CN100467520C - Dip forming composition and dip formed article - Google Patents

Abstract

A dip formed article that has good texture, excelling in not only tensile strength but also flexing fatigue and that itself does not tend to suffer coloration even when the article is worn and operation is continued; and a dip forming composition capable of providing such a dip formed article. There is provided a dip forming composition comprising a conjugated diene rubber latex and an organic peroxide, wherein providing that X refers to the 10 hr half-life temperature ( DEG C) of organic peroxide and Y refers to the octanol-water distribution coefficient of organic peroxide, the organic peroxide satisfies the formulae: 11 >= Y >= 2 (1), and 100 - 2Y >= X >= 70 - 2Y (2). There is further provided a dip formed article obtained from the composition.

Description

Dipping composition and dipping goods

Technical field

The present invention relates to dipping composition and dipping goods.

Background technology

Rubber gloves is widely used in household application, industrial application, the application during for example foodstuffs industry and electronics are made, and medical applications.Require rubber gloves to have various characteristics, make it to be stretched and, be unlikely to tired (promptly wearing) wearing the time spent hand for a long time like this with comfortable along with finger motion by more weak power, and its should not break (being enough tensile strengths) during operation.

In addition, especially, have such problem sometimes, promptly when operate continuously makes the finger motion that has on them, point crotch can ftracture (promptly low flexing fatigue life) for thin rubber gloves.

Usually, rubber gloves as oil-proofness with high tensile and excellence, usually use those rubber glovess by the dipping acquisition of dipping composition, described dipping composition comprises carboxylation acrylonitrile butadiene copolymer latex, sulphur and curing catalyst.

For example, patent documentation 1 discloses the dipping rubber gloves by the dipping composition production, and described dipping composition comprises carboxylation acrylonitrile-butadiene rubber latex, zinc oxide, sulphur and curing catalyst.Such gloves are being worn the time spent as snug as a bug in a rug, but have poor tensile strength.Therefore wear with during break easily.

In addition, patent documentation 2 discloses the dipping gloves from a kind of dipping composition production, and this dipping composition comprises carboxylation acrylonitrile butadiene copolymer latex, sulphur and curing catalyst, but oxygen-free zinc.Such gloves have high tensile, have reduced and have worn the danger of time spent generation disruptive, but worn with uncomfortable.

In addition, patent documentation 3 discloses the dipping rubber gloves from the dipping composition production, this dipping composition comprises the acrylonitrile butadiene copolymer latex of the carboxylic group that contains specified quantitative, small amounts of zinc, relatively large sulphur and curing catalyst.Yet when having on the operation of its long-time continuous, itself takes place variable color in such gloves sometimes, and this greatly reduces its commercial value.

In addition, the above-mentioned rubber gloves of making by the dipping of dipping composition (it comprises as the sulphur of necessary component and curing catalyst), though aspect flexing fatigue life, be more excellent, but the time occur paintedly sometimes when having on the operation of its long-time continuous, this has reduced its commercial value significantly.

On the other hand, also after deliberation a kind of like this method of making the dipping goods, wherein organo-peroxide is used as linking agent, and does not use sulphur and curing catalyst.

For example, patent documentation 4 discloses the dipping by the dipping composition, dipping goods that obtain in chemically inactive molten salt bath, carrying out crosslinked under the quite high temperature then, yet wherein said dipping composition comprises and the organo-peroxide natural or synthetic rubber latex of dicumyl peroxide or di-t-butyl peroxide preparation for example., such rubber gloves, though it has wearing comfort and enough tensile strengths, but have at production period painted problem takes place when being exposed to high temperature, and low flexing fatigue life problem, the latter causes causing finger crotch cracking in 2-3 hour use.

Patent documentation 1: United States Patent (USP) 5,014,362

Patent documentation 2:WO 97/48765

Patent documentation 3:WO 00/21451

Patent documentation 4:WO 01/77210

Summary of the invention

The problem to be solved in the present invention

Based on above-mentioned viewpoint, the purpose of this invention is to provide the dipping goods, it has wearing comfort, excellent tensile strength and high flexing fatigue life, and even when described goods worn continuously with and itself also be not inclined to painted when operating; And the dipping composition that such dipping goods can be provided.

Solve the means of described problem

The present inventor has carried out deep research to using organo-peroxide as the dipping goods of linking agent preparation, and finds that above-mentioned purpose can reach by the dipping composition that use comprises conjugated diene rubber latex and specific organo-peroxide.Based on this discovery, they have finished the present invention.

Therefore, the invention provides the dipping composition, it comprises conjugated diene rubber latex and organo-peroxide, wherein said organo-peroxide satisfies following formula (1) and (2), condition be X 10-hour half life temperature referring to organo-peroxide (℃), and Y refers to the octanol-water partition coefficient of organo-peroxide:

11≥Y≥2 (1)

100-2Y≥X≥70-2Y (2)

In addition, the invention provides the dipping goods of the dipping preparation by above-mentioned dipping composition.

Advantageous effects of the present invention

The invention provides a kind of dipping goods, it has wearing comfort, excellent tensile strength and high flexing fatigue life, and even worn when these goods and itself also to be not inclined to painted with operate continuously the time; And the dipping composition that such dipping goods can be provided.

