WO2021132075A1 - Xanthogen compound dispersion, conjugated diene-based polymer latex composition, film molded body, dip molded body and adhesive composition - Google Patents
Xanthogen compound dispersion, conjugated diene-based polymer latex composition, film molded body, dip molded body and adhesive composition Download PDFInfo
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- WO2021132075A1 WO2021132075A1 PCT/JP2020/047421 JP2020047421W WO2021132075A1 WO 2021132075 A1 WO2021132075 A1 WO 2021132075A1 JP 2020047421 W JP2020047421 W JP 2020047421W WO 2021132075 A1 WO2021132075 A1 WO 2021132075A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/36—Feeding the material on to the mould, core or other substrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/10—Latex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J107/00—Adhesives based on natural rubber
- C09J107/02—Latex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
- C09J109/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/10—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Definitions
- the present invention relates to a xanthogen compound dispersion, a conjugated diene polymer latex composition, a film molded body, a dip molded body, and an adhesive composition, and more specifically, promotes calcification of a polymer such as a conjugated diene polymer.
- a polymer such as a conjugated diene polymer.
- a xanthogen compound dispersion capable of making a film polymer such as a body excellent in tensile strength and tear strength, and also excellent in tensile strength and tear strength stability, using such a xantogen compound dispersion.
- the present invention relates to the obtained conjugated diene polymer latex composition, and a film molded article, a dip molded article, and an adhesive composition comprising such a conjugated diene polymer latex composition.
- a latex composition containing a latex of natural rubber is dip-molded to obtain a dip-molded body that is used in contact with the human body such as a nipple, a balloon, a glove, a balloon, and a sack.
- the latex of natural rubber contains a protein that causes the symptoms of immediate allergy (Type I) in the human body, there may be a problem as a dip molded product that comes into direct contact with the living mucosa or organs. Therefore, studies have been conducted on using synthetic rubber latex instead of natural rubber latex.
- Patent Document 1 discloses a latex composition obtained by blending zinc oxide, sulfur, and a vulcanization accelerator with a latex of synthetic polyisoprene, which is a synthetic rubber, as a composition for dip molding.
- the technique of Patent Document 1 can prevent the occurrence of immediate allergy (Type I) due to a protein derived from natural rubber, while the vulcanization accelerator contained in the dip molded product when it is used as a dip molded product. When it comes into contact with the human body, it may cause allergic symptoms of delayed type allergy (Type IV).
- the present invention has been made in view of such an actual situation, and when it is used as a vulcanization accelerator for a polymer such as a conjugated diene polymer and used as a film molded product such as a dip molded product, it is an immediate allergy.
- a vulcanization accelerator for a polymer such as a conjugated diene polymer
- a film molded product such as a dip molded product
- the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and has tensile strength.
- a xanthogen compound dispersion capable of having excellent tear strength stability a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and such a conjugated diene system. It is an object of the present invention to provide a film molded product, a dip molded product, and an adhesive composition obtained by using a polymer
- the present inventors have contained a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol. It has been found that the xanthate compound dispersion can solve the above-mentioned problems, and based on such findings, the present invention has been completed.
- a xanthate compound dispersion containing a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
- the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant is "anionic surfactant having no polyoxyalkylene structure: nonion".
- the weight ratio of the "based surfactant” is preferably 99: 1 to 10:90.
- the anionic surfactant having no polyoxyalkylene structure is preferably an aromatic compound.
- the number average molecular weight of the nonionic surfactant is preferably 100 to 5,000.
- a conjugated diene polymer latex composition containing a latex of a conjugated diene polymer, a vulcanizing agent, and the xanthogen compound dispersion of the present invention.
- the conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound.
- the conjugated diene polymer latex composition of the present invention it is preferable that the conjugated diene polymer is a synthetic polyisoprene, a styrene-isoprene-styrene block copolymer, or a natural rubber from which proteins have been removed.
- a film molded product made of such a conjugated diene polymer latex composition and a film molded product made of such a conjugated diene polymer latex composition, a dip molded product, and an adhesive.
- the agent composition is provided.
- a delayed type allergy (Type I) is added to a delayed type allergy (Type I). It is possible to suppress the occurrence of Type IV) symptoms, and the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and also has excellent tensile strength and tear strength stability.
- a xanthogen compound dispersion which can be used, a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and a film molded product comprising such a conjugated diene polymer latex composition.
- a dip molded product and an adhesive composition can be provided.
- the xanthate compound dispersion of the present invention contains a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
- the xanthogen compound used in the present invention is a compound that acts as a vulcanization accelerator. Therefore, the xanthogen compound dispersion of the present invention can be suitably used as a vulcanization accelerator for a polymer such as a conjugated diene polymer. it can.
- the xanthogen compound acts as a vulcanization accelerator during vulcanization, and after vulcanization, it is decomposed into alcohol, carbon disulfide, and the like by the heat applied during vulcanization. In addition, alcohol, carbon disulfide, etc.
- a vulcanization accelerator for example, a thiuram-based vulcanization accelerator, a dithiocarbamate-based vulcanization accelerator, thiazole
- Type IV delayed type allergy
- a system vulcanization accelerator for example, a film such as a dip molded product
- the xanthogen compound used in the present invention is not particularly limited, and examples thereof include xanthate acid and xanthogenate.
- R is a linear or branched hydrocarbon
- Z is a metal atom.
- X is a number corresponding to the valence of Z, and is usually 1 to 4, preferably 2 to 4, particularly preferably 2.
- the compound represented by is preferable.
- the zinc salt of xanthate is more preferable.
- Dibutylxanthogenates are more preferable, zinc diisopropylxanthogenate and zinc dibutylxanthogenate are further preferable, and zinc diisopropylxanthogenate is particularly preferable.
- xanthogen compounds may be used alone or in combination of two or more.
- the xanthate compound used in the present invention is dispersed in the xanthate compound dispersion in the form of particles or powder.
- the volume average particle size of the xanthogen compound in the xantogen compound dispersion is preferably in the range of 0.001 to 9 ⁇ m, more preferably in the range of 0.05 to 7 ⁇ m, and further preferably in the range of 0.05 to 5 ⁇ m. Particularly preferably, it is in the range of 0.07 to 3 ⁇ m.
- the xanthogen compound dispersion of the present invention was used as a vulcanization accelerator for a polymer such as a conjugated diene polymer to obtain a film molded product such as a dip molded product.
- the obtained film-molded article such as a dip-molded article can be made superior in tensile strength and tear strength, and also in stability of tensile strength and tear strength.
- the 95% volume cumulative diameter (D95) of the xanthate compound in the xanthate compound dispersion is preferably in the range of 0.1 to 43 ⁇ m, more preferably in the range of 0.1 to 40 ⁇ m, and further preferably in the range of 0.1 to 0.1 to 40 ⁇ m. It is in the range of 35 ⁇ m, particularly preferably 0.1 to 20 ⁇ m.
- the volume average particle diameter and the 95% volume cumulative diameter (D95) of the xantogen compound can be measured using, for example, a laser diffraction / scattering type particle size distribution meter.
- the content ratio of the xanthate compound in the xanthate compound dispersion of the present invention is preferably 1 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 20 to the total weight of the xanthate compound dispersion. It is 50% by weight, particularly preferably 30 to 50% by weight.
- the xanthate compound dispersion of the present invention contains, in addition to the above-mentioned xanthate compound, an anionic surfactant and a nonionic surfactant having no polyoxyalkylene structure, and these are dispersed in water or alcohol. It is a dispersion.
- the xanthate compound Since the xanthate compound is solid at room temperature and does not dissolve in water or alcohol, it is usually used in a powder state. However, the powdered xanthogen compound tends to have insufficient dispersibility when blended in a latex composition containing a polymer such as a conjugated diene polymer, and therefore, sufficiently exerts its effect as a vulcanization accelerator. There was a problem that it could not be done.
- a xanthogen compound is used as a vulcanization accelerator, and this is blended with the latex of a polymer such as a conjugated diene polymer to obtain a latex composition, and a film molded product such as a dip molded product is produced.
- a xanthogen compound is used as a vulcanization accelerator, and this is blended with the latex of a polymer such as a conjugated diene polymer to obtain a latex composition, and a film molded product such as a dip molded product is produced.
- the same latex composition will be used for several days.
- the aging (pre-vulcanization) of the latex composition proceeds when several days have passed from the start of use, and therefore, several days from the start of use.
- the film-molded article obtained by using the latex composition that has passed the above period may have a significantly lower tensile strength and tear strength than the film-molded article obtained immediately after the start of use, and the obtained film-molded article may be significantly reduced. There is a problem that the stability of tensile strength and tear strength (aging stability) of the latex is insufficient.
- a xanthate compound an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol were used.
- a dispersion in which the xanthate compound is well dispersed can be obtained, and further, in the state of such a dispersion, the latex of the conjugated diene polymer is mixed with the sulfide. It has been found that a latex composition in which the xanthate compound is well dispersed can be obtained.
- the obtained film molded product such as a dip molded product can be made excellent in tensile strength and tear strength, and also in stability of tensile strength and tear strength. I found that I could do it.
- the latex composition is excellent in aging stability, so that even when the latex composition is used for a longer period of time, the tensile strength and the tear strength can be improved. It is possible to produce a film molded product such as a dip molded product without extremely reducing it, and as a result, it contributes to improvement in the production efficiency of the film molded product such as a dip molded product.
- the anionic surfactant having no polyoxyalkylene structure used in the present invention may be any anionic compound having no polyoxyalkylene structure, and is not particularly limited, but has better dispersibility of the xanthogen compound. From this point of view, aromatic compounds such as aromatic sulfonic acid compounds and aromatic carboxylic acid compounds are preferable, and aromatic sulfonic acid compounds are more preferable.
- an aromatic sulfonic acid compound represented by the following general formula (1) is preferable.
- R 1 and R 2 are independently hydrogen atoms or arbitrary organic groups, and M + is a monovalent cation.
- R 1 and R 2 are mutually. They may be combined to form a ring structure.
- M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
- the organic group can be an R 1 and R 2, but not limited to, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group , Se-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 30 carbon atoms.
- Cycloalkyl group having 3 to 30 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; aryl having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group and anthranyl group Group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, phenoxy group, etc.
- these organic groups may have a substituent, and the position of the substituent can be any position.
- the ring structure is not particularly limited, but an aromatic compound is preferable, and an aromatic compound having a benzene ring such as benzene or naphthalene is used. More preferably, naphthalene is particularly preferable.
- these ring structures may have a substituent, and the position of the substituent can be any position.
- R 1 and R 2 are bonded to each other to form a ring structure.
- the benzene ring structure is formed in the above general formula (1). More specifically, it is preferable to use a compound having a structure represented by the following general formula (2).
- R 3 is a divalent hydrocarbon group which may have a substituent, and M + is a monovalent cation.
- M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
- R 3 may be a divalent hydrocarbon group which may have a substituent, and is not particularly limited, but an alkylene group having 1 to 10 carbon atoms is preferable, and a methylene group is preferable. Is particularly preferable.
- the anionic surfactant having no polyoxyalkylene structure preferably has the structure represented by the general formula (2) repeatedly, and the number of repeating units of the structure represented by the general formula (2) is Although not particularly limited, the number is preferably 10 to 100, more preferably 20 to 50.
- the anionic surfactant having no polyoxyalkylene structure As the anionic surfactant having no polyoxyalkylene structure, the general formula (1) or of an aromatic sulfonic acid compound represented by Formula (2), sulfonate ion group (-SO 3 -) the carboxylic acid ion group (-COO -) was replaced, it is also possible to use an aromatic carboxylic acid compound.
- R 1 and R 2 in the general formula (1) and R 3 in the general formula (2) are the same as described above.
- anionic surfactant having no polyoxyalkylene structure used in the present invention is not limited to those described above, and is not limited to those described above, but is limited to sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and rosin.
- Fatty acid salts such as sodium acid acid
- alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate, etc.
- Alkyl sulfosuccinates such as sodium (2-ethylhexyl) sulfosuccinate, potassium di (2-ethylhexyl) sulfosuccinate, sodium dioctyl sulfosuccinate
- alkyl sulphate esters such as sodium lauryl sulfate and potassium lauryl sulfate
- sodium lauryl phosphate, lauryl Monoalkyl phosphates such as potassium phosphate; etc. can also
- the weight average molecular weight (Mw) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 200 to 20000, more preferably 400 to 10000.
- the number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 100 to 5000, more preferably 200 to 1000.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure are values converted to standard polystyrene by gel permeation chromatography analysis.
- the content of the anionic surfactant having no polyoxyalkylene structure in the xanthate compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the xanthate compound. , More preferably 1 to 20 parts by weight, still more preferably 2 to 18 parts by weight, particularly preferably 3 to 15 parts by weight, and most preferably 5 to 10 parts by weight.
