plastic cement dairy compositions that dips in.
When above-mentioned aqueous solution of cationic surfactant active has 13 or during bigger the total number of carbon atoms in its substituting group, the preferred basic cpd that adds, its pH is preferably 9 or higher like this, more preferably 9.5 or higher, preferred especially 9.5-13 is when the total number of carbon atoms in the substituting group is 5-12, the preferred pH that regulates, make it to be preferably at least 5.5, more preferably be at least 6, preferred especially 6-8.When the pH of aqueous solution of cationic surfactant active to be added crosses when low, rubber latex may condense.
Described basic cpd there is not special restriction; Can adopt potassium hydroxide, sodium hydroxide, ammonium hydroxide etc., preferred especially potassium hydroxide or sodium hydroxide.
After cats product is added rubber latex, the ageing that mixture was stood under 5 ℃-50 ℃ 30 minutes-24 hours.This ageing makes cats product be evenly dispersed in the latex polymer and makes and prepares more that the dip-molded articles of low surface resistivity becomes possibility.
Except that above-mentioned main points, be used for preparation method 2 dip in the plastic cement dairy compositions aspects such as vulcanizing agent, vulcanization accelerator, other additive, solids content concn, pH taked with preparation method 1 in identical condition.
Preparation method 2 is included in to dip on the mold tool to form to comprise and above-mentionedly dips in dipping in of plastic cement dairy compositions and mould layer, vulcanizes this then and dips in and mould layer.
Adopt among the preparation method 2 dip in the mold tool, dip in molding process, describe among the method for cure conditions, demoulding vulcanizate etc. and the preparation method 1 those are identical.Yet, in preparation method 2, owing to use the above-mentioned plastic cement dairy compositions that dips in that the dip-molded articles with enough low surface resistivities can be provided, needn't make dipping in of being obtained mould layer and contact with cats product.
Can make dip-molded articles of the present invention have the thickness of the about 3mm of about 0.1-, and be especially suitable for use as the slim product that thickness is the about 0.3mm of 0.1-through preparation.Its specific examples comprises curable product such as baby milk bottle neck, dropper, flexible pipe or thermos flask; Toy or sports equipment such as balloon, doll or ball; Industrial products such as pressure forming bag or gas-storing bag; Various gloves; And fingerstall.It is suitable as gloves, and the example comprises surgery, family, agricultural, fishery and industrial no bearing type gloves and bearing type gloves.Dip-molded articles of the present invention has low surface resistivity, and it is suitable as precision electronic element production and semiconductor element production gloves.
(embodiment)
Below illustrate in greater detail the present invention by reference example.' part ' and ' % ' in below describing is all based on the weight meter, except as otherwise noted.
By following rubber gloves are evaluated.
(immersing ultrapure water surface resistivity and volume specific resistance before)
Downcut the square sample of 10cm from the palm portion of the rubber gloves that obtain.
After this sample being placed spend the night, under the measuring voltage of 250V,, under identical atmosphere, measure the surface resistivity and the volume specific resistance of this sample according to ASTM D257-93 in 20 ℃, the climatic chamber of 65% relative humidity.The higher limit of this measurement is respectively 3.8 * 10
10Ω/sum of squares 3.8 * 10
11Ω cm.
(immersing ultrapure water surface resistivity and volume specific resistance afterwards)
Downcut the square sample of 10cm from the palm portion of the rubber gloves that obtain, and be in the ultrapure water that 30 ℃, resistivity are 18.3M Ω cm at 500ml and soaked 2 hours, after the immersion, at 70 ℃ of dry samples down.After the drying, after this sample being placed spend the night, under the measuring voltage of 250V,, under identical atmosphere, measure the surface resistivity and the volume specific resistance of this sample in 20 ℃, the climatic chamber of 65% relative humidity according to ASTMD257-93.The higher limit of this measurement is respectively 3.8 * 10
10Ω/sum of squares 3.8 * 10
11Ω cm.
(embodiment 1)
By being dispersed in 3.5 parts of water, 1 part of sulphur, 0.5 part of zinc diethyldithiocarbamate, 0.5 part of zinc oxide and 1.5 parts of titanium oxide prepared the vulcanizing agent dispersion liquid.
7 parts of above-mentioned vulcanizing agent dispersion liquids are being added 250 parts of acrylonitrile-butadiene-Sipacril 2739OF latex (1, the 3-butadiene unit accounts for 67.5%, acrylonitrile unit accounts for 27%, methacrylic acid unit accounts for 5.5%, solids content concn is 40%, the pH=8.5 of latex) afterwards, potassium hydroxide solution and water are 9.5 to obtain pH to wherein adding, solids content concn be 30% dip in the plastic cement dairy compositions.