Embodiment

Below will describe the present invention in detail.

Dipping composition of the present invention comprises conjugated diene rubber latex and specific organo-peroxide.

(conjugated diene rubber latex)

The conjugated diene rubber latex that is used for the present invention is not limited especially, as long as it comprises conjugated diene monomeric unit.For example, can mention the synthetic rubber latex of the emulsion polymerization prepared of natural rubber latex and the monomer mixture by comprising conjugate diene monomer necessarily.The preferred synthetic rubber latex that uses in the middle of them is because can at random regulate the various characteristics of dipping product.Preferred synthetic rubber latex be by comprise conjugate diene monomer, ethylenic unsaturated acid monomer and another kind of can with the conjugated diene rubber latex of the emulsion polymerization prepared of the monomeric monomer mixture of their copolymerizations.Use the ethylenic unsaturated acid monomer to provide to have the dipping goods of excellent tensile strength necessarily.

As conjugate diene monomer, for example can mention 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-divinyl, 1,3 one pentadienes, chloroprene or the like. especially, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is preferred.These conjugate diene monomers can use individually or use with two or more mixture.

The amount of conjugate diene monomer accounts for total monomer and is preferably 30-90 weight %, more preferably 50-84 weight %, especially preferably 55-81 weight %.Too small amount tends to obtain having the goods of poor feel, and excessive amount tends to obtain having the goods of low tensile strength.

As the ethylenic unsaturated acid monomer, can mention the ethylenically unsaturated monomer that for example comprises carboxyl, comprise sulfonic ethylenically unsaturated monomer, comprise ethylenically unsaturated monomer of phosphate or the like.

As the ethylenically unsaturated monomer that comprises carboxyl, can mention for example olefinic unsaturated monocarboxylic, for example vinylformic acid, methacrylic acid, Ba Dousuan or the like; The unsaturated poly carboxylic acid of olefinic or its acid anhydrides be fumaric acid, toxilic acid, methylene-succinic acid, maleic anhydride, itaconic anhydride or the like for example; And the unsaturated polycarboxylic partial ester of olefinic, oxysuccinic acid methyl esters for example, methylene-succinic acid methyl esters or the like.

As comprising sulfonic ethylenically unsaturated monomer, can mention for example vinyl sulfonic acid, methyl ethylene sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid, 2-alkylsulfonyl ethyl (methyl) acrylate, 2-acrylamido-2-hydroxy-propanesulfonic acid or the like.

As the ethylenically unsaturated monomer that comprises phosphate, can mention 3-chloro-2-propyl group phosphoryl (methyl) vinylformic acid, 2-ethyl phosphoryl (methyl) vinylformic acid, 3-allyloxy-2-hydroxy propane phosphoric acid or the like.

These ethylenic unsaturated acid monomers can be used as an alkali metal salt or ammonium salt is used, and can use individually or use with two or more mixture.

In the middle of above-mentioned ethylenic unsaturated acid monomer, the ethylenically unsaturated monomer that comprises carboxyl is preferred. the olefinic unsaturated monocarboxylic is preferred, and methacrylic acid is particularly preferred.

The monomeric amount of ethylenic unsaturated acid accounts for total monomer and is preferably 0.5-10 weight %, more preferably 1-9 weight %, and preferred especially 2-8 weight %.Too small amount tends to obtain having the goods of low tensile strength, and excessive amount tends to obtain having the goods of poor feel.

As can with the another kind of monomer of conjugate diene monomer and ethylenic unsaturated acid monomer copolymerizable, though do not limited especially, can be mentioned for example aromatic vinyl monomer, for example vinylbenzene, alpha-methyl styrene, monochloro vinylbenzene, dichlorostyrene, trichlorobenzene ethene, monomethyl vinylbenzene, dimethyl styrene, Three methyl Benzene ethene, hydroxymethyl vinylbenzene or the like; The olefinically unsaturated nitriles monomer, vinyl cyanide for example, methacrylonitrile, 2-chloroacrylonitrile, 2-butylene nitrile or the like; The unsaturated carboxylic acid amides monomer of olefinic, acrylamide for example, Methacrylamide, N,N-DMAA, N hydroxymethyl acrylamide or the like; The ethylenically unsaturated carboxylic acids alkyl ester monomer, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA or the like; Vinyl carboxylic acid ester monomers, vinyl acetate for example, propionate, vinyl barthatate or the like; Halogenated vinyl monomer, vinylchlorid for example, vinylidene chloride, vinyl fluoride, vinylidene fluoride or the like; Olefinic monomer is ethene for example, propylene, 1-butylene, iso-butylene or the like; Vinyl ether monomers, methylvinylether for example, n-propyl vinyl ether, isobutyl vinyl ether, dodecyl vinyl or the like; (methyl) allylic cpd, allyl acetate for example, methylallyl acetate, chlorallylene, methylallyl chloride or the like; The vinyl silyl compound is trimethoxyvinylsilane for example; Vinyl pyridine; With N-vinyl pyrrolidone or the like.These can use separately or use with two or more mixture.