- the nonionic surfactant used in the present invention has a segment in its molecular main chain that acts as a nonionic surfactant.
- a polyoxyalkylene structure is preferably mentioned as a segment that acts as such a nonionic surfactant.
- nonionic surfactants include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene styrene phenyl ether, polyoxyethylene (hardened) castor oil, and polyoxyethylene alkyl.
- examples include amines and fatty acid alkanolamides.
- polyoxyalkylene glycol examples include polyoxypropylene glycol ethylene oxide adducts such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene glycol.
- polyoxyalkylene alkyl ether examples include linear or branched chain ethers to which 1 to 50 (preferably 1 to 10) propylene oxide and / or ethylene oxide are added.
- Examples include chain-shaped or branched-chain ethers, and linear or branched-chain ethers in which a total of 2 to 50 (preferably 2 to 10) blocks of ethylene oxide and propylene oxide are added or randomly added.
- polyoxyalkylene alkyl ether examples include polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene dodecyl ether, polyoxyethylene lauryl ether, and the like, among these, polyoxyethylene oleyl ether and polyoxy. Polyethylene octyldodecyl ether is preferred.
- polyoxyalkylene alkyl phenyl ether examples include compounds in which 1 to 50 (preferably 1 to 10) of propylene oxide and / or ethylene oxide are added to the alkyl phenol.
- polyoxyethylene styrene phenyl ether examples include ethylene oxide adducts of (mono, di, tri) styrene phenol, and among these, polyoxyethylene di, which is an ethylene oxide adduct of distyrene phenol. Polyethylene phenyl ether is preferred.
- polyoxyethylene (hardened) castor oil examples include castor oil and ethylene oxide adducts of hardened castor oil.
- fatty acid alkanolamide examples include lauric acid diethanolamide, palmitic acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, palm oil fatty acid diethanolamide, and coconut oil fatty acid diethanolamide.
- nonionic surfactants a nonionic surfactant having a polyoxyalkylene structure is preferable, a nonionic surfactant having a polyoxyethylene structure is more preferable, and a hydrocarbylated ether of polyoxyethylene is more preferable.
- Polyoxyethylene alkyl ethers and polyoxyethylene distyrene phenyl ethers are more preferred, and polyoxyethylene alkyl ethers are particularly preferred.
- the nonionic surfactant may be used alone or in combination of two or more.
- the nonionic surfactant used in the present invention is a nonionic anionic surfactant having a segment acting as an anionic surfactant in addition to a segment acting as a nonionic surfactant. There may be.
- the nonionic surfactant used in the present invention preferably does not have a segment that acts as an anionic surfactant.
- nonionic anionic surfactant examples include compounds represented by the following general formula (3).
- R 4- O- (CR 5 R 6 CR 7 R 8 ) n- SO 3 M (3)
- R 4 is an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 6 to 16 carbon atoms or an alkyl group having 1 to 25 carbon atoms
- R 5 to R 8 is a group independently selected from the group consisting of hydrogen and methyl groups
- M is an alkali metal atom or ammonium ion
- n is 3 to 40.
- Specific examples of the compound represented by the above general formula (3) include polyoxyethylene lauryl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, polyoxyethylene oleyl ether sulfate, and the like.
- nonionic anionic surfactants the nonionic anionic surfactant having a polyoxyalkylene structure is preferable, and the nonionic anionic surfactant having a polyoxyethylene structure is more preferable.
- the nonionic anionic surfactant may be used alone or in combination of two or more.
- the number average molecular weight (Mn) of the nonionic surfactant used in the present invention is preferably 100 to 5000, more preferably 150 to 3500, still more preferably 180 to 2500, and particularly preferably 200 to 1000.
- the number average molecular weight of the nonionic surfactant is, for example, a measurement sample obtained by dissolving the nonionic surfactant in tetrahydrofuran to prepare a 0.2 wt% solution and then filtering with a 0.45 ⁇ m membrane filter. It can be determined as a standard polystyrene-equivalent number average molecular weight by measuring under the following conditions using gel permeation chromatography (GPC).
- Measuring device HLC-8220GPC (manufactured by Tosoh) Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh) Eluent: tetrahydrofuran (THF) Elution rate: 0.3 ml / min Detector: RI (polarity (+)) Column temperature: 40 ° C
- the content of the nonionic surfactant in the xanthogen compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the xanthogen compound. It is by weight, more preferably 1.2 to 15 parts by weight, particularly preferably 1.5 to 10 parts by weight, and most preferably 2 to 5 parts by weight.
- the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant in the xanthogen compound dispersion of the present invention is "anionic surfactant having no polyoxyalkylene structure: nonionic.
- the weight ratio of the "surfactant” is preferably 99: 1 to 10:90, more preferably 97: 3 to 15:85, and even more preferably 95: 5 to 55:45. , 90:10 to 55:45, most preferably 85:15 to 70:30.
- the water or alcohol used in the present invention is preferably at least one selected from water, methanol, ethanol, propanol and butanol, and more preferably water. That is, the xanthate compound dispersion of the present invention is preferably an aqueous dispersion.
- an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, water or an alcohol are mixed, and then the obtained mixed solution is used.
- a method of performing a crushing treatment is preferable.
- the crushing treatment may be any treatment that can alleviate the crushing and aggregation of the xanthate compound contained in the dispersion, and is not particularly limited, but for example, shearing action or grinding. Examples thereof include a method using a known crusher, such as a method using a crusher utilizing the action and a method using a stirring type crusher.
- a crushing device such as a roll mill, a hammer mill, a vibration mill, a jet mill, a ball mill, a planetary ball mill, a bead mill, a sand mill, or a three-roll mill can be used.
- a method of performing the crushing treatment using a ball mill, a planetary ball mill, or a bead mill is preferable.
- a medium having a media size of preferably ⁇ 5 to ⁇ 50 mm, more preferably ⁇ 10 to ⁇ 35 mm is used, and the rotation speed is preferably 10 to 300 rpm. It is preferable to carry out the crushing treatment under the conditions of more preferably 10 to 100 rpm and a treatment time of preferably 24 to 120 hours, more preferably 24 to 72 hours.
- a medium having a media size of preferably ⁇ 0.1 to ⁇ 5 mm, more preferably ⁇ 0.3 to ⁇ 3 mm is used, and the rotation speed is high.
- the crushing treatment is preferably carried out under the conditions of preferably 100 to 1000 rpm, more preferably 100 to 500 rpm, and a treatment time of preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours. is there. Further, when the crushing treatment is performed using a bead mill, a medium having a media size of preferably ⁇ 0.1 to ⁇ 3 mm, more preferably ⁇ 0.1 to ⁇ 1 mm is used, and the rotation speed is preferably high. Is preferably 1000 to 10000 rpm, more preferably 1000 to 5000 rpm, and the treatment time is preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours.
- the conjugated diene polymer latex composition of the present invention contains the latex of the conjugated diene polymer, a vulcanizing agent, and the above-mentioned xanthogen compound dispersion of the present invention.
- the conjugated diene polymer constituting the latex of the conjugated diene polymer is not particularly limited, and for example, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile.
- examples thereof include group-containing conjugated diene-based copolymers. Among these, those containing isoprene units such as synthetic polyisoprene, SIS, and natural rubber from which proteins have been removed are preferable, and synthetic polyisoprene is particularly preferable.
- the conjugated diene polymer may be an acid-modified conjugated diene polymer obtained by modifying with a monomer having an acidic group.
- the synthetic polyisoprene may be a homopolymer of isoprene, or may be a copolymer of isoprene and another ethylenically unsaturated monomer copolymerizable with isoprene. It may be a polymer.
- the content of the isoprene unit in the synthetic polyisoprene is preferably 70% by weight or more with respect to all the monomer units because it is easy to obtain a film molded product such as a dip molded product which is flexible and has excellent tensile strength. It is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 100% by weight (a homopolymer of isoprene).
- ethylenically unsaturated monomers copolymerizable with isoprene include conjugated diene monomers other than isoprene such as butadiene, chloroprene, 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -.
- Ethylene unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate (meaning "methyl acrylate and / or methyl methacrylate” and below.
- Synthetic polyisoprene is prepared in an inert polymerization solvent using a conventionally known method, for example, a Cheegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
- a Cheegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
- Isoprene and other copolymerizable ethylenically unsaturated monomers used as needed can be obtained by solution polymerization.
- the polymer solution of synthetic polyisoprene obtained by solution polymerization may be used as it is for the production of synthetic polyisoprene latex, but after taking out solid synthetic polyisoprene from the polymer solution, it is dissolved in an organic solvent. It can also be used in the production of synthetic polyisoprene latex. Further, when a polymer solution of synthetic polyisoprene is obtained by the above-mentioned method, impurities such as the residue of the polymerization catalyst remaining in the polymer solution may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid synthetic polyisoprene can be used.
- the content ratio of the cis bond unit in the isoprene unit contained in the synthetic polyisoprene is preferably 70% by weight or more with respect to the total isoprene unit. It is more preferably 90% by weight or more, still more preferably 95% by weight or more.
- the weight average molecular weight of the synthetic polyisoprene is preferably 10,000 to 5,000,000, more preferably 500,000 to 5,000,000, more preferably 500,000 to 5,000,000, in terms of standard polystyrene by gel permeation chromatography analysis. Is between 800,000 and 3,000,000.
- the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the synthetic polyisoprene is preferably 50 to 85, more preferably 60 to 85, and even more preferably 70 to 85.
- a solution or a fine suspension of synthetic polyisoprene dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of an anionic surfactant. Then, if necessary, a method for producing a synthetic polyisoprene latex by removing an organic solvent, (2) isoprene alone or a mixture of isoprene and an ethylenically unsaturated monomer copolymerizable therewith, anionic surface activity.
- a method of directly producing a synthetic polyisoprene latex by emulsification polymerization or suspension polymerization in the presence of an agent can be mentioned, but synthetic polyisoprene having a high ratio of cis-bonding units in isoprene units can be used.
- the production method (1) above is preferable from the viewpoint that a film-formed body such as a dip-formed body having excellent mechanical properties such as tensile strength can be easily obtained.
- Examples of the organic solvent used in the production method (1) above include aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane and cyclohexene; pentane, hexane and the like.
- An aliphatic hydrocarbon solvent such as heptane; a halogenated hydrocarbon solvent such as methylene chloride, chloroform and ethylene dichloride; and the like can be mentioned.
- an alicyclic hydrocarbon solvent is preferable, and cyclohexane is particularly preferable.
- the amount of the organic solvent used is preferably 2,000 parts by weight or less, more preferably 20 to 1,500 parts by weight, and further preferably 500 to 1,500 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
- anionic surfactant used in the production method (1) above examples include fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and sodium loginate; dodecylbenzene sulfonate.
- Alkylbenzene sulfonates such as sodium acid, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate, di (2-Ethylhexyl) Alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; sodium polyoxyethylene lauryl ether sulfate, potassium polyoxyethylene lauryl ether sulfate, etc. Polyoxyethylene alkyl ether sulfate ester salt; monoalkyl phosphate such as sodium lau
- fatty acid salts, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates are preferable, and fatty acid salts and alkylbenzene sulfonates are particularly preferable.
- a trace amount of the polymerization catalyst (particularly aluminum and fatty acid) derived from synthetic polyisoprene can be removed more efficiently, and the generation of agglomerates in the production of the conjugated diene polymer latex composition is suppressed. Therefore, it is preferable to use at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates in combination with fatty acid salts. It is particularly preferable to use the alkylbenzene sulfonate in combination with the fatty acid salt.
- fatty acid salt sodium loginate and potassium loginate are preferable, and as the alkylbenzene sulfonate, sodium dodecylbenzene sulfonate and potassium dodecylbenzene sulfonate are preferable.
- these surfactants may be used alone or in combination of two or more.
- At least one selected from the group consisting of alkylbenzene sulfonates, alkylsulfosuccinates, alkylsulfate salts and polyoxyethylene alkylether sulfates should be used in combination with fatty acid salts.
- the resulting latex contains at least one selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates, and fatty acid salts. ..
- a surfactant other than the anionic surfactant may be used in combination, and the surfactant other than the anionic surfactant may be ⁇ , ⁇ -non.
- examples thereof include copolymerizable surfactants such as sulfoesters of saturated carboxylic acids, sulfate esters of ⁇ , ⁇ -unsaturated carboxylic acids, and sulfoalkylaryl ethers.
- the amount of the anionic surfactant used in the production method (1) is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the synthetic polyisoprene. is there.
- the total amount of these surfactants used is in the above range. That is, for example, when at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkylsulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination with a fatty acid salt, these It is preferable that the total amount used is in the above range. If the amount of anionic surfactant used is too small, a large amount of agglomerates may be generated during emulsification. May occur.
- alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination as an anionic surfactant
- a fatty acid salt is used in combination.