Will be after 60 ℃ down the hand shape moulds of heating immerse 25% calcium nitrate aqueous solution (agglutinant solution), with its 60 ℃ dry 10 minutes down.This hand shape mould that has adhered to agglutinant is immersed above-mentioned dipping in 10 seconds in the plastic cement dairy compositions, on this hand shape mould, form to dip in and mould layer.Then it was soaked 2 minutes in 30 ℃ 1% the cetyltrimethylammonium chloride aqueous solution, leached 5 minutes with deionized water at 40 ℃ then.Then 60 ℃ dry 10 minutes down, then 120 ℃ down sulfuration this dip in and moulded layer 20 minutes.The upset gloves with the demoulding from the hand shape mould of the vulcanizate that obtained, obtain rubber gloves.Evaluate these rubber gloves and in table 1, provide the result.
(embodiment 2)
With with embodiment 1 in identical mode obtained rubber gloves, except the concentration with cetyltrimethylammonium chloride becomes 2% from 1%.Evaluate these rubber gloves and in table 1, provide the result.
(embodiment 3)
With with embodiment 1 in identical mode obtained rubber gloves, except replacing cetyltrimethylammonium chloride with Trimethyllaurylammonium chloride.Evaluate these rubber gloves and in table 1, provide the result.
(embodiment 4)
With with embodiment 1 in identical mode obtained rubber gloves, except replacing cetyltrimethylammonium chloride with cetylpyridinium chloride.Evaluate these rubber gloves and in table 1, provide the result.
(embodiment 5)
With with embodiment 1 in identical mode obtained rubber gloves, except replacing cetyltrimethylammonium chloride with chlorination lauryl benzyl dimethyl ammonium.Evaluate these rubber gloves and in table 1, provide the result.
(embodiment 6)
With with embodiment 1 in identical mode obtained rubber gloves, except moulding layer sulfuration back and before the demoulding from hand shape mould dipping in, add following program: it is immersed in aqueous sodium hypochlorite solution with the surface of this vulcanizate of chlorination, neutralize with potassium hydroxide aqueous solution then.Evaluate these rubber gloves and in table 1, provide the result.
(Comparative Examples 1)
With with embodiment 1 in identical mode obtained rubber gloves, except not carrying out the immersion in the 1% cetyltrimethylammonium chloride aqueous solution.Evaluate these rubber gloves and in table 1, provide the result.
Table 1
| Embodiment | Comparative Examples | ||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 1 | |
| Surface resistivity (* 10 before in ultrapure water, soaking 9Ω/square) volume specific resistance (* 10 10Ωcm) | 0.65 1.4 | 0.72 0.78 | 0.28 0.29 | 0.51 1.0 | 0.25 0.95 | 1.3 2.1 | 38＜ 2.2 |
| Surface resistivity (* 10 after in ultrapure water, soaking 9Ω/square) volume specific resistance (* 10 10Ωcm) | 4.7 3.7 | 2.0 2.5 | 0.87 0.38 | 3.2 6.5 | 1.9 5.9 | 1.2 1.7 | 38＜ 38＜ |
Following as can be seen from Table 1 result.
The surface resistivity of conventional rubber gloves surpasses 10
10Ω/square, by it is soaked its volume specific resistance further raise (Comparative Examples 1) in ultrapure water.
Compare with this Comparative Examples, have low surface resistivity by contact the rubber gloves of the present invention that obtain with cats product, even they are immersed in the ultrapure water, its surface resistivity still is lower than 10
10Ω/square (embodiment 1-6).Rubber gloves of the present invention are suitable for the production of precision electronic element or semiconductor element.
(embodiment 7)
By the potassium hydroxide aqueous solution of adding 5% in 10% the cetyltrimethylammonium chloride aqueous solution pH is transferred to 10 and prepared aqueous solution of cationic surfactant active.
With 1 part of sulphur, 0.5 part zinc diethyldithiocarbamate, 0.5 part zinc oxide and 1.5 parts of titanium oxide add 250 parts of acrylonitrile-butadiene-Sipacril 2739OF latex (1, the 3-butadiene unit accounts for 67.5%, acrylonitrile unit accounts for 27%, methacrylic acid unit accounts for 5.5%, solids content concn is 40%, the pH=8.5 of latex) after, to wherein adding potassium hydroxide and water to form 9.5 pH value and 30% solids content concn, then with 0.5 part of cetyltrimethylammonium chloride with respect to 100 parts of rubber latex polymer ratio to wherein adding above-mentioned aqueous solution of cationic surfactant active, obtain dipping in the plastic cement dairy compositions.Under agitation, make this dip in the plastic cement dairy compositions, filter with 80 purpose wire-mesh screens 30 ℃ of following ageings 16 hours.Do not observe agglutinator.