In the middle of these other monomers, preferably use aromatic vinyl monomer, olefinically unsaturated nitriles monomer and ethylenically unsaturated carboxylic acids alkyl ester monomer.Considering to provide the goods of the dipping with high tensile, and aromatic monomer and olefinically unsaturated nitriles monomer are preferred.In addition, considering to provide the dipping of oil-proofness excellence goods, and the olefinically unsaturated nitriles monomer is preferred.

It is preferred 0-69.5 weight % that above-mentioned other monomeric amounts account for total monomer, more preferably 7-49 weight %, and preferred especially 11-43 weight %.In this scope, the tensile strength of goods, oil-proofness and feel have obtained good maintenance.

Spendable in the present invention synthetic rubber latex is by the emulsion polymerization prepared of above-mentioned monomer mixture.As method of emulsion polymerization, can use methods known in the art, and not restriction especially.

For the letex polymerization of above-mentioned monomer mixture, can use to be used for the polymeric auxiliary agent for example normally used emulsifying agent, initiator and molecular weight regulator. the adding mode of these auxiliary agents is not limited especially.They can be added at first at once, add in batches or add continuously.

As emulsifying agent, though restriction especially can be mentioned for example anionic emulsifier, alkylbenzene sulfonate for example, aliphatic sulfonate, salt of the sulfuric ester of higher alcohols or the like; Nonionic emulsifying agent, polyethylene glycol alkyl ether for example, polyalkylene glycol alkyl ester, polyalkylene glycol alkyl phenyl ether or the like; Amphoteric emulsifier, it comprises carboxylate salt, sulphate esters, sulfonate, phosphoric acid ester or phosphate ester as anionicsite, and amine salt or quaternary ammonium are as cationic moiety.Especially, preferably use anionic emulsifier.

The amount of emulsifying agent is based on total monomer of 100 weight parts 0.5-10 weight part normally, preferred 1-8 weight part, and more preferably 2-5 weight part.

As initiator, though restriction especially can be mentioned for example inorganic peroxide, Sodium Persulfate for example, Potassium Persulphate, ammonium persulphate, potassium superphosphate, hydrogen peroxide or the like; Organo-peroxide, tert-butyl peroxide for example, cumene hydroperoxide, right The alkane hydroperoxide, di-t-butyl peroxide, tert butyl isopropyl benzene peroxide, acetyl peroxide, peroxidation isobutyryl, peroxidation decoyl, dibenzoyl peroxide, 3,5,5-trimethyl acetyl base superoxide, t-butyl peroxy isobutyrate or the like; Azo-compound, Diisopropyl azodicarboxylate for example, azo is two-2,4-methyl pentane nitrile, the two cyclohexanenitriles of azo, two isobutyrates of dimethyl azo or the like.These initiators can use separately or use with two or more mixture.Superoxide can also with reductive agent for example sodium bisulfite use as redox initiator.As initiator, preferably using inorganic or organo-peroxide. inorganic peroxide is preferred, and persulphate is particularly preferred.

The amount of initiator is generally the 0.01-2 weight part based on total monomer of 100 weight parts, preferred 0.05-1.5 weight part.

As molecular weight regulator, though not restriction especially can be mentioned for example alpha-methyl styrene dimer; Mercaptan, uncle's lauryl mercaptan for example, n-dodecyl mercaptan, spicy thioalcohol or the like; Halohydrocarbon, tetracol phenixin for example, methylene dichloride, methylene bromide or the like; And sulfocompound, tetraethylthiuram disulfide for example, dipentamethylene thiuram disulfide, curing di-isopropyl xanthan or the like.These can use separately or use with two or more mixture.Especially, preferably use mercaptan, and uncle's lauryl mercaptan is particularly preferred.

The preferred amount of molecular weight regulator though depend on the kind of conditioning agent, is the 0.1-0.8 weight part based on total monomer of 100 weight parts.0.2-0.7 the scope of weight part is preferred.

Mode as the monomer adding, can mention the monomer that for example wherein will react and once be added mode in the reactor, wherein they are along with polymeric carries out by continuously or the mode that adds step by step, wherein a part of monomer is added into and reacts up to specific transformation efficiency, add residual monomers then continuously or step by step in further polymeric mode or the like, and can make in any way.When monomer mixture is added fashionablely continuously or step by step, the composition of mixture can be constant or variation.

In addition, every kind of monomer can be pre-mixed by the monomer that will use and add reactor or add reactor respectively.

Letex polymerization is carried out in water usually.The amount that is used for the water of letex polymerization is generally the 80-500 weight part based on total monomer of 100 weight parts, preferred 100-200 weight part.

In addition, if necessary, can make for example sequestrant of used additives, dispersion agent, pH regulator agent, oxygen scavenger, size of particles conditioning agent or the like. the kind of auxiliary agent and amount are unrestricted.

Though polymerization temperature is not particularly limited, be generally 0-95 ℃, preferred 5-70 ℃.

When monomer mixture carries out letex polymerization and reaches predetermined transformation efficiency, by system cools or adding terminator are stopped polyreaction.Transformation efficiency when polymerization is terminated is preferably 90 weight % or higher, more preferably 93 weight % or higher.