- the ratio of these to be used is "fatty acid salt”: "alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt".
- the weight ratio of "total of agents” is preferably in the range of 1: 1 to 10: 1, and more preferably in the range of 1: 1 to 7: 1. Too much of the surfactant selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates will result in the handling of synthetic polyisoprenes. Foaming may become intense, which requires operations such as standing for a long time and adding an antifoaming agent, which may lead to deterioration of workability and cost increase.
- the amount of water used in the production method (1) is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, most preferably 30 parts by weight, based on 100 parts by weight of the organic solvent solution of synthetic polyisoprene. Is 50 to 100 parts by weight.
- Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, zeolite water and the like, and soft water, ion-exchanged water and distilled water are preferable.
- the method of adding the anionic surfactant to the synthetic polyisoprene solution or microsuspension is not particularly limited, and it is previously added to water, the synthetic polyisoprene solution or the fine suspension, or both. It may be added, may be added to the emulsified solution during the emulsification operation, may be added all at once, or may be added in portions.
- emulsifying device examples include batch emulsification such as the product name "homogenizer” (manufactured by IKA), the product name “Polytron” (manufactured by Kinematica), and the product name “TK autohomo mixer” (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).
- Membrane emulsifiers such as the product name "Membrane Emulsifier” (manufactured by Refrigeration Industry Co., Ltd.); Vibration type emulsifiers such as the product name "Vibro Mixer” (manufactured by Refrigeration Industry Co., Ltd.); Product name “Ultrasonic Homogenizer” (Branson) Ultrasonic emulsifiers such as (manufactured by the company); etc.
- the conditions for the emulsification operation by the emulsification device are not particularly limited, and the treatment temperature, treatment time, and the like may be appropriately selected so as to obtain a desired dispersed state.
- the organic solvent from the emulsion obtained through the emulsification operation.
- a method for removing the organic solvent from the emulsion a method in which the content of the organic solvent (preferably alicyclic hydrocarbon solvent) in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less is preferable.
- methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
- the total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent as the organic solvent in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less.
- Such a method is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
- a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
- a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
- centrifugation it is preferable to carry out centrifugation from the viewpoint that the solid content concentration of the synthetic polyisoprene latex can be increased and the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
- Centrifugation uses, for example, a continuous centrifuge to centrifuge the centrifugal force, preferably 100 to 10,000 G, and the solid content concentration of the synthetic polyisoprene latex before centrifugation, preferably 2 to 15% by weight.
- the flow velocity to be sent to the machine is preferably 500 to 1700 kg / hr, and the back pressure (gauge pressure) of the centrifuge is preferably -0.05 to 1.6 MPa, more preferably 0.03 to 1.6 MPa.
- Synthetic polyisoprene latex can be obtained as a light liquid after centrifugation. As a result, the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
- the solid content concentration of the synthetic polyisoprene latex is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that the film-formed body such as the obtained dip-molded body becomes thin and easily torn. On the other hand, if the solid content concentration is too high, the viscosity of the synthetic polyisoprene latex becomes high, which may make it difficult to transfer the synthetic polyisoprene latex or stir it in the compounding tank.
- the volume average particle size of the synthetic polyisoprene latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 2.0 ⁇ m.
- synthetic polyisoprene latex contains additives such as pH adjusters, defoamers, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. May be blended.
- the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
- SIS styrene-isoprene-styrene block copolymer
- SIS can be obtained by block copolymerization of isoprene and styrene in an inert polymerization solvent using a conventionally known method, for example, an active organometallic such as n-butyllithium as an initiator.
- the obtained SIS polymer solution may be used as it is in the production of SIS latex, but after taking out the solid SIS from the polymer solution, the solid SIS is dissolved in an organic solvent to SIS. It can also be used in the production of latex.
- the method for producing SIS latex is not particularly limited, but a SIS solution or fine suspension dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of a surfactant, and the organic solvent is removed if necessary.
- the method for producing the SIS latex is preferable. At this time, impurities such as the residue of the polymerization catalyst remaining in the polymer solution after the synthesis may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid SIS can be used.
- the organic solvent the same solvent as in the case of the synthetic polyisoprene can be used, and aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents are preferable, and cyclohexane and toluene are particularly preferable.
- the amount of the organic solvent used is usually 50 to 2,000 parts by weight, preferably 80 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, still more preferably 150 to 300 parts by weight, based on 100 parts by weight of SIS. It is a part by weight.
- anionic surfactant is preferable, and sodium loginate and sodium dodecylbenzenesulfonate are particularly preferable.
- the amount of the surfactant used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of SIS. If this amount is too small, the stability of the latex tends to be poor, and conversely, if it is too large, foaming tends to occur, which may cause problems during dip molding.
- the amount of water used in the above-mentioned method for producing SIS latex is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 50 parts by weight with respect to 100 parts by weight of the organic solvent solution of SIS. ⁇ 100.
- Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, and zeolite water. Further, a polar solvent typified by alcohol such as methanol may be used in combination with water.
- the same method as in the case of the above synthetic polyisoprene can be exemplified.
- an apparatus for emulsifying an organic solvent solution or a fine suspension of SIS in water in the presence of a surfactant can be exemplified as the same as in the case of the synthetic polyisoprene described above.
- the method of adding the surfactant is not particularly limited, and the surfactant may be added to water, an organic solvent solution of SIS, a fine suspension, or both in advance, or during the emulsification operation. In addition, it may be added to the emulsion, may be added all at once, or may be added separately.
- the organic solvent from the emulsion obtained through the emulsification operation it is preferable to remove the organic solvent from the emulsion obtained through the emulsification operation to obtain SIS latex.
- the method for removing the organic solvent from the emulsion is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
- a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
- the solid content concentration of the SIS latex is preferably 30 to 70% by weight, more preferably 50 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that when a film molded product such as a dip molded product is formed, the film thickness becomes thin and it becomes easy to tear. On the contrary, if the solid content concentration is too high, the viscosity of the SIS latex becomes high, and it becomes difficult to transfer the SIS latex by piping or to stir it in the compounding tank.
- SIS latex contains additives such as pH adjusters, antifoaming agents, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. You may.
- pH adjuster the same as in the case of the above synthetic polyisoprene can be exemplified, and alkali metal hydroxide or ammonia is preferable.
- the content of the styrene unit in the styrene block in the SIS contained in the SIS latex thus obtained is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, based on all the monomer units. , More preferably 100% by weight.
- the content of the isoprene unit in the isoprene block in SIS is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, still more preferably 100% by weight, based on all the monomer units.
- the content ratio of the styrene unit and the isoprene unit in the SIS is a weight ratio of "styrene unit: isoprene unit", which is usually 1:99 to 90:10, preferably 3:97 to 70:30, and more preferably 5. : 95 to 50:50, more preferably 10:90 to 30:70.
- the weight average molecular weight of SIS is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, still more preferably 100,000 in terms of standard polystyrene by gel permeation chromatography analysis. ⁇ 300,000.
- the volume average particle size of the latex particles (SIS particles) in the SIS latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 2.0 ⁇ m.
- natural rubber from which proteins have been removed can also be used.
- natural rubber contained in latex obtained from a natural rubber tree and natural rubber contained in latex treated with the latex can be used, for example.
- Natural rubber contained in field latex collected from a natural rubber tree, natural rubber contained in commercially available natural rubber latex obtained by treating field latex with ammonia or the like can be used.
- the method for removing the protein from the natural rubber in obtaining the natural rubber from which the protein has been removed is not particularly limited, but the natural rubber latex is reacted with a urea compound in the presence of a surfactant to obtain the natural rubber. After denaturing the protein contained therein, the natural rubber latex containing such a modified protein is subjected to treatments such as centrifugation, coagulation of rubber content, and ultrafiltration to obtain the natural rubber and the modified protein. By separating and removing this denatured protein, a natural rubber latex from which the protein has been removed can be obtained.
- conjugated diene-based polymer as described above, a nitrile group-containing conjugated diene-based copolymer can also be used.
- the nitrile group-containing conjugated diene-based copolymer is a copolymer obtained by copolymerizing an ethylenically unsaturated nitrile monomer with a conjugated diene monomer, and in addition to these, these are used as needed. It may be a copolymer obtained by copolymerizing another ethylenically unsaturated monomer copolymerizable with.
- conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. Be done. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable.
- These conjugated diene monomers can be used alone or in combination of two or more.
- the content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 56 to 78% by weight, more preferably 56 to 73% by weight. , More preferably 56 to 68% by weight. By setting the content of the conjugated diene monomer unit in the above range, the obtained film molded product such as a dip molded product can be made excellent in texture and elongation.
- the ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a nitrile group, and for example, acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethylacrylonitrile. And so on. Of these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable. These ethylenically unsaturated nitrile monomers can be used alone or in combination of two or more.
- the content ratio of the ethylenically unsaturated nitrile monomer unit formed of the ethylenically unsaturated nitrile monomer in the nitrile group-containing conjugated diene copolymer is preferably 20 to 40% by weight, more preferably 20 to 40% by weight. Is 25 to 40% by weight, more preferably 30 to 40% by weight.
- ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer and the ethylenically unsaturated nitrile monomer include, for example, ethylenically unsaturated, which is an ethylenically unsaturated monomer containing a carboxyl group.
- Saturated carboxylic acid monomer Vinyl aromatic monomer such as styrene, alkylstyrene, vinylnaphthalene; Fluoroalkylvinyl ether such as fluoroethyl vinyl ether; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol Ethylene unsaturated amide monomers such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Butyl acrylate, -2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate, methoxy (me
- Crosslinkable monomer and the like.
- These ethylenically unsaturated monomers can be used alone or in combination of two or more.
- an ethylenically unsaturated carboxylic acid monomer as another copolymerizable ethylenically unsaturated monomer, the nitrile group-containing conjugated diene copolymer is provided with a carboxyl group. be able to.
- the ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group, but for example, a single amount of an ethylenically unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid.
- Esterically unsaturated polycarboxylic acid monomer such as itaconic acid, maleic acid, fumaric acid; ethylenically unsaturated polycarboxylic acid anhydride such as maleic anhydride, citraconic anhydride; monobutyl fumarate, maleic acid
- ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl and mono-2-hydroxypropyl maleate.
- ethylenically unsaturated monocarboxylic acid is preferable, and methacrylic acid is particularly preferable.
- These ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts.
- the ethylenically unsaturated carboxylic acid monomer can be used alone or in combination of two or more.
- the content ratio of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 2 to 5% by weight. It is more preferably 2 to 4.5% by weight, still more preferably 2.5 to 4.5% by weight.
- the content ratio of the other monomer unit formed by the other ethylenically unsaturated monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 10% by weight or less, more preferably 5% by weight. % Or less, more preferably 3% by weight or less.
- the nitrile group-containing conjugated diene-based copolymer can be obtained by copolymerizing a monomer mixture containing the above-mentioned monomer, and a method of copolymerizing by emulsion polymerization is preferable.
- a method of copolymerizing by emulsion polymerization is preferable.
- the emulsion polymerization method a conventionally known method can be adopted.
- the number average particle size of the latex of the nitrile group-containing conjugated diene copolymer is preferably 60 to 300 nm, more preferably 80 to 150 nm.
- the particle size can be adjusted to a desired value by a method such as adjusting the amount of the emulsifier and the polymerization initiator used.
- conjugated diene-based polymer used in the present invention as described above, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile group-containing conjugated diene-based polymer are used.
- SIS styrene-isoprene-styrene block copolymer
- Polymers and the like can be used, but the present invention is not limited to these, and butadiene polymers, styrene-butadiene copolymers and the like may be used.
- the butadiene polymer may be a homopolymer of 1,3-butadiene as a conjugated diene monomer, or another ethylenically non-polymerizable copolymer with 1,3-butadiene as a conjugated diene monomer. It may be a copolymer obtained by copolymerizing with a saturated monomer.
- the styrene-butadiene copolymer is a copolymer obtained by copolymerizing 1,3-butadiene as a conjugated diene monomer with styrene, and in addition to these, it is used as needed. It may be a copolymer obtained by copolymerizing another copolymerizable ethylenically unsaturated monomer.
- the conjugated diene-based polymer used in the present invention may be an acid-modified conjugated diene-based polymer obtained by modifying with a monomer having an acidic group, or a carboxy-modified carboxy-modified conjugated diene-based polymer. Is preferable.
- the carboxy-modified conjugated diene-based polymer can be obtained by modifying the above-mentioned conjugated diene-based polymer with a monomer having a carboxyl group.
- an ethylenically unsaturated carboxylic acid monomer is used as the other possible ethylenically unsaturated monomer as the nitrile group-containing conjugated diene copolymer, it has already been carboxy-modified. Modification with a monomer having a carboxyl group, which will be described later, is not always necessary.
- the method for modifying the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but for example, a monomer having a carboxyl group is graft-polymerized on the conjugated diene polymer in an aqueous phase.