Will 60 ℃ down the ceramic hand shape moulds of heating be immersed in 25% the calcium nitrate aqueous solution, this solution is moulded agglutinant solution for dipping in, and takes out and 60 ℃ of dryings 10 minutes down.This hand shape mould that will adhere to agglutinant soaks 10 seconds and taking-up above-mentioned dipping in the plastic cement dairy compositions, form to dip in thus on this hand shape mould and mould layer.Then it is stood 5 minutes leaching in 40 ℃ deionized water, drying is 10 minutes under 60 ℃, this is dipped in mould layer 120 ℃ of sulfurations 20 minutes then.The upset gloves are with the demoulding from the hand shape mould of the vulcanizate that obtained, to obtain rubber gloves.Before immersing ultrapure water and measure the surface resistivity of these rubber gloves afterwards and result that volume specific resistance is obtained is provided in the table 2.
(embodiment 8)
Repeat the program of embodiment 1, dip in the plastic cement dairy compositions with respect to the ratio preparation of 100 parts of latex polymers except change into 1 part of cetyltrimethylammonium chloride by the amount that embodiment 7 is added the aqueous solution of cationic surfactant active in the rubber latex.Be provided in the table 2 measuring the surface resistivity of the rubber gloves that obtained and the result that volume specific resistance obtains.
(embodiment 9)
1% aqueous sodium hypochlorite solution, soaked for 10 seconds with implementing the rubber gloves that the demoulding obtains from hand shape mould by upset in 7, in 0.64% aqueous hydrochloric acid, soaked for 10 seconds then, make the surface chlorination of dip-molded articles thus.Washed these gloves 20 minutes with 30 ℃ flowing water then, then 80 ℃ dry 1 hour down, nurse one's health by it was placed yesterday in the environment of 20 ℃ and 65% relative humidity then.Measurement is through the surface resistivity and the volume specific resistance of the gloves of conditioning.The result is provided in the table 2.
(embodiment 10)
With with embodiment 7 in identical mode prepared gloves, except prepare the 10% chlorination diallyl dimethyl ammonium aqueous solution as cats product, after pH is transferred to 6.5, add this solution and obtain dipping in the plastic cement dairy compositions with respect to 100 parts of rubber latex polymer ratio with 1 part of chlorination diallyl dimethyl ammonium.With with embodiment 9 in identical mode chlorination, washing, drying and conditioning are carried out to obtain rubber gloves in the surface of these gloves.Will be before immersing ultrapure water and measure the surface resistivity of these rubber gloves afterwards and result that volume specific resistance is obtained is provided in the table 2.
(Comparative Examples 2)
Repeat the program of embodiment 7, except in rubber latex, not adding aqueous solution of cationic surfactant active.The result that the rubber gloves surface resistivity that measure to obtain and volume specific resistance are obtained is provided in the table 2.
(Comparative Examples 3)
Will with Comparative Examples 1 in the gloves that obtain of same way as be immersed in the aqueous sodium hypochlorite solution, stand subsequently with embodiment 9 in the processing of same way as.Measurement is through the surface resistivity and the volume specific resistance of the gloves of conditioning.The result is provided in the table 2.
Table 2
| Embodiment | Comparative Examples | |||||
| 7 | 8 | 9 | 10 | 2 | 3 | |
| Surface resistivity (* 10 before in ultrapure water, soaking 9Ω/square) volume specific resistance (* 10 10Ωcm) | 0.89 1.7 | 0.17 0.68 | 1.6 3.3 | 1.0 2.9 | 38＜ 38＜ | 28 19＜ |
| Surface resistivity (* 10 after in ultrapure water, soaking 9Ω/square) volume specific resistance (* 10 10Ωcm) | 0.99 1.2 | 0.58 2.6 | 5.6 4.9 | 2.3 3.5 | 38＜ 38＜ | 38＜ 38＜ |
As shown in table 2, the dip-molded articles that method produced according to the invention obtains all has and is lower than 10
10Ω/square surface resistivity and be lower than 10
11The volume specific resistance of Ω/cm is low-resistivity, even and after immersing ultrapure water still low (embodiment 7-10).
On the other hand, conventional rubber gloves have above 10
10Ω/square surface resistivity and surpass 10
11The volume specific resistance of Ω/cm (Comparative Examples 2 and 3)
Can obtain to have the dip-molded articles of low surface resistivity in accordance with the present production process, even after with the ultrapure water washing, this surface resistivity still is lower than the surface resistivity of conventional moulded parts.
Claims (20)
1, a kind of dip-molded articles, its surface resistivity that has is measured as 10 under the atmosphere of 20 ℃ and 65% relative humidity
7-10
10Ω/square.