After polymerization is terminated, as required, unreacted monomer is removed, and solids content and pH value are regulated, with preparation synthetic rubber latex.

If necessary, can in the conjugated diene rubber latex that is used for the present invention, add antioxidant, sanitas, sterilant, dispersion agent, UV light absorber, pH regulator agent or the like.

(organo-peroxide)

The invention is characterized in the use organo-peroxide, wherein organo-peroxide satisfies following formula (1) and (2), condition be X refer to its 10-hour half life temperature (℃), and Y refers to its octanol-water partition coefficient.

11≥Y≥2 (1)

100-2Y≥X≥70-2Y (2)

In the middle of this class organo-peroxide, those that satisfy following formula (3) and (4) are preferably, and those of satisfied following formula (5) and (6) are preferred.

10≥Y≥2 (3)

95-2Y≥X≥72-2Y (4)

7≥X≥2 (5)

88-2Y≥X≥74-2Y (6)

If use the organo-peroxide that can not satisfy above-mentioned standard, then can not obtain effect of the present invention.

Described 10-hour half life temperature (℃) refer to such temperature, reduce to half of its original bulk during at 10 hours owing to thermolysis at organo-peroxide under this temperature.

This lower temperature value means that it is easier to decompose, and higher value means to have higher anti-decomposability.

Octanol-water partition coefficient is meant, if Co (mcg/ml) is for being dissolved in the compound concentrations in the 1-octanol, and Cw (mcg/ml) is the identical compound concentrations that is dissolved in the water, as the value of log (Co/Cw) calculating, and the wetting ability-hydrophobicity balance of expression compound.

In addition, the octanol-water partition coefficient that is used for the present invention is based on the structure of organo-peroxide, uses software ACD/LogP DB (version 6.00; Advanced ChemistryDevelopment, Inc.) value of Ji Suaning.

The particular instance that is used for the present invention's organo-peroxide is listed in as follows.The 10-of every kind of compound hour half life temperature (X: ℃) and octanol-water partition coefficient (Y) are shown in the bracket.

Dibenzoyl peroxide (X=73.6, Y=3.46)

Benzoyl (3-methyl benzoyl) superoxide (X=73.1, Y=3.93)

Two-positive sim peroxides (X=61.5, Y=6.34)

1,1,3, and 3-tetramethyl butyl peroxide-2-ethylhexanoate (X=65.3, Y=6.34)

Uncle's hexyl peroxide-2-ethylhexanoate (X=69.9, Y=5.65)

Two (4-methyl benzoyl) superoxide (X=70.6, Y=4.39)

T-butyl peroxy-2-ethylhexanoate (X=72.1, Y=4.59)

The t-butyl peroxy isobutyrate (X=77.3, Y=2.46)

1, and 1-two (t-butyl peroxy)-2-methylcyclohexane (X=83.2, Y=5.88)

Two (3,5,5-trimethyl acetyl base) superoxide (X=59.4, Y=6.31)

2,5-dimethyl-2,5-two (2-ethyl hexanoyl base peroxide) hexane (X=66.2, Y=8.87)

Two bay acyl peroxides (X=61.6, Y=10.6)

In view of it provides the goods of the dipping with well balanced performance, dibenzoyl peroxide is preferably used as organo-peroxide.

As the organo-peroxide that does not satisfy above-mentioned standard, for example can mention dicumyl peroxide (X=116.4, Y=5.71), di-t-butyl peroxide (X=123.7, Y=3.19) or the like.

(dipping composition)

Dipping composition of the present invention comprises above-mentioned conjugated diene rubber latex and above-mentioned organo-peroxide.

The content of organo-peroxide is preferably the 0.01-5 weight part based on the solids content of 100 weight parts in above-mentioned conjugated diene rubber latex, more preferably 0.05-3 weight part, and preferred especially 0.1-2 weight part.Too small amount tends to obtain having the goods of poor flexing fatigue life, and excessive amount tends to obtain the goods of feel or poor tensile strength.

As the method that organo-peroxide is joined in the conjugated diene rubber latex, though not restriction especially, can mention the method that for example (1) wherein adds the organo-peroxide of powdered or liquid conjugated diene rubber latex, (2) organic solution that wherein will be dissolved with organo-peroxide adds the method in the conjugated diene rubber latex, (3) use emulsifying agent will be dissolved with organic solution emulsification in water of organo-peroxide, then emulsion is added the method in the conjugated diene rubber latex, or the like.In addition, for the easy to handle purpose, can before using, organo-peroxide be mixed with mineral filler, to form powder.

The organic solvent that dissolves above-mentioned organo-peroxide is not limited especially, as long as it can dissolve described organo-peroxide.For example, can mention organic solvent, acetone for example, tetrahydrofuran (THF), dioxane, Anaesthetie Ether, ethyl acetate, hexane, hexanaphthene, benzene, toluene or the like with the boiling point that is lower than 200 ℃; And boiling point is 200 ℃ or higher organic solvent; dimethyl phthalate for example; diethyl phthalate; dibutyl phthalate; phthalic acid two (2-ethylhexyl) ester; dinoctyl phthalate; dimixo-octyl phthalate; Di Iso Decyl Phthalate; ditridecyl phthalate; diisononyl phthalate; dimethyl isophthalate; tetrahydrophthalic acid two (2-ethylhexyl) ester; Polycizer W 260, dimethyl adipate, hexanodioic acid two (2-ethylhexyl) ester; diisobutyl adipate; diisodecyl adipate, di n octyl adipate, di n decyl adipate; diisononyl adipate; dibutyl Diethylene Glycol adipic acid ester, two (butoxy ethoxyethyl group) adipic acid ester, two (2-ethylhexyl) azelate; di n hexyl azelate; three (2-ethylhexyl) trimellitate, three n-octyl trimellitates, three iso-octyl trimellitates; glyceryl monooleate; methyl acetyl ricinoleate (acetylricinolate), butyl ethanoyl ricinoleate, normal-butyl stearate; triethyl phosphate; tributyl phosphate, tri-2-ethylhexyl phosphate, phosphoric acid 2-(ethyl hexyl) ester diphenyl; tributyloxyethyl phosphate, triphenylphosphate or the like.

In addition, in the time will being dissolved in organo-peroxide in the organic solvent, can make its dissolving by in its temperature range of promptly not decomposing, heating.

Be dissolved in the concentration of the organo-peroxide in the organic solvent, though not restriction especially is generally 5-60 weight %, and preferred 8-50 weight %.Cross when low when this concentration, organic solvent tends to be difficult to remove from the dipping goods, perhaps tends to remain in a large number in the goods, reduces its tensile strength.On the contrary, when excessive concentration, it is difficult that the preparation of solution becomes.

When adding organo-peroxide, the pH value of conjugated diene rubber latex is preferably 8.5 or higher.Preferred range is 9 to 11.In view of preventing to form big agglomerate, such pH scope is preferred.

Because dipping composition of the present invention comprises the organo-peroxide as linking agent, when normally used sulphur and/or curing catalyst were added in the said composition, the balance in the middle of the dipping physical properties of articles of preparation was tended to worsen.

Therefore, based on the solids content in above-mentioned conjugated diene rubber latex of 100 weight parts, the sulphur loading level is preferably 0.5 weight part or following, and more preferably 0.3 weight part or following.

In addition, based on the solids content in above-mentioned conjugated diene rubber latex of 100 weight parts, the loading level of curing catalyst is preferably 0.3 weight part or following, more preferably 0.1 weight part or following.Consider the balance between the dipping physical properties of articles, most preferably neither add sulphur and also do not add curing catalyst.

If zinc oxide does not disturb effect of the present invention in fact, then can in dipping composition of the present invention, add zinc oxide.The loading level of zinc oxide is preferably 2 weight parts or following, and more preferably 1 weight part or following, and preferred especially 0.6 weight part or following is based on the solids content in above-mentioned conjugated diene rubber latex of 100 weight parts.

To be dissolved in boiling point be in 200 ℃ or the higher organic solvent and when adding in the dipping composition, this solvent tends to remain in the dipping goods that obtained, and reduces its tensile strength when organic superoxide.In this case, if zinc oxide is preferred 0.1-1 weight part with the solids content in above-mentioned conjugated diene rubber latex based on 100 weight parts, more preferably the amount of 0.2-0.6 weight part adds, can obtain to have the excellent equilibrated feel and the dipping goods of tensile strength, also influence this performance though have the content of the organic solvent of 200 ℃ or higher boiling point.

In dipping composition of the present invention, can suitably add common additive, mineral dye for example, tinting material, dispersion agent, pH regulator agent, wetting agent, sanitas, sterilant, wax, sizing agent or the like.

The concentration of the solids in the dipping composition is preferably 20-40 weight %, more preferably 25-35 weight %.

The pH value of dipping composition is preferably 8.5 or higher, and more preferably 9 to 11.

When use has the dipping composition of above-mentioned solids content and pH value, can easily make dipping goods with uniform film thickness.

(dipping goods)

Dipping goods of the present invention prepare by the dipping of above-mentioned dipping composition.

As the method for dipping, can use known method in the ability city, direct dipping process for example, anode peptizer dipping method, teague peptizer dipping method or the like.Especially, in view of the goods with uniform thickness can easily be provided, anode peptizer dipping method is preferred.

In anode peptizer dipping method, for example the dipping mould is immersed in the coagulant solution, make peptizer be attached to its surface, then this mould is immersed in the dipping composition, to form the dipping rubber layer thereon.

As the dipping mould, can use various moulds, for example those that make by pottery, glass, metal, plastics or the like.The shape of mould is corresponding to the dipping shape of products that is the finished product.When the dipping goods were gloves, the dipping mould can have different shape, the shape from the wrist to the finger tip for example, shape from the ancon to the finger tip or the like.In addition, the surface of dipping mould can be a surface-treated, for example generally or partly polishing, semipolish, non-polishing, textile designization or the like.

As peptizer, can mention for example metal halide, for example bariumchloride, calcium chloride, magnesium chloride, zinc chloride, aluminum chloride or the like; Nitrate is nitrate of baryta, nitrocalcite, zinc nitrate or the like for example; Acetate is barium acetate, lime acetate, zinc acetate or the like for example; With vitriol for example calcium sulfate, sal epsom, Tai-Ace S 150 or the like.Especially, calcium chloride and nitrocalcite are preferred.

Peptizer uses as the solution in water, alcohol or its mixture usually.The concentration of peptizer is 5-70 weight % normally, preferred 10-50 weight %.

The dipping rubber layer of preparation carries out crosslinked (cross-linking step) by thermal treatment usually.

Before thermal treatment, the dipping rubber layer can be flooded in water, be dipping 1-60 minute in 30-70 ℃ the warm water preferably, to remove water miscible impurity (for example excessive emulsifying agent, peptizer or the like) in temperature.This step can be carried out after thermal treatment, but it preferably carried out before thermal treatment, because water miscible impurity can more effectively be removed.

The dipping rubber layer that so obtains was descended heat treated 5-120 minute at 70-150 ℃, preferred 80-140 ℃, crosslinked to carry out.

If the dipping rubber layer comprises a large amount of water, then before cross-linking step, randomly be added in 40-100 ℃ of dry 5-60 minute step down.

As heat-treating methods, can use the indirect heating of utilizing ir radiation or warm air, and the inside heating that utilizes ratio-frequency heating.Especially, it is preferred utilizing warm air beating.

By remove crosslinked dipping rubber layer from the dipping mould, the dipping goods have been obtained.At this, this layer can be manually the demoulding from the mould, perhaps use hydraulic pressure or compressed-air ejection.

After removing, this layer can be further in 60-120 ℃ of following thermal treatment 10-120 minute (back cross-linking step).

The dipping goods have by chlorination on portion and/or the outer surface within it, the surface-treated layer that coating or the like forms.

The thickness of dipping goods of the present invention is about 0.1 to about 3 millimeters.Especially, it is preferred for the thin goods of 0.1-0.3 millimeter thickness. as specific application, can mention medical article, nipple for example, dropper, conduit, water pillow or the like; Toy or moving articles, for example balloon, doll, ball or the like; Mechanicals, for example pressure-molding bag, gas-storage bag or the like; The gloves of surgery application, household application, agricultural application, fishery application or industrial application; And fingerstall or the like.Gloves can have the base material type or not have the base material type.In the middle of these, the surgical glove that described goods are suitable for approaching.

Embodiment

The present invention further describes by following examples and Comparative Examples, yet the present invention is not limited to these embodiment.In these embodiments, part and % represent part and the % based on weight, unless otherwise mentioned.

(production of production example 1:NBR latex)

In polymerization reactor, add 28 parts vinyl cyanide, 66 parts 1,3-butadiene, 6 parts methacrylic acid, 0.3 part of uncle's lauryl mercaptan, 132 parts ion exchanged water, 3 parts Sodium dodecylbenzene sulfonate, 0.5 part sodium salt, 0.3 part Potassium Persulphate and 0.05 part the sodium ethylene diamine tetracetate of beta-naphthalenesulfonic-acid-formaldehyde condensation products.Polymerization uses the polymerization temperature that remains under 37 ℃ to begin.

When 60% transformation efficiency, add uncle's lauryl mercaptan of 0.15 part, and temperature is brought up to 40 ℃.When 80% transformation efficiency, add uncle's lauryl mercaptan of 0.15 part, continuous polymerization directly reaches 94% transformation efficiency, by the Sodium dimethyldithiocarbamate 40min as terminator that adds 0.1 part polymerization is stopped then.

After from the copolymer emulsion of preparation, removing unreacted monomer, its pH value and solids content are regulated, with preparation conjugated diene rubber latex A, its solids concn is 40%, and the pH value is 8.

(production of production example 2:SBR latex)

In polymerization reactor, add 42 parts vinylbenzene, 54 parts 1,3-butadiene, 4 parts methacrylic acid, uncle's lauryl mercaptan of 0.3 part, 132 parts ion exchanged water, 3 parts Sodium dodecylbenzene sulfonate, 0.5 part sodium salt, 0.3 part Potassium Persulphate and 0.05 part the sodium ethylene diamine tetracetate of beta-naphthalenesulfonic-acid-formaldehyde condensation products.Polymerization uses the polymerization temperature that remains on 60 ℃ to begin.

When 60% transformation efficiency, add uncle's lauryl mercaptan of 0.15 part, and temperature is brought up to 70 ℃.When 80% transformation efficiency, add uncle's lauryl mercaptan of 0.15 part, continuous polymerization directly reaches 95% transformation efficiency, by the Sodium dimethyldithiocarbamate 40min as terminator that adds 0.1 part polymerization is stopped then.

After from the copolymer emulsion of preparation, removing unreacted monomer, its pH value and solids content are regulated, with preparation conjugated diene rubber latex B, its solids concn is 40%, and the pH value is 8.

(embodiment 1)

In 10 parts of toluene, dissolving 5 parts of dibenzoyl peroxide under 45 ℃. in this solution, add 15 parts 1.7% sodium dodecyl benzene sulfonate aqueous solution, with preparation dibenzoyl peroxide emulsion.

In conjugated diene rubber latex A, add 5% potassium hydroxide aqueous solution, pH regulator to 10. is joined above-mentioned emulsion in the described latex under 45 ℃, make that the amount of dibenzoyl peroxide is 1 part based on 100 parts the solids content in described latex.Further add ion exchanged water, having 30% solids concn and pH value with preparation is 10 dipping composition.

In the aqueous coagulant solution for preparing by the water that mixes 20 parts nitrocalcite, 0.05 part polyethylene oxide octyl phenyl ether (it is a nonionic emulsifying agent) and 80 parts, gloves-mould was flooded for 5 seconds, extract out and 50 ℃ dry 10 minutes down, so that peptizer is adhered on gloves-mould.

Then, the gloves-mould that will have the peptizer of adhesion flooded for 6 seconds in above-mentioned dipping composition, extracted out, and drying is 10 minutes under 50 ℃, and flooded 3 minutes in 40 ℃ of warm water, to leach water miscible impurity.

Then, gloves-mould was descended dry 10 minutes at 70 ℃, then 120 ℃ of following thermal treatments 20 minutes, so that the dipping rubber layer is crosslinked.At last, crosslinked dipping rubber layer is peeled off from gloves-mould, obtained the rubber gloves of 0.1 millimeter thickness.

The performance of the gloves of preparation is estimated by the following method.The results are shown in table 1.

(feel, tensile strength and elongation)

Use the dumbbell #2 of little improvement to prepare dumbbell specimen from the gloves that prepare.

Pulling speed with 500 mm/min stretches said sample, to measure the tensile strength (Md300% when elongation reaches 300%; MPa), fracture tensile strength (MPa) and elongation at break (%).

The Md300% value is more little, means that feel is good more.

(flexing fatigue life)

Ten laboratory technicians have on prepared gloves and carry out gravy jobs.

Whether visual inspection in per 1 hour cracking occurs at the finger crotch of gloves after having on described gloves.

Determine to take place the rimose time by the gloves that the laboratory technician wears usefulness for each, and get rid of the shortest and the longest value and calculate arithmetical av.This is worn with testing progress row 6 hours.

The long higher flexing fatigue life of time representation.

(variable color that causes by cupric ion)

The gloves of preparation floods for 30 seconds in 3% copper sulfate solution, and the degree of color change when checking 1 hour by visual observation, the result is expressed as follows.

The rubber gloves color does not change: A

Rubber gloves color change: B

The rubber gloves of color change itself tends to painted in prolonged application in above-mentioned test.

(embodiment 2)

The solids content in latex that changes into based on 100 parts except the amount of the dibenzoyl peroxide that will add is 0.5 part, prepares rubber gloves by the program identical with embodiment 1.

(embodiment 3)

In conjugated diene rubber latex A, add 5% potassium hydroxide aqueous solution, with adjusting pH value to 10, and add ion exchanged water, so that solids content is adjusted to 30%.Based on 100 parts the solids content in this latex, add 1 part dibenzoyl peroxide, with preparation dipping composition.

Use this dipping composition, prepare rubber gloves, under 120 ℃, carried out 30 minutes except crosslinked by the program the same with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

(embodiment 4)

Use conjugated diene rubber latex B to replace conjugated diene rubber latex A, prepare rubber gloves, under 120 ℃, carried out 30 minutes except crosslinked by the program identical with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

(Comparative Examples 1)

Except using dicumyl peroxide to replace dibenzoyl peroxide, prepare rubber gloves by the program identical with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

(Comparative Examples 2)

Except using the disuccinic acid superoxide to replace dibenzoyl peroxide, prepare rubber gloves by the program identical with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

(Comparative Examples 3)

Except using peroxidation 2,4 dichloro benzene formyl to replace dibenzoyl peroxide, prepare rubber gloves by the program identical with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

(Comparative Examples 4)

With 1.5 parts sulphur, 1 part zinc dibutyl dithiocarbamate, 1 part zinc oxide, 1.5 parts titanium oxide, the water of 0.03 part potassium hydroxide and 5.03 parts mixes, and prepares 10.06 parts the curing solution with 50% solids concn.

To add conjugated diene rubber latex A based on the above-mentioned curing solution of 10.06 parts of the solids contents of 100 parts rubber latex A, add 5% potassium hydroxide aqueous solution and ion exchanged water then, preparation pH value be 10 and solids concn be 30% dipping composition.

Except using above-mentioned dipping composition, prepare rubber gloves by the program identical with embodiment 1.

Estimate the performance of this gloves, the results are shown in table 1.

Table 1 has shown following result.

Use the rubber latex of the organo-peroxide preparation of the dissatisfied standard of definition in the present invention to have poor flexing fatigue life, and in 2-3 hour uses, locate to occur cracking (Comparative Examples 1-3) again at the finger branch.

The rubber gloves that obtains from the dipping composition that comprises sulphur, curing catalyst and zinc oxide has poor feel, and itself tends to painted being worn with operate continuously the time (Comparative Examples 4).

Different with these Comparative Examples is, the rubber gloves that obtains from dipping composition of the present invention has wearing comfort, excellent tensile strength and high flexing fatigue life, and gloves this during being had on operate continuously not painted (embodiment 1-4).

(embodiment 5)

In 43 parts dibutyl phthalate, 45 ℃ of dibenzoyl peroxide of dissolving 5 parts down.1.7% sodium dodecyl benzene sulfonate aqueous solution that adds 48 parts in this solution is with preparation dibenzoyl peroxide emulsion.

In conjugated diene rubber latex A, add 5% potassium hydroxide aqueous solution, with pH regulator to 10.Above-mentioned emulsion is added in this latex under 45 ℃, make based on 100 parts the solids content in this latex, the amount of dibenzoyl peroxide is 0.5 part, and further adds ion exchanged water, with the preparation solids concn be 30% and pH be 10 dipping composition.

Except using above-mentioned dipping composition, prepare rubber gloves by the program identical with embodiment 1.Measure the performance of this gloves, the results are shown in the table 2.

(embodiment 6)

In 21 parts dibutyl Diethylene Glycol adipic acid ester, 45 ℃ of dibenzoyl peroxide of dissolving 3 parts down.1.7% sodium dodecyl benzene sulfonate aqueous solution that under agitation adds 24 parts in this solution is with preparation dibenzoyl peroxide emulsion.

5 parts zinc oxide are dispersed in 5 parts the ion exchanged water, with the aqueous dispersion of preparation zinc oxide.

In conjugated diene rubber latex A, add 5% potassium hydroxide aqueous solution, with pH regulator to 10.In this latex,, make that the amount of dibenzoyl peroxide and zinc oxide is respectively 0.3 part and 0.5 part based on 100 parts the solids content in this latex 45 ℃ of dispersions that add down above-mentioned emulsion and zinc oxide.Further add ion exchanged water, having 30% solids concn and pH value with preparation is 10 dipping composition.

Except using above-mentioned dipping composition, prepare rubber gloves by the program identical with embodiment 1.Measure the performance of this gloves, the results are shown in the table 2.

(embodiment 7)

In 39 parts dibutyl Diethylene Glycol adipic acid ester, 45 ℃ of dibenzoyl peroxide of dissolving 5 parts down.1.7% sodium dodecyl benzene sulfonate aqueous solution that under agitation adds 44 parts in this solution is with preparation dibenzoyl peroxide emulsion.

5 parts zinc oxide are dispersed in 5 parts the ion exchanged water, with the aqueous dispersion of preparation zinc oxide.

In conjugated diene rubber latex A, add 5% potassium hydroxide aqueous solution, with pH regulator to 10.In this latex,, make that the amount of dibenzoyl peroxide and zinc oxide is respectively 0.5 part and 0.5 part based on 100 parts the solids content in this latex 45 ℃ of dispersions that add down above-mentioned emulsion and zinc oxide.Further add ion exchanged water, having 30% solids concn and pH value with preparation is 10 dipping composition.

Except using above-mentioned dipping composition, prepare rubber gloves by the program identical with embodiment 1.Measure the performance of this gloves, the results are shown in the table 2.

Table 2

Table 2 has shown following result.

When use is dissolved in the organo-peroxide that has in the high boiling organic solvent when preparing dipping composition of the present invention, prepared rubber gloves (embodiment 5) with well balanced performance.

When use is dissolved in the organo-peroxide that uses in the high boiling organic solvent and zinc oxide when preparing dipping composition of the present invention, prepared rubber gloves (embodiment 6 and 7) with well balanced performance.

Claims (8)

1. dipping composition, it comprises conjugated diene rubber latex and organo-peroxide, wherein conjugated diene rubber latex is by the emulsion polymerization prepared of monomer mixture, this monomer mixture comprises 1 of 30-90 weight %, the 3-divinyl, 0.5-10 the another kind of the ethylenic unsaturated acid monomer of weight % and 0-69.5 weight % can with the monomer of these copolymerizations, and organo-peroxide satisfies following formula (1) and (2), condition is X ℃ and refers to its 10-hour half life temperature, and Y refers to its octanol-water partition coefficient:

11≥Y≥2 (1)，

100-2Y≥X≥70-2Y (2).

2. the dipping composition of claim 1, its solids content in conjugated diene rubber latex that comprises based on 100 weight parts is the organo-peroxide of 0.01-5 weight part.

3. claim 1 or 2 dipping composition are that 0.5 weight part or following amount add sulphur with the solids content in conjugated diene rubber latex based on 100 weight parts wherein.

4. claim 1 or 2 dipping composition are that 2 weight parts or following amount add zinc oxide with the solids content in conjugated diene rubber latex based on 100 weight parts wherein.

5. claim 1 or 2 dipping composition are that 0.3 weight part or following amount add curing catalyst with the solids content in conjugated diene rubber latex based on 100 weight parts wherein.

6. the dipping composition of claim 1, wherein other can be aromatic vinyl monomer and/or olefinically unsaturated nitriles monomer with the monomer of 1,3-butadiene and ethylenic unsaturated acid monomer copolymerizable.

7. dipping goods, it is by any one the dipping preparation of dipping composition of claim 1 to 6.

8. the dipping goods of claim 7, it is gloves.