- the method can be mentioned.
- the method for graft-polymerizing a monomer having a carboxyl group in the conjugated diene polymer in the aqueous phase is not particularly limited, and a conventionally known method may be used. For example, in the latex of the conjugated diene polymer.
- a method in which a monomer having a carboxyl group and a graft polymerization catalyst are added and then the conjugated diene polymer is reacted with the monomer having a carboxyl group in an aqueous phase is preferable.
- the graft polymerization catalyst is not particularly limited, and for example, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc.
- inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide
- diisopropylbenzene hydroperoxide diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc.
- Organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, isobutyryl peroxide, benzoyl peroxide; 2,2'- Azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azo compounds such as methyl azobisisobutyrate; and the like; From this point of view, organic peroxide is preferable, and 1,1,3,3-tetramethylbutylhydroperoxide is particularly preferable.
- These graft polymerization catalysts may be used alone or in combination of two or more.
- the above graft polymerization catalysts can be used alone or in combination of two or more.
- the amount of the graft polymerization catalyst used varies depending on the type, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the conjugated diene polymer.
- the method for adding the graft polymerization catalyst is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
- the organic peroxide can be used as a redox-based polymerization initiator in combination with a reducing agent.
- the reducing agent is not particularly limited, but for example, a compound containing a metal ion in a reduced state such as ferrous sulfate and ferrous naphthenate; a sulfinate such as sodium hydroxymethanesulfinate; a dimethylaniline and the like. Amine compounds; etc. These reducing agents may be used alone or in combination of two or more.
- the amount of the reducing agent added is not particularly limited, but is preferably 0.01 to 1 part by weight with respect to 1 part by weight of the organic peroxide.
- the method for adding the organic peroxide is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be used, respectively.
- the reaction temperature when reacting the conjugated diene polymer with the monomer having a carboxyl group is not particularly limited, but is preferably 15 to 80 ° C, more preferably 30 to 50 ° C.
- the reaction time for reacting the conjugated diene polymer with the monomer having a carboxyl group may be appropriately set according to the above reaction temperature, but is preferably 30 to 300 minutes, more preferably 60 to 120 minutes. is there.
- the solid content concentration of the latex of the conjugated diene polymer in reacting the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 10 to 60% by weight. It is 40% by weight.
- Examples of the monomer having a carboxyl group include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; and ethylenically unsaturated polyvalents such as itaconic acid, maleic acid, fumaric acid, and butentricarboxylic acid.
- ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid
- ethylenically unsaturated polyvalents such as itaconic acid, maleic acid, fumaric acid, and butentricarboxylic acid.
- Carboxylic acid monomer Partial ester monomer of ethylenically unsaturated polyvalent carboxylic acid such as monobutyl fumarate, monobutyl maleate, mono2-hydroxypropyl maleate; polyvalent carboxylic acid such as maleic anhydride and citraconic anhydride Acid anhydrides; and the like can be mentioned, but ethylenically unsaturated monocarboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are particularly preferable, because the effect of carboxy modification becomes even more remarkable. It should be noted that these monomers may be used alone or in combination of two or more. Further, the above-mentioned carboxyl group includes those which are salts with alkali metals, ammonia and the like.
- the amount of the monomer having a carboxyl group to be used is preferably 0.01 parts by weight to 100 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, and further, with respect to 100 parts by weight of the conjugated diene polymer. It is preferably 0.5 parts by weight to 20 parts by weight.
- the method of adding the monomer having a carboxyl group to the latex of the conjugated diene polymer is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
- the modification rate of the carboxy-modified conjugated diene-based polymer by the monomer having a carboxyl group may be appropriately controlled according to the intended use of the obtained conjugated diene-based polymer latex composition, but is preferably 0.01 to 10. It is% by weight, more preferably 0.2 to 5% by weight, still more preferably 0.3 to 3% by weight, and particularly preferably 0.4 to 2% by weight.
- the denaturation rate is expressed by the following formula.
- Degeneration rate (% by weight) (X / Y) x 100
- X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified conjugated diene-based polymer
- Y represents the weight of the carboxy-modified conjugated diene-based polymer.
- X is calculated from a method of performing 1 H-NMR measurement on a carboxy-modified conjugated diene polymer and calculating from the result of 1 H-NMR measurement, or obtaining an acid amount by neutralization titration and calculating from the obtained acid amount. It can be obtained by a method or the like.
- the latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention contains a pH adjuster, an antifoaming agent, an antiseptic, and a chelating agent, which are usually blended in the field of latex. , Oxygen trapping agent, dispersant, antiaging agent and other additives may be blended.
- Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
- the solid content concentration of the latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention is preferably 30 to 70% by weight, more preferably 40 to 70% by weight.
- the conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention and a vulcanizing agent in addition to the above-mentioned latex of the conjugated diene polymer.
- the blending amount of the xanthogen compound dispersion in the conjugated diene polymer latex composition of the present invention is not particularly limited, but the content of the xanthogen compound with respect to 100 parts by weight of the conjugated diene polymer is preferably 0.01.
- the amount is up to 10 parts by weight, more preferably 0.1 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight.
- the xanthogen compound contained in the xanthogen compound dispersion exists in the form of a xanthate salt due to the action of the activator contained in the conjugated diene polymer latex composition of the present invention, and as a result, it is conjugated.
- Two or more kinds of xanthogen compounds may be contained in the diene polymer latex composition.
- the conjugated diene polymer latex composition contains sulfur as a sulfur-based vulcanizing agent or the like, a part of the xanthogen compound is contained in the conjugated diene polymer latex composition due to the action of sulfur.
- Xantogen disulfide or xanthogen polysulfide may be present in the form.
- a sulfur-based vulcanizing agent is preferably used.
- the sulfur-based sulfurizing agent include sulfur powder, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur; sulfur chloride, sulfur dichloride, morpholin disulfide, alkylphenol disulfide, and caprolactam disulfide (N). , N'-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfide, high molecular weight polysulfide, 2- (4'-morpholinodithio) benzothiazole and other sulfur-containing compounds.
- sulfur can be preferably used.
- the sulfur-based vulcanizing agent may be used alone or in combination of two or more.
- the content of the vulcanizing agent in the latex composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 parts by weight, based on 100 parts by weight of the conjugated diene polymer. It is up to 5 parts by weight, more preferably 0.5 to 3 parts by weight.
- the conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound, and more preferably at least a metal oxide.
- the metal oxide and the main group metal compound act as an activator when used together with the xanthate compound contained in the xanthate compound dispersion. Further, the metal oxide and the typical metal compound also act as a cross-linking agent for cross-linking an acidic group when an acid-modified conjugated diene-based polymer is used as the conjugated diene-based polymer, whereby a dip molded product obtained by the above. It is possible to further increase the tensile strength and tear strength of the film-molded article such as.
- the metal oxide is not particularly limited, but includes zinc oxide, magnesium oxide, titanium oxide, calcium oxide, lead oxide, iron oxide, copper oxide, tin oxide, nickel oxide, chromium oxide, cobalt oxide, and aluminum oxide. Can be mentioned. Among these, zinc oxide is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These metal oxides may be used alone or in combination of two or more.
- the typical metal compound may be a typical metal compound other than an oxide, and is not particularly limited, but is not particularly limited, but is a typical metal hydroxide, carbon oxide, sulfate, glass oxide, phosphor oxide, chloride, bromide, or iodide. Of these, carbon oxides, which are typical metals, are preferable.
- typical metal compounds include compounds such as zinc, magnesium, calcium, lead, tin, and aluminum, and among them, zinc compounds are preferable. Among these, zinc carbonate is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These typical metal compounds may be used alone or in combination of two or more.
- the total content of the metal oxide and / or the typical metal compound in the conjugated diene polymer latex composition of the present invention is not particularly limited, but is preferably 0 with respect to 100 parts by weight of the conjugated diene polymer. It is 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.5 to 5 parts by weight.
- the conjugated diene polymer latex composition of the present invention is further provided with a xanthogen compound as long as it can suppress the occurrence of delayed type allergy (Type IV) symptoms in the obtained film molded product such as a dip molded product.
- a vulcanization accelerator other than the above may be contained.
- the content of the vulcanization accelerator other than the xanthate compound is preferably 20% by weight or less, preferably 10% by weight, based on the total content of the xanthate compound and the vulcanization accelerator other than the xanthate compound. It is more preferably 0% by weight (that is, it does not contain a vulcanization accelerator other than the xanthate compound).
- sulfide accelerator other than the xanthogen compound those usually used in film molding such as dip molding can be used, and for example, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, dicyclohexyldithiocarbamic acid, diphenyldithiocarbamine.
- Dithiocarbamic acids such as acids, dibenzyldithiocarbamic acid and their zinc salts; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazolin, dibenzothiazyl disulfide, 2- (2,4-dinitrophenylthio) ) Benzothiazole, 2- (N, N-diethylthio carbamoylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, 2- (4'-morpholino dithio) benzothiazole, 4 -Morphorinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea and the like can be mentioned.
- vulcanization accelerators other than thiuram-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators, and thiazole-based vulcanization accelerators are preferable to use.
- the vulcanization accelerator other than the xanthate compound can be used alone or in combination of two or more.
- the conjugated diene polymer latex composition of the present invention further includes an antiaging agent; a dispersant; a reinforcing agent such as carbon black, silica and talc; a filler such as calcium carbonate and clay; an ultraviolet absorber; a plasticizer; Etc. can be blended as needed.
- Anti-aging agents include 2,6-di-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2'-methylene-bis (6- ⁇ -methyl-benzyl-p-cresol), 4, Butylation of 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), alkylated bisphenol, p-cresol and dicyclopentadiene Phenolic antioxidants that do not contain sulfur atoms such as reaction products; 2,2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (6-t-butyl-) O-cresol), 2,6-d
- the content of the antioxidant in the conjugated diene polymer latex composition of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0, based on 100 parts by weight of the carboxy-modified conjugated diene polymer. .1 to 5 parts by weight.
- the method for preparing the conjugated diene polymer latex composition of the present invention is not particularly limited, but for example, the latex of the conjugated diene polymer described above, a vulcanizing agent, a xanthogen compound dispersion, and if necessary. Examples thereof include a method of mixing various compounding agents used in the above. In this case, a method of preparing an aqueous dispersion of a compounding component other than the latex of the conjugated diene polymer and then mixing the aqueous dispersion with the latex of the conjugated diene polymer can also be adopted.
- the solid content concentration of the conjugated diene polymer latex composition of the present invention is preferably 10 to 60% by weight, more preferably 10 to 55% by weight.
- the conjugated diene-based polymer of the present invention may be prepared before being subjected to film-molding such as dip molding.
- the latex composition is preferably aged (pre-vulcanized).
- the aging (pre-vulcanization) time is not particularly limited, but is preferably 8 to 120 hours, more preferably 24-72 hours.
- the temperature of aging (pre-vulcanization) is not particularly limited, but is preferably 20 to 40 ° C.
- the conjugated diene polymer latex composition of the present invention when using the conjugated diene polymer latex composition of the present invention, after aging (pre-vulcanization) for a predetermined time, the aging (pre-vulcanization) conditions are maintained (aging (pre-vulcanization)). ), Film molding such as dip molding may be continuously performed, and the aging (pre-vulcanization) time and aging (pre-vulcanization) temperature in this case may be within the above ranges.
- the conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention, the tensile strength even when the aging (pre-vulcanization) time is relatively long as described above.
- the film-molded article of the present invention is a film-shaped molded article composed of the above-mentioned conjugated diene-based polymer latex composition of the present invention.
- the film thickness of the film molded product of the present invention is preferably 0.03 to 0.50 mm, more preferably 0.05 to 0.40 mm, and particularly preferably 0.08 to 0.30 mm.
- the film molded product of the present invention is not particularly limited, but a dip molded product obtained by dip molding the conjugated diene polymer latex composition of the present invention is preferable.
- Dip molding involves immersing a mold in a conjugated diene polymer latex composition, depositing the composition on the surface of the mold, then pulling the mold out of the composition, and then depositing the composition on the surface of the mold. Is a method of drying.
- the mold before being immersed in the conjugated diene polymer latex composition may be preheated. Further, a coagulant can be used as needed before immersing the mold in the conjugated diene polymer latex composition or after pulling the mold out of the conjugated diene polymer latex composition.
- the method of using the coagulant include a method of immersing the mold before being immersed in the conjugated diene polymer latex composition in a solution of the coagulant to attach the coagulant to the mold (anode adhesion immersion method).
- anode adhesion immersion method There is a method of immersing a mold in which a conjugated diene polymer latex composition is deposited in a coagulant solution (Teeg adhesion immersion method), but it is possible to obtain a dip molded body with less uneven thickness, so that it is immersed in an anode adhesion. The method is preferred.
- the coagulant include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; nitrates such as barium nitrate, calcium nitrate and zinc nitrate; acetic acid such as barium acetate, calcium acetate and zinc acetate. Salts; water-soluble polyvalent metal salts such as calcium sulfate, magnesium sulfate, sulfates such as aluminum sulfate; Of these, calcium salts are preferable, and calcium nitrate is more preferable. These water-soluble polyvalent metal salts can be used alone or in combination of two or more.
- the coagulant can usually be used as a solution of water, alcohol, or a mixture thereof, and is preferably used in the state of an aqueous solution.
- This aqueous solution may further contain a water-soluble organic solvent such as methanol or ethanol or a nonionic surfactant.
- the concentration of the coagulant varies depending on the type of the water-soluble polyvalent metal salt, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
- the mold After the mold is pulled up from the conjugated diene polymer latex composition, it is usually heated to dry the deposits formed on the mold.
- the drying conditions may be appropriately selected.
- the obtained dip molded layer is heat-treated and vulcanized.
- the mixture before the heat treatment, the mixture is immersed in water, preferably warm water at 30 to 70 ° C. for about 1 to 60 minutes to remove water-soluble impurities (for example, excess emulsifier, coagulant, etc.). You may.
- the operation for removing water-soluble impurities may be performed after the dip molding layer has been heat-treated, but it is preferably performed before the heat treatment because the water-soluble impurities can be removed more efficiently.
- Vulcanization of the dip molded layer is usually carried out by heat treatment at a temperature of 80 to 150 ° C., preferably for 10 to 130 minutes.
- a method of external heating by infrared rays or heated air or internal heating by high frequency can be adopted. Of these, external heating with heated air is preferable.
- the dip molded body can be obtained as a film-shaped film molded body.
- a desorption method a method of manually peeling from the molding mold or a method of peeling by water pressure or compressed air pressure can be adopted. After desorption, heat treatment may be further performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
- the film-molded product of the present invention is a film-like conjugated diene-based polymer latex composition of the present invention described above. Any method may be used as long as it can be molded into (for example, a coating method).
- the film molded product of the present invention can suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I), and also has tensile strength and tear strength. It is excellent in stability of tensile strength and tear strength, and can be particularly preferably used as a glove, for example.
- gloves are made of inorganic fine particles such as talc and calcium carbonate or organic fine particles such as starch particles. It may be sprayed on the surface, an elastomer layer containing fine particles may be formed on the surface of the glove, or the surface layer of the glove may be chlorinated.
- the film molded product of the present invention including the dip molded product of the present invention includes medical supplies such as baby bottle nipples, droppers, tubes, water pillows, balloon sack, catheters, condoms; balloons, dolls, etc. , Balls and other toys; industrial products such as pressure molding bags and gas storage bags; can also be used for finger cots and the like.
- the above-mentioned conjugated diene polymer latex composition of the present invention can be used as the adhesive composition.
- the content (solid content) of the conjugated diene-based polymer latex composition of the present invention in the adhesive composition is preferably 5 to 60% by weight, more preferably 10 to 30% by weight.
- the adhesive composition preferably contains an adhesive resin in addition to the conjugated diene polymer latex composition of the present invention.
- the adhesive resin is not particularly limited, but for example, resorcin-formaldehyde resin, melamine resin, epoxy resin and isocyanate resin can be preferably used, and among these, resorcin-formaldehyde resin is preferable.
- resorcin-formaldehyde resin known ones (for example, those disclosed in JP-A-55-142635) can be used.
- the reaction ratio of resorcin to formaldehyde is a molar ratio of "resorcin: formaldehyde", usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3.
- the adhesive composition contains 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or the like conventionally used.
- Compounds, isocyanates, blocked isocyanates, ethylene ureas, polyepoxides, modified polyvinyl chloride resins and the like can be contained.
- the adhesive composition can contain a cross-linking aid.
- a cross-linking aid By containing the cross-linking aid, the mechanical strength of the complex described later obtained by using the adhesive composition can be improved.
- the cross-linking aid include quinone dioximes such as p-quinone dioxime; methacrylate esters such as lauryl methacrylate and methyl methacrylate; DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (triallyl cyanurate), and TAIC. Allyl compounds such as (triallyl isocyanurate); maleimide compounds such as bismaleimide, phenylmaleimide, N, Nm-phenylenedi maleimide; sulfur; and the like can be mentioned.
- ⁇ Modification rate of carboxy-modified synthetic polyisoprene> The number of carboxyl groups in the carboxy-modified synthetic polyisoprene was determined by neutralization titration using an aqueous sodium hydroxide solution for the carboxy-modified synthetic polyisoprene constituting the latex of the carboxy-modified synthetic polyisoprene. Then, based on the obtained number of carboxyl groups, the modification rate of the monomer having a carboxyl group was determined according to the following formula.
- Degeneration rate (% by weight) (X / Y) x 100
- X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified synthetic polyisoprene
- Y represents the weight of the carboxy-modified synthetic polyisoprene
- ⁇ Number average molecular weight (Mn) of nonionic surfactant> A nonionic surfactant was dissolved in tetrahydrofuran to prepare a 0.2 wt% solution, and then filtered through a 0.45 ⁇ m membrane filter as a measurement sample, which was subjected to gel permeation chromatography (GPC) under the following conditions. The number average molecular weight (Mn) of the nonionic surfactant in terms of standard polystyrene was determined by the measurement.
- Measuring device HLC-8220GPC (manufactured by Tosoh) Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh) Eluent: tetrahydrofuran (THF) Elution rate: 0.3 ml / min Detector: RI (polarity (+)) Column temperature: 40 ° C
- the measurement was performed on 5 test pieces, and the tensile strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tensile strength. It can be judged that the higher the tensile strength, the better the tensile strength. Further, it can be judged that the smaller the difference between the tensile strength of the 24-hour aged product and the tensile strength of the 72-hour aged product, the better the stability of the tensile strength.
- the measurement was performed on 5 test pieces, and the tear strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tear strength. It can be judged that the higher the tear strength, the better the tear strength. Further, it can be judged that the smaller the difference between the tear strength of the 24-hour aged product and the tear strength of the 72-hour aged product, the better the stability of the tear strength.
- ⁇ Manufacturing example 1> (Manufacture of latex of carboxy-modified synthetic polyisoprene) Synthetic polyisoprene having a weight average molecular weight of 1,300,000 (trade name "NIPOL IR2200L", manufactured by Nippon Zeon Co., Ltd., isoprene homopolymer, cis bond unit amount 98%) is mixed with cyclohexane and heated while stirring. Was dissolved by raising the temperature to 60 ° C. to prepare a cyclohexane solution (a) of synthetic polyisoprene having a viscosity of 12,000 mPa ⁇ s measured by a B-type viscosity meter (solid content concentration: 8% by weight).
- an aqueous anionic surfactant solution (b) having a concentration of 1.5% by weight 20 parts of sodium rosinate was added to water, the temperature was raised to 60 ° C. and dissolved to prepare an aqueous anionic surfactant solution (b) having a concentration of 1.5% by weight.
- the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) are mixed in a mixer (trade name “Multiline Mixer MS26-MMR-5” so as to have a weight ratio of 1: 1.5. .5L ”, manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.), and then mixed and emulsified using an emulsifying device (trade name“ Milder MDN310 ”, manufactured by Pacific Kiko Co., Ltd.) at a rotation speed of 4100 rpm to emulsify. Liquid (c) was obtained.
- a mixer trade name “Multiline Mixer MS26-MMR-5” so as to have a weight ratio of 1: 1.5. .5L ”, manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.
- an emulsifying device trade name“ Milder MDN310 ”, manufactured by Pacific Kiko Co., Ltd.
- the total feed flow velocity of the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) was 2,000 kg / hr, the temperature was 60 ° C., and the back pressure (gauge pressure) was 0.5 MPa.
- the emulsion (c) was heated to 80 ° C. under a reduced pressure of ⁇ 0.01 to ⁇ 0.09 MPa (gauge pressure), cyclohexane was distilled off, and an aqueous dispersion (d) of synthetic polyisoprene was added. Obtained.
- an antifoaming agent (trade name "SM5515", manufactured by Toray Dow Corning Co., Ltd.) was continuously added while spraying so as to have an amount of 300 ppm by weight based on the synthetic polyisoprene in the emulsion (c). ..
- the emulsion (c) When distilling off cyclohexane, the emulsion (c) is adjusted to be 70% by volume or less of the volume of the tank, and a three-stage inclined paddle blade is used as the stirring blade, and the mixture is slowly stirred at 60 rpm. Was carried out.
- the obtained aqueous dispersion (d) of synthetic polyisoprene is used in a continuous centrifuge (trade name "SRG510", manufactured by Alfa Laval) from 4,000 to Centrifugation at 5,000 G gave a latex (e) of synthetic polyisoprene as a light liquid.
- the conditions for centrifugation are as follows: the solid content concentration of the aqueous dispersion (d) before centrifugation is 10% by weight, the flow velocity during continuous centrifugation is 1300 kg / hr, and the back pressure (gauge pressure) of the centrifuge is 1. It was set to 5 MPa.
- the obtained synthetic polyisoprene latex (e) had a solid content concentration of 60% by weight.
- the latex (e) of synthetic polyisoprene to which a dispersant was added was charged into a reaction vessel equipped with a stirrer substituted with nitrogen, and the temperature was heated to 30 ° C. while stirring. Further, using another container, 3 parts of methacrylic acid as a monomer having a carboxyl group and 16 parts of distilled water were mixed to prepare a diluted methacrylic acid solution. This diluted methacrylic acid solution was added to a reaction vessel heated to 30 ° C. over 30 minutes.
- the carboxy-modified synthetic polyisoprene was concentrated with a centrifuge to obtain a light liquid having a solid content concentration of 55%. Then, with respect to the obtained latex of the carboxy-modified synthetic polyisoprene, the modification rate of the obtained monomer having a carboxyl group was measured according to the above method, and the modification rate was 0.5% by weight.
- ⁇ Manufacturing example 2> Manufacturing of SIS latex
- SIS trade name "Quintac 3620", manufactured by Nippon Zeon Co., Ltd.
- the solid content concentration of the obtained SIS latex was 60% by weight.
- Example 1> (Preparation of xanthate compound dispersion) Zinc diisopropylxanthogenate as a xanthogen compound (trade name "Noxeller ZIX”, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., volume average particle size: 14 ⁇ m, 95% volume cumulative diameter (D95): 55 ⁇ m) 2.5 parts, polyoxy Sodium salt of ⁇ -naphthalene sulfonic acid formalin condensate as an anionic surfactant having no alkylene structure (trade name "Demor T-45”, manufactured by Kao, weight average molecular weight: 7,000) 0.22 parts, 0.06 parts of polyoxyethylene oleyl ether as a nonionic surfactant (trade name "Emargen 404", manufactured by Kao, number average molecular weight (Mn): 421), and 4.5 parts of water, ball mill (trade name) A xanthate compound dispersion was obtained by crushing by mixing with a "Noxeller
- a styrene-maleic acid mono-sec-butyl ester-maleic acid monomethyl ester polymer (trade name "Scripest550", manufactured by Hercules) was prepared, and sodium hydroxide was used to contain 100% of the carboxyl groups in the polymer.
- an aqueous sodium salt solution (concentration: 10% by weight) was prepared.
- this aqueous sodium salt solution was added to the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1 so that the solid content was 0.8 parts with respect to 100 parts of the carboxy-modified synthetic polyisoprene in the latex. Addition gave a mixture.
- the aqueous dispersion of each compounding agent was added so as to have 1.5 parts of zinc oxide, 1.5 parts of sulfur, and 2 parts of an antiaging agent (trade name "Wingstay L", manufactured by Goodyear Tire and Rubber Co., Ltd.) in terms of solid content. Addition gave a latex composition. Then, the obtained latex composition was divided into two, one of which was aged for 24 hours (pre-vulcanization) in a constant temperature water bath adjusted to 25 ° C., and the other was a constant temperature water tank adjusted to 25 ° C. By carrying out aging (pre-vulcanization) for 72 hours in the above, a 24-hour aged latex composition and a 72-hour aged latex composition were obtained.
- the hand mold coated with the coagulant was taken out from the oven and immersed in the 24-hour aged latex composition obtained above for 10 seconds.
- the hand mold was air-dried at room temperature for 10 minutes and then immersed in warm water at 60 ° C. for 5 minutes to elute water-soluble impurities to form a dip molding layer on the hand mold.
- the dip-molded layer formed in the hand mold is vulcanized by heating it in an oven at a temperature of 130 ° C. for 30 minutes, cooled to room temperature, sprayed with talc, and then peeled off from the hand mold.
- a glove-shaped dip molded product (aged for 24 hours) was obtained.
- a glove-shaped dip molded product (72-hour aged product) was obtained in the same manner as above except that the 72-hour aged latex composition was used instead of the 24-hour aged latex composition. Then, using the obtained dip molded products (24-hour aged product and 72-hour aged product), the tensile strength and the tear strength were measured according to the above method. The results are shown in Table 1.
- Example 2 Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was 0.14 parts and the amount of the polyoxyethylene oleyl ether was 0.14 parts. I got a body.
- the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 ⁇ m, and the 95% cumulative volume diameter (D95) was 3.9 ⁇ m.
- Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
- Example 3 Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was 0.06 part and the amount of the polyoxyethylene oleyl ether was 0.22 part. I got a body.
- the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.8 ⁇ m, and the 95% cumulative volume diameter (D95) was 4.4 ⁇ m.
- Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
- Example 4 Except for using 0.06 parts of polyoxyethylene octyldodecyl ether (trade name "Emargen 2025G", manufactured by Kao Corporation, number average molecular weight (Mn): 2450) instead of 0.06 parts of polyoxyethylene oleyl ether.
- a xanthogen compound dispersion was obtained in the same manner as in Example 1.
- the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found.
- Example 5 The 24-hour aged latex composition and the latex aged in the same manner as in Example 4 except that the latex of SIS obtained in Production Example 2 was used instead of the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1.
- a 72-hour aged latex composition and a dip molded product were obtained and measured in the same manner. The results are shown in Table 1.
- ⁇ Comparative example 1> A xanthogen compound dispersion was obtained in the same manner as in Example 1 except that the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was used in an amount of 0.28 parts and polyoxyethylene oleyl ether was not used.
- the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.1 ⁇ m and the 95% cumulative volume diameter (D95) was 3.8 ⁇ m.
- Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
- a xanthate compound dispersion containing a xanthogen compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol is used as a vulcanization accelerator.
- a vulcanization accelerator for example, thiuram-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator, thiazole-based vulcanization accelerator, etc.
- a vulcanized product could be obtained without use, and it was possible to suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I).
- the obtained dip molded product was excellent in tensile strength and tear strength, and was also excellent in stability of tensile strength and tear strength. Further, according to the above-mentioned xanthogen compound dispersion, the obtained latex composition is aged for 24 hours before the production of the dip molded product is started, and the production of the dip molded product is continued for 48 hours or more while maintaining the aging conditions. Even when the above was continuously performed, it was possible to stably produce a dip molded product having excellent tensile strength and tear strength. That is, the obtained latex composition was excellent in aging stability (Examples 1 to 5).
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Abstract
Provided is a xanthogen compound dispersion that comprises a xanthogen compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant and water or an alcohol.
Description
本発明は、キサントゲン化合物分散体、共役ジエン系重合体ラテックス組成物、膜成形体、ディップ成形体、および接着剤組成物に関し、さらに詳しくは、共役ジエン系重合体などの重合体の加硫促進剤として用い、ディップ成形体などの膜成形体とした場合に、即時型アレルギー(Type I)に加えて遅延型アレルギー(Type IV)の症状の発生を抑制可能であり、しかも、得られるディップ成形体などの膜成形体を、引張強度および引裂強度に優れ、かつ、引張強度および引裂強度の安定性に優れたものとすることができるキサントゲン化合物分散体、このようなキサントゲン化合物分散体を用いて得られる共役ジエン系重合体ラテックス組成物、およびこのような共役ジエン系重合体ラテックス組成物からなる膜成形体、ディップ成形体、および接着剤組成物に関する。
The present invention relates to a xanthogen compound dispersion, a conjugated diene polymer latex composition, a film molded body, a dip molded body, and an adhesive composition, and more specifically, promotes calcification of a polymer such as a conjugated diene polymer. When used as an agent to form a film polymer such as a dip molded product, it is possible to suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I), and the obtained dip molding is possible. A xanthogen compound dispersion capable of making a film polymer such as a body excellent in tensile strength and tear strength, and also excellent in tensile strength and tear strength stability, using such a xantogen compound dispersion. The present invention relates to the obtained conjugated diene polymer latex composition, and a film molded article, a dip molded article, and an adhesive composition comprising such a conjugated diene polymer latex composition.
従来、天然ゴムのラテックスを含有するラテックス組成物をディップ成形して、乳首、風船、手袋、バルーン、サック等の人体と接触して使用されるディップ成形体が得られることが知られている。しかしながら、天然ゴムのラテックスは、人体に即時型アレルギー(Type I)の症状を引き起こすような蛋白質を含有するため、生体粘膜又は臓器と直接接触するディップ成形体としては問題がある場合があった。そのため、天然ゴムのラテックスではなく、合成ゴムのラテックスを用いる検討がされてきている。
Conventionally, it is known that a latex composition containing a latex of natural rubber is dip-molded to obtain a dip-molded body that is used in contact with the human body such as a nipple, a balloon, a glove, a balloon, and a sack. However, since the latex of natural rubber contains a protein that causes the symptoms of immediate allergy (Type I) in the human body, there may be a problem as a dip molded product that comes into direct contact with the living mucosa or organs. Therefore, studies have been conducted on using synthetic rubber latex instead of natural rubber latex.
たとえば、特許文献1には、ディップ成形用組成物として、合成ゴムである合成ポリイソプレンのラテックスに、酸化亜鉛、硫黄および加硫促進剤を配合してなるラテックス組成物が開示されている。しかしながら、この特許文献1の技術では、天然ゴムに由来する蛋白質による即時型アレルギー(Type I)の発生を防止できる一方で、ディップ成形体とした場合に、ディップ成形体に含まれる加硫促進剤が原因で、人体に触れた際に、遅延型アレルギー(Type IV)のアレルギー症状を発生させることがあった。
For example, Patent Document 1 discloses a latex composition obtained by blending zinc oxide, sulfur, and a vulcanization accelerator with a latex of synthetic polyisoprene, which is a synthetic rubber, as a composition for dip molding. However, the technique of Patent Document 1 can prevent the occurrence of immediate allergy (Type I) due to a protein derived from natural rubber, while the vulcanization accelerator contained in the dip molded product when it is used as a dip molded product. When it comes into contact with the human body, it may cause allergic symptoms of delayed type allergy (Type IV).
本発明は、このような実状に鑑みてなされたものであり、共役ジエン系重合体などの重合体の加硫促進剤として用い、ディップ成形体などの膜成形体とした場合に、即時型アレルギー(Type I)に加えて遅延型アレルギー(Type IV)の症状の発生を抑制可能であり、しかも、得られるディップ成形体などの膜成形体を、引張強度および引裂強度に優れ、かつ、引張強度および引裂強度の安定性に優れたものとすることができるキサントゲン化合物分散体、ならびに、このようなキサントゲン化合物分散体を用いて得られる共役ジエン系重合体ラテックス組成物、およびこのような共役ジエン系重合体ラテックス組成物を用いて得られる膜成形体、ディップ成形体、および接着剤組成物を提供することを目的とする。
The present invention has been made in view of such an actual situation, and when it is used as a vulcanization accelerator for a polymer such as a conjugated diene polymer and used as a film molded product such as a dip molded product, it is an immediate allergy. In addition to (Type I), it is possible to suppress the occurrence of delayed type allergy (Type IV) symptoms, and the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and has tensile strength. And a xanthogen compound dispersion capable of having excellent tear strength stability, a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and such a conjugated diene system. It is an object of the present invention to provide a film molded product, a dip molded product, and an adhesive composition obtained by using a polymer latex composition.
本発明者等は、上記課題を解決すべく鋭意研究した結果、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有するキサントゲン化合物分散体によれば、上記課題を解決できることを見出し、このような知見に基づき、本発明を完成させるに至った。
As a result of diligent research to solve the above problems, the present inventors have contained a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol. It has been found that the xanthate compound dispersion can solve the above-mentioned problems, and based on such findings, the present invention has been completed.
すなわち、本発明によれば、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有するキサントゲン化合物分散体が提供される。
本発明のキサントゲン化合物分散体において、前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、前記ノニオン系界面活性剤との比率が、「ポリオキシアルキレン構造を有しないアニオン系界面活性剤:ノニオン系界面活性剤」の重量比で、99:1~10:90であることが好ましい。
本発明のキサントゲン化合物分散体において、前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤が、芳香族化合物であることが好ましい。
本発明のキサントゲン化合物分散体において、前記ノニオン系界面活性剤の数平均分子量が、100~5,000であることが好ましい。 That is, according to the present invention, there is provided a xanthate compound dispersion containing a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
In the xanthogen compound dispersion of the present invention, the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant is "anionic surfactant having no polyoxyalkylene structure: nonion". The weight ratio of the "based surfactant" is preferably 99: 1 to 10:90.
In the xanthate compound dispersion of the present invention, the anionic surfactant having no polyoxyalkylene structure is preferably an aromatic compound.
In the xanthate compound dispersion of the present invention, the number average molecular weight of the nonionic surfactant is preferably 100 to 5,000.
本発明のキサントゲン化合物分散体において、前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、前記ノニオン系界面活性剤との比率が、「ポリオキシアルキレン構造を有しないアニオン系界面活性剤:ノニオン系界面活性剤」の重量比で、99:1~10:90であることが好ましい。
本発明のキサントゲン化合物分散体において、前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤が、芳香族化合物であることが好ましい。
本発明のキサントゲン化合物分散体において、前記ノニオン系界面活性剤の数平均分子量が、100~5,000であることが好ましい。 That is, according to the present invention, there is provided a xanthate compound dispersion containing a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
In the xanthogen compound dispersion of the present invention, the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant is "anionic surfactant having no polyoxyalkylene structure: nonion". The weight ratio of the "based surfactant" is preferably 99: 1 to 10:90.
In the xanthate compound dispersion of the present invention, the anionic surfactant having no polyoxyalkylene structure is preferably an aromatic compound.
In the xanthate compound dispersion of the present invention, the number average molecular weight of the nonionic surfactant is preferably 100 to 5,000.
また、本発明によれば、共役ジエン系重合体のラテックスと、加硫剤と、上記本発明のキサントゲン化合物分散体とを含有する共役ジエン系重合体ラテックス組成物が提供される。
本発明の共役ジエン系重合体ラテックス組成物は、さらに、金属酸化物および/または典型金属化合物を含むことが好ましい。
本発明の共役ジエン系重合体ラテックス組成物において、前記共役ジエン系重合体が、合成ポリイソプレン、スチレン-イソプレン-スチレンブロック共重合体、または蛋白質を除去した天然ゴムであることが好ましい。
さらに、本発明によれば、このような共役ジエン系重合体ラテックス組成物からなる膜成形体、および、このような共役ジエン系重合体ラテックス組成物からなる膜成形体、ディップ成形体、および接着剤組成物が提供される。 Further, according to the present invention, there is provided a conjugated diene polymer latex composition containing a latex of a conjugated diene polymer, a vulcanizing agent, and the xanthogen compound dispersion of the present invention.
The conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound.
In the conjugated diene polymer latex composition of the present invention, it is preferable that the conjugated diene polymer is a synthetic polyisoprene, a styrene-isoprene-styrene block copolymer, or a natural rubber from which proteins have been removed.
Further, according to the present invention, a film molded product made of such a conjugated diene polymer latex composition, and a film molded product made of such a conjugated diene polymer latex composition, a dip molded product, and an adhesive. The agent composition is provided.
本発明の共役ジエン系重合体ラテックス組成物は、さらに、金属酸化物および/または典型金属化合物を含むことが好ましい。
本発明の共役ジエン系重合体ラテックス組成物において、前記共役ジエン系重合体が、合成ポリイソプレン、スチレン-イソプレン-スチレンブロック共重合体、または蛋白質を除去した天然ゴムであることが好ましい。
さらに、本発明によれば、このような共役ジエン系重合体ラテックス組成物からなる膜成形体、および、このような共役ジエン系重合体ラテックス組成物からなる膜成形体、ディップ成形体、および接着剤組成物が提供される。 Further, according to the present invention, there is provided a conjugated diene polymer latex composition containing a latex of a conjugated diene polymer, a vulcanizing agent, and the xanthogen compound dispersion of the present invention.
The conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound.
In the conjugated diene polymer latex composition of the present invention, it is preferable that the conjugated diene polymer is a synthetic polyisoprene, a styrene-isoprene-styrene block copolymer, or a natural rubber from which proteins have been removed.
Further, according to the present invention, a film molded product made of such a conjugated diene polymer latex composition, and a film molded product made of such a conjugated diene polymer latex composition, a dip molded product, and an adhesive. The agent composition is provided.
本発明によれば、共役ジエン系重合体などの重合体の加硫促進剤として用い、ディップ成形体などの膜成形体とした場合に、即時型アレルギー(Type I)に加えて遅延型アレルギー(Type IV)の症状の発生を抑制可能であり、しかも、得られるディップ成形体などの膜成形体を、引張強度および引裂強度に優れ、かつ、引張強度および引裂強度の安定性に優れたものとすることができるキサントゲン化合物分散体、ならびに、このようなキサントゲン化合物分散体を用いて得られる共役ジエン系重合体ラテックス組成物、およびこのような共役ジエン系重合体ラテックス組成物からなる膜成形体、ディップ成形体、および接着剤組成物を提供することができる。
According to the present invention, when a polymer such as a conjugated diene polymer is used as a vulcanization accelerator to form a film molded product such as a dip molded product, a delayed type allergy (Type I) is added to a delayed type allergy (Type I). It is possible to suppress the occurrence of Type IV) symptoms, and the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and also has excellent tensile strength and tear strength stability. A xanthogen compound dispersion which can be used, a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and a film molded product comprising such a conjugated diene polymer latex composition. A dip molded product and an adhesive composition can be provided.
<キサントゲン化合物分散体>
本発明のキサントゲン化合物分散体は、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有する。 <Xanthate compound dispersion>
The xanthate compound dispersion of the present invention contains a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
本発明のキサントゲン化合物分散体は、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有する。 <Xanthate compound dispersion>
The xanthate compound dispersion of the present invention contains a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
本発明で用いるキサントゲン化合物は、加硫促進剤として作用する化合物であり、そのため、本発明のキサントゲン化合物分散体は、共役ジエン系重合体などの重合体の加硫促進剤として好適に用いることができる。キサントゲン化合物は、加硫時においては、加硫促進剤として作用し、加硫が行われた後には、加硫時に加わる熱等により、アルコールおよび二硫化炭素等に分解されるものである。また、分解により生成したアルコールおよび二硫化炭素等は、加硫時に加わる熱等により、通常、揮発するため、これにより、得られる共役ジエン系重合体などの重合体の加硫物中の、キサントゲン化合物の残留量を抑えることができる。そのため、本発明によれば、従来、遅延型アレルギー(Type IV)の症状の発生原因となっていた加硫促進剤(たとえば、チウラム系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤、チアゾール系加硫促進剤など)を使用することなく、本発明に係るキサントゲン化合物分散体を用いることにより、得られる共役ジエン系重合体などの重合体の加硫物(たとえば、ディップ成形体などの膜成形体)中における、アレルギーの原因となる物質の含有量を低減できるため、即時型アレルギー(Type I)に加えて、遅延型アレルギー(Type IV)の症状の発生を抑制できるものである。
The xanthogen compound used in the present invention is a compound that acts as a vulcanization accelerator. Therefore, the xanthogen compound dispersion of the present invention can be suitably used as a vulcanization accelerator for a polymer such as a conjugated diene polymer. it can. The xanthogen compound acts as a vulcanization accelerator during vulcanization, and after vulcanization, it is decomposed into alcohol, carbon disulfide, and the like by the heat applied during vulcanization. In addition, alcohol, carbon disulfide, etc. produced by decomposition usually volatilize due to heat applied during vulcanization, etc., and thus xanthogen in the vulcanized product of the obtained polymer such as a conjugated diene polymer. The residual amount of the compound can be suppressed. Therefore, according to the present invention, a vulcanization accelerator (for example, a thiuram-based vulcanization accelerator, a dithiocarbamate-based vulcanization accelerator, thiazole) which has conventionally caused the occurrence of delayed type allergy (Type IV) symptoms. A vulcanized product of a polymer such as a conjugated diene polymer obtained by using the xanthogen compound dispersion according to the present invention without using a system vulcanization accelerator (for example, a film such as a dip molded product). Since the content of the substance that causes allergy can be reduced in the polymer), the occurrence of the symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I) can be suppressed.
本発明で用いるキサントゲン化合物としては、特に限定されないが、たとえば、キサントゲン酸、キサントゲン酸塩などが挙げられる。
The xanthogen compound used in the present invention is not particularly limited, and examples thereof include xanthate acid and xanthogenate.
キサントゲン酸塩としては、キサントゲン酸構造を有する塩化合物であればよく、特に限定されないが、キサントゲン酸の金属塩であることが好ましく、なかでも、一般式(ROC(=S)S)x-Z(ここで、Rは直鎖状または分岐状の炭化水素、Zは金属原子である。xはZの原子価と一致する数で、通常1~4、好ましくは2~4、特に好ましくは2である。)で表される化合物が好適である。また、キサントゲン酸の金属塩の中でも、キサントゲン酸の亜鉛塩がより好ましい。
The xanthogenate may be a salt compound having a xanthate structure, and is not particularly limited, but is preferably a metal salt of xanthate, and among them, the general formula (ROC (= S) S) xZ. (Here, R is a linear or branched hydrocarbon, Z is a metal atom. X is a number corresponding to the valence of Z, and is usually 1 to 4, preferably 2 to 4, particularly preferably 2. The compound represented by) is preferable. Further, among the metal salts of xanthate, the zinc salt of xanthate is more preferable.
上記一般式(ROC(=S)S)x-Zで表されるキサントゲン酸塩としては、特に限定されないが、たとえば、ジメチルキサントゲン酸亜鉛、ジエチルキサントゲン酸亜鉛、ジプロピルキサントゲン酸亜鉛、ジイソプロピルキサントゲン酸亜鉛、ジブチルキサントゲン酸亜鉛、ジペンチルキサントゲン酸亜鉛、ジヘキシルキサントゲン酸亜鉛、ジヘプチルキサントゲン酸亜鉛、ジオクチルキサントゲン酸亜鉛、ジ(2-エチルヘキシル)キサントゲン酸亜鉛、ジデシルキサントゲン酸亜鉛、ジドデシルキサントゲン酸亜鉛、ジメチルキサントゲン酸カリウム、エチルキサントゲン酸カリウム、プロピルキサントゲン酸カリウム、イソプロピルキサントゲン酸カリウム、ブチルキサントゲン酸カリウム、ペンチルキサントゲン酸カリウム、ヘキシルキサントゲン酸カリウム、ヘプチルキサントゲン酸カリウム、オクチルキサントゲン酸カリウム、2-エチルヘキシルキサントゲン酸カリウム、デシルキサントゲン酸カリウム、ドデシルキサントゲン酸カリウム、メチルキサントゲン酸ナトリウム、エチルキサントゲン酸ナトリウム、プロピルキサントゲン酸ナトリウム、イソプロピルキサントゲン酸ナトリウム、ブチルキサントゲン酸ナトリウム、ペンチルキサントゲン酸ナトリウム、ヘキシルキサントゲン酸ナトリウム、ヘプチルキサントゲン酸ナトリウム、オクチルキサントゲン酸ナトリウム、2-エチルヘキシルキサントゲン酸ナトリウム、デシルキサントゲン酸ナトリウム、ドデシルキサントゲン酸ナトリウム等が挙げられる。これらのなかでも、イソプロピルキサントゲン酸塩類、ブチルキサントゲン酸塩類であってよく、上記一般式(ROC(=S)S)x-Zにおけるxが2以上であるキサントゲン酸塩が好ましく、ジイソプロピルキサントゲン酸塩類、ジブチルキサントゲン酸塩類がより好ましく、ジイソプロピルキサントゲン酸亜鉛、ジブチルキサントゲン酸亜鉛がさらに好ましく、ジイソプロピルキサントゲン酸亜鉛が特に好ましい。
The xanthogenate represented by the above general formula (ROC (= S) S) xZ is not particularly limited, and is, for example, zinc dimethylxanthate, zinc diethylxanthogenate, zinc dipropylxanthate, diisopropylxanthate. Zinc, Zinc dibutylxanthate, Zinc dipentylxanthate, Zinc dihexylxanthate, Zinc diheptylxanthate, Zinc dioctylxanthate, Zinc di (2-ethylhexyl) xanthate, Zinc didecylxanthate, Zinc didodecylxanthate, Potassium dimethylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, potassium butylxanthate, potassium pentylxanthate, potassium hexylxanthate, potassium heptylxanthate, potassium octylxanthate, 2-ethylhexanthate Potassium, potassium decylxanthate, potassium dodecylxanthate, sodium methylxanthate, sodium ethylxanthate, sodium propylxanthate, sodium isopropylxanthate, sodium butylxanthate, sodium pentylxanthate, sodium hexylxanthate, heptylxanthate Examples thereof include sodium, sodium octylxanthate, sodium 2-ethylhexanthate, sodium decylxanthate, and sodium dodecylxanthate. Among these, isopropylxanthogenates and butylxanthogenates may be used, and xanthogenates having x of 2 or more in the above general formula (ROC (= S) S) xZ are preferable, and diisopropylxanthogenates. , Dibutylxanthogenates are more preferable, zinc diisopropylxanthogenate and zinc dibutylxanthogenate are further preferable, and zinc diisopropylxanthogenate is particularly preferable.
なお、これらのキサントゲン化合物は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
Note that these xanthogen compounds may be used alone or in combination of two or more.
本発明で用いるキサントゲン化合物は、キサントゲン化合物分散体中において、粒子状あるいは粉末状で分散しているものである。
The xanthate compound used in the present invention is dispersed in the xanthate compound dispersion in the form of particles or powder.
キサントゲン化合物分散体中におけるキサントゲン化合物の体積平均粒子径は、好ましくは0.001~9μmの範囲であり、より好ましくは0.05~7μmの範囲であり、さらに好ましくは0.05~5μmの範囲、特に好ましくは0.07~3μmの範囲である。体積平均粒子径を上記範囲とすることにより、キサントゲン化合物分散体中におけるキサントゲン化合物の分散性を高めることができる。また、体積平均粒子径を上記範囲とすることにより、本発明のキサントゲン化合物分散体を、共役ジエン系重合体などの重合体の加硫促進剤として用い、ディップ成形体などの膜成形体とした場合に、得られるディップ成形体などの膜成形体を、引張強度および引裂強度により優れ、かつ、引張強度および引裂強度の安定性により優れたものとすることができる。
The volume average particle size of the xanthogen compound in the xantogen compound dispersion is preferably in the range of 0.001 to 9 μm, more preferably in the range of 0.05 to 7 μm, and further preferably in the range of 0.05 to 5 μm. Particularly preferably, it is in the range of 0.07 to 3 μm. By setting the volume average particle size in the above range, the dispersibility of the xanthate compound in the xanthate compound dispersion can be enhanced. Further, by setting the volume average particle size in the above range, the xanthogen compound dispersion of the present invention was used as a vulcanization accelerator for a polymer such as a conjugated diene polymer to obtain a film molded product such as a dip molded product. In some cases, the obtained film-molded article such as a dip-molded article can be made superior in tensile strength and tear strength, and also in stability of tensile strength and tear strength.
キサントゲン化合物分散体中におけるキサントゲン化合物の95%体積累積径(D95)は、0.1~43μmの範囲にあることが好ましく、より好ましくは0.1~40μmの範囲、さらに好ましくは0.1~35μm、特に好ましくは0.1~20μmの範囲である。95%体積累積径(D95)を上記範囲とすることにより、得られるディップ成形体などの膜成形体を、引張強度および引裂強度により優れ、かつ、引張強度および引裂強度の安定性により優れたものとすることができる。なお、キサントゲン化合物の体積平均粒子径および95%体積累積径(D95)は、たとえば、レーザー回折散乱式粒度分布計を用いて測定することができる。
The 95% volume cumulative diameter (D95) of the xanthate compound in the xanthate compound dispersion is preferably in the range of 0.1 to 43 μm, more preferably in the range of 0.1 to 40 μm, and further preferably in the range of 0.1 to 0.1 to 40 μm. It is in the range of 35 μm, particularly preferably 0.1 to 20 μm. By setting the 95% volume cumulative diameter (D95) in the above range, the obtained film molded body such as a dip molded body is excellent in tensile strength and tear strength, and is excellent in stability of tensile strength and tear strength. Can be. The volume average particle diameter and the 95% volume cumulative diameter (D95) of the xantogen compound can be measured using, for example, a laser diffraction / scattering type particle size distribution meter.
本発明のキサントゲン化合物分散体中における、キサントゲン化合物の含有割合は、キサントゲン化合物分散体全体に対して、好ましくは1~60重量%であり、より好ましくは10~50重量%、さらに好ましくは20~50重量%、特に好ましくは30~50重量%である。キサントゲン化合物の含有割合を上記範囲とすることにより、キサントゲン化合物分散体を、保存安定性により優れたものとすることができる。
The content ratio of the xanthate compound in the xanthate compound dispersion of the present invention is preferably 1 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 20 to the total weight of the xanthate compound dispersion. It is 50% by weight, particularly preferably 30 to 50% by weight. By setting the content ratio of the xanthate compound in the above range, the xanthate compound dispersion can be made more excellent in storage stability.
本発明のキサントゲン化合物分散体は、上述したキサントゲン化合物に加えて、ポリオキシアルキレン構造を有しないアニオン系界面活性剤およびノニオン系界面活性剤を含有し、これらを、水またはアルコールに分散させてなる分散体である。
The xanthate compound dispersion of the present invention contains, in addition to the above-mentioned xanthate compound, an anionic surfactant and a nonionic surfactant having no polyoxyalkylene structure, and these are dispersed in water or alcohol. It is a dispersion.
キサントゲン化合物は、常温で固体であり、水にもアルコールにも溶解しないため、通常は、粉末状態で用いられるものである。しかしながら、粉末状態のキサントゲン化合物は、共役ジエン系重合体などの重合体を含むラテックス組成物に配合した場合に、分散性が不十分となりやすく、そのため、加硫促進剤としての効果を十分に発揮できないという問題があった。
Since the xanthate compound is solid at room temperature and does not dissolve in water or alcohol, it is usually used in a powder state. However, the powdered xanthogen compound tends to have insufficient dispersibility when blended in a latex composition containing a polymer such as a conjugated diene polymer, and therefore, sufficiently exerts its effect as a vulcanization accelerator. There was a problem that it could not be done.
また、このようなキサントゲン化合物を加硫促進剤として用い、これを、共役ジエン系重合体などの重合体のラテックスに配合して、ラテックス組成物とし、ディップ成形体などの膜成形体を製造する場合には、生産効率の観点より、同じラテックス組成物を用いて、多数のディップ成形体などの膜成形体を連続的に製造することが望ましい。そして、この場合には、同じラテックス組成物が、数日間にわたり使用されることとなる。その一方で、同じラテックス組成物を数日間にわたり使用した場合、使用開始から数日間が経過した場合に、ラテックス組成物の熟成(前加硫)が進行してしまい、そのため、使用開始から数日間が経過したラテックス組成物を用いて得られる膜成形体は、使用開始直後に得られる膜成形体と比較して、引張強度や引裂強度が大きく低下してしまう場合があり、得られる膜成形体の引張強度や引裂強度の安定性(熟成安定性)が不十分であるという課題があった。
Further, such a xanthogen compound is used as a vulcanization accelerator, and this is blended with the latex of a polymer such as a conjugated diene polymer to obtain a latex composition, and a film molded product such as a dip molded product is produced. In some cases, from the viewpoint of production efficiency, it is desirable to continuously produce a large number of film-molded products such as dip-molded products using the same latex composition. And in this case, the same latex composition will be used for several days. On the other hand, when the same latex composition is used for several days, the aging (pre-vulcanization) of the latex composition proceeds when several days have passed from the start of use, and therefore, several days from the start of use. The film-molded article obtained by using the latex composition that has passed the above period may have a significantly lower tensile strength and tear strength than the film-molded article obtained immediately after the start of use, and the obtained film-molded article may be significantly reduced. There is a problem that the stability of tensile strength and tear strength (aging stability) of the latex is insufficient.
これらの問題を解決するために、本発明者等が鋭意検討したところ、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有するキサントゲン化合物分散体によれば、キサントゲン化合物を良好に分散した分散体が得られること、さらには、このような分散体の状態で、共役ジエン系重合体のラテックスと、加硫剤と混合することでキサントゲン化合物が良好に分散したラテックス組成物が得られることを見出した。そして、これにより、得られるディップ成形体などの膜成形体を、引張強度および引裂強度に優れたものとすることができ、かつ、引張強度および引裂強度の安定性にも優れたものとすることができることを見出したものである。特に、本発明のキサントゲン化合物分散体によれば、ラテックス組成物とした際における、熟成安定性に優れたものであるため、ラテックス組成物をより長期間使用した場合でも、引張強度および引裂強度を極端に低下させることなく、ディップ成形体などの膜成形体を生産することが可能であり、結果として、ディップ成形体などの膜成形体の生産効率の向上に資するものである。
In order to solve these problems, the present inventors have diligently studied and found that a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol were used. According to the xanthate compound dispersion contained therein, a dispersion in which the xanthate compound is well dispersed can be obtained, and further, in the state of such a dispersion, the latex of the conjugated diene polymer is mixed with the sulfide. It has been found that a latex composition in which the xanthate compound is well dispersed can be obtained. As a result, the obtained film molded product such as a dip molded product can be made excellent in tensile strength and tear strength, and also in stability of tensile strength and tear strength. I found that I could do it. In particular, according to the xanthogen compound dispersion of the present invention, the latex composition is excellent in aging stability, so that even when the latex composition is used for a longer period of time, the tensile strength and the tear strength can be improved. It is possible to produce a film molded product such as a dip molded product without extremely reducing it, and as a result, it contributes to improvement in the production efficiency of the film molded product such as a dip molded product.
本発明で用いるポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、ポリオキシアルキレン構造を有しないアニオン性の化合物であればよく、特に限定されないが、キサントゲン化合物の分散性をより良好なものとする観点から、芳香族スルホン酸化合物、芳香族カルボン酸化合物などの芳香族化合物が好ましく、芳香族スルホン酸化合物であることがより好ましい。
The anionic surfactant having no polyoxyalkylene structure used in the present invention may be any anionic compound having no polyoxyalkylene structure, and is not particularly limited, but has better dispersibility of the xanthogen compound. From this point of view, aromatic compounds such as aromatic sulfonic acid compounds and aromatic carboxylic acid compounds are preferable, and aromatic sulfonic acid compounds are more preferable.
ポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、下記一般式(1)で表される芳香族スルホン酸化合物が好ましい。
(上記一般式(1)中、R1およびR2は、それぞれ独立して、水素原子または任意の有機基であり、M+は、1価の陽イオンである。R1およびR2は互いに結合して環構造を形成していてもよい。)
As the anionic surfactant having no polyoxyalkylene structure, an aromatic sulfonic acid compound represented by the following general formula (1) is preferable.
(In the above general formula (1), R 1 and R 2 are independently hydrogen atoms or arbitrary organic groups, and M + is a monovalent cation. R 1 and R 2 are mutually. They may be combined to form a ring structure.)
上記一般式(1)において、M+は、1価の陽イオンであればよく、特に限定されないが、H+、アルカリ金属イオン、Ag+、Cu+、NH4
+が好ましく、アルカリ金属イオンがより好ましく、Na+、K+がさらに好ましく、Na+が特に好ましい。
In the general formula (1), M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
R1およびR2が互いに結合しない場合に、R1およびR2となりうる有機基としては、特に限定されないが、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基などの炭素数1~30のアルキル基;シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などの炭素数3~30のシクロアルキル基;フェニル基、ビフェニル基、ナフチル基、アントラニル基などの炭素数6~30のアリール基;メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、t-ブトキシ基、n-ペンチルオキシ基、n-ヘキシルオキシ基、フェノキシ基などの炭素数1~30のアルコキシ基;などが挙げられる。なお、これらの有機基は、置換基を有していてもよく、該置換基の位置としては、任意の位置とすることができる。
When the R 1 and R 2 are not bonded to each other, as the organic group can be an R 1 and R 2, but not limited to, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group , Se-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 30 carbon atoms. Cycloalkyl group having 3 to 30 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; aryl having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group and anthranyl group Group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, phenoxy group, etc. An alkoxy group having 1 to 30 carbon atoms; and the like. In addition, these organic groups may have a substituent, and the position of the substituent can be any position.
また、R1およびR2が互いに結合して環構造を形成する場合には、環構造としては、特に限定されないが、芳香族化合物が好ましく、ベンゼン、ナフタレンなどのベンゼン環を有する芳香族化合物がより好ましく、ナフタレンが特に好ましい。なお、これらの環構造は、置換基を有していてもよく、該置換基の位置としては、任意の位置とすることができる。
When R 1 and R 2 are bonded to each other to form a ring structure, the ring structure is not particularly limited, but an aromatic compound is preferable, and an aromatic compound having a benzene ring such as benzene or naphthalene is used. More preferably, naphthalene is particularly preferable. In addition, these ring structures may have a substituent, and the position of the substituent can be any position.
ポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、上記一般式(1)で表される芳香族スルホン酸化合物の中でも、特に好ましいものとして、R1およびR2が互いに結合して環構造を形成して、上記一般式(1)においてベンゼン環構造を形成しているものが挙げられる。より具体的には、下記一般式(2)で表される構造を有する化合物を用いることが好ましい。
(上記一般式(2)中、R3は、置換基を有していてもよい2価の炭化水素基であり、M+は、1価の陽イオンである。)
As the anionic surfactant having no polyoxyalkylene structure, among the aromatic sulfonic acid compounds represented by the above general formula (1), particularly preferable ones, R 1 and R 2 are bonded to each other to form a ring structure. , And the benzene ring structure is formed in the above general formula (1). More specifically, it is preferable to use a compound having a structure represented by the following general formula (2).
(In the above general formula (2), R 3 is a divalent hydrocarbon group which may have a substituent, and M + is a monovalent cation.)
上記一般式(2)において、M+は、1価の陽イオンであればよく、特に限定されないが、H+、アルカリ金属イオン、Ag+、Cu+、NH4
+が好ましく、アルカリ金属イオンがより好ましく、Na+、K+がさらに好ましく、Na+が特に好ましい。
In the general formula (2), M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
上記一般式(2)において、R3は、置換基を有していてもよい2価の炭化水素基であればよく、特に限定されないが、炭素数1~10のアルキレン基が好ましく、メチレン基が特に好ましい。
In the above general formula (2), R 3 may be a divalent hydrocarbon group which may have a substituent, and is not particularly limited, but an alkylene group having 1 to 10 carbon atoms is preferable, and a methylene group is preferable. Is particularly preferable.
ポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、上記一般式(2)で表される構造を繰り返して有することが好ましく、上記一般式(2)で表される構造の繰り返し単位数は、特に限定されないが、好ましくは10~100個、より好ましくは20~50個である。
The anionic surfactant having no polyoxyalkylene structure preferably has the structure represented by the general formula (2) repeatedly, and the number of repeating units of the structure represented by the general formula (2) is Although not particularly limited, the number is preferably 10 to 100, more preferably 20 to 50.
また、ポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、上記一般式(1)または(2)で表される芳香族スルホン酸化合物中の、スルホン酸イオン性基(-SO3
-)を、カルボン酸イオン性基(-COO-)に置き換えた、芳香族カルボン酸化合物を用いることもできる。この場合、上記一般式(1)中のR1およびR2、ならびに、上記一般式(2)中のR3は、上記と同様である。
As the anionic surfactant having no polyoxyalkylene structure, the general formula (1) or of an aromatic sulfonic acid compound represented by Formula (2), sulfonate ion group (-SO 3 -) the carboxylic acid ion group (-COO -) was replaced, it is also possible to use an aromatic carboxylic acid compound. In this case, R 1 and R 2 in the general formula (1) and R 3 in the general formula (2) are the same as described above.
さらに、本発明で用いるポリオキシアルキレン構造を有しないアニオン系界面活性剤としては、上述したものに限定されず、ラウリン酸ナトリウム、ミリスチン酸カリウム、パルミチン酸ナトリウム、オレイン酸カリウム、リノレン酸ナトリウム、ロジン酸ナトリウム等の脂肪酸塩;ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウム、デシルベンゼンスルホン酸ナトリウム、デシルベンゼンスルホン酸カリウム、セチルベンゼンスルホン酸ナトリウム、セチルベンゼンスルホン酸カリウム等のアルキルベンゼンスルホン酸塩;ジ(2-エチルヘキシル)スルホコハク酸ナトリウム、ジ(2-エチルヘキシル)スルホコハク酸カリウム、ジオクチルスルホコハク酸ナトリウム等のアルキルスルホコハク酸塩;ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等のアルキル硫酸エステル塩;ラウリルリン酸ナトリウム、ラウリルリン酸カリウム等のモノアルキルリン酸塩;等を用いることもできる。
Further, the anionic surfactant having no polyoxyalkylene structure used in the present invention is not limited to those described above, and is not limited to those described above, but is limited to sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and rosin. Fatty acid salts such as sodium acid acid; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate, etc.; Alkyl sulfosuccinates such as sodium (2-ethylhexyl) sulfosuccinate, potassium di (2-ethylhexyl) sulfosuccinate, sodium dioctyl sulfosuccinate; alkyl sulphate esters such as sodium lauryl sulfate and potassium lauryl sulfate; sodium lauryl phosphate, lauryl Monoalkyl phosphates such as potassium phosphate; etc. can also be used.
本発明で用いるポリオキシアルキレン構造を有しないアニオン系界面活性剤の重量平均分子量(Mw)は、好ましくは200~20000、より好ましくは400~10000である。本発明で用いるポリオキシアルキレン構造を有しないアニオン系界面活性剤の数平均分子量(Mn)は、好ましくは100~5000、より好ましくは200~1000である。ポリオキシアルキレン構造を有しないアニオン系界面活性剤の重量平均分子量(Mw)および数平均分子量(Mn)は、ゲル・パーミーエーション・クロマトグラフィー分析による標準ポリスチレン換算の値である。
The weight average molecular weight (Mw