2, the dip-molded articles of claim 1, wherein dip-molded articles surface resistivity after 2 hours in being immersed in 30 ℃ ultrapure water is measured as 10 under the atmosphere of 20 ℃ and 65% relative humidity
7-10
10Ω/square.
3, claim 1 or 2 dip-molded articles, wherein the volume specific resistance of dip-molded articles is measured as 10 under the atmosphere of 20 ℃ and 65% relative humidity
8-10
11Ω 2cm.
4, any one dip-molded articles among the claim 1-3, wherein dip-molded articles volume specific resistance after 2 hours in being immersed in 30 ℃ ultrapure water is measured as 10 under the atmosphere of 20 ℃ and 65% relative humidity
9-10
11Ω 2cm.
5, any one dip-molded articles among the claim 1-4, wherein dip-molded articles is gloves.
6, any one dip-molded articles among the claim 1-5, wherein dip-molded articles is the gloves that are used for precision electronic element production or semiconductor element production.
7, the preparation method of dip-molded articles, this method are included in to dip on the mold tool to form to comprise and dip in dipping in of plastic cement dairy compositions and mould layer, this is dipped in mould layer and contact with cats product.
8, the dip-molded articles preparation method of claim 7, cats product wherein is that the form of the aqueous solution, alcoholic solution or its mixing solutions of 0.1～10 weight % is used with concentration.
9, claim 7 or 8 dip-molded articles preparation method, cats product wherein is a quaternary ammonium salt.
10, the dip-molded articles preparation method of claim 9, quaternary ammonium salt wherein is a cetyltrimethylammonium chloride.
11, a kind of plastic cement dairy compositions that dips in, it comprises the rubber latex that is added with cats product.
12, claim 11 dip in the plastic cement dairy compositions, composition wherein comprises the aqueous solution of cationic surfactant active that cationic surfactant concentration is 0.1-20 weight %.
13, claim 11 or 12 dip in the plastic cement dairy compositions, wherein the consumption of cats product is the 0.01-5 weight part, forms the polymkeric substance of described rubber latex with respect to 100 weight parts.
14, any one plastic cement dairy compositions that dips among the claim 11-13, cats product wherein is a quaternary ammonium salt.
15, claim 14 dip in the plastic cement dairy compositions, quaternary ammonium salt wherein is a cetyltrimethylammonium chloride.
16, claim 14 dip in the plastic cement dairy compositions, quaternary ammonium salt wherein is the chlorination diallyl dimethyl ammonium.
17, any one plastic cement dairy compositions that dips among the claim 11-16, rubber latex wherein is a conjugated diene rubber latex.
18, claim 17 dips in the plastic cement dairy compositions, conjugated diene rubber latex wherein is copolymer emulsion, this multipolymer comprises the conjugated diene monomeric unit of 30-89.5 weight %, the ethylenically unsaturated carboxylic acids monomeric unit of the olefinically unsaturated nitriles monomeric unit of 10-50 weight % and 0.5-20 weight %.
19, the preparation method of dip-molded articles, this method are included in to dip on the mold tool to form and comprise the dipping in of plastic cement dairy compositions of dipping in any among the claim 11-18 and mould layer, vulcanize this then and dip in and mould layer.
20, the dip-molded articles preparation method of claim 19 wherein as dipping in the formation method of moulding layer, adopts anode agglutinant dipping method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003027771 | 2003-02-05 | ||
| JP27771/2003 | 2003-02-05 | ||
| JP111226/2003 | 2003-04-16 |
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| Publication Number | Publication Date |
|---|---|
| CN1745126A true CN1745126A (en) | 2006-03-08 |
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ID=36139980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480003410 Pending CN1745126A (en) | 2003-02-05 | 2004-02-02 | Dip molded article with low surface resistivity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172187A (en) * | 2019-05-30 | 2019-08-27 | 深圳市兴业卓辉实业有限公司 | A kind of formula, technique and the latex finger cot of high-cleanness antistatic latex finger cot raw material |
| EP3749515A4 (en) * | 2018-02-08 | 2021-11-17 | Shen Wei (USA) Inc. | Multilayered thin chemical resistant article and manufacturing method |
-
2004
- 2004-02-02 CN CN 200480003410 patent/CN1745126A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3749515A4 (en) * | 2018-02-08 | 2021-11-17 | Shen Wei (USA) Inc. | Multilayered thin chemical resistant article and manufacturing method |
| CN110172187A (en) * | 2019-05-30 | 2019-08-27 | 深圳市兴业卓辉实业有限公司 | A kind of formula, technique and the latex finger cot of high-cleanness antistatic latex finger cot raw material |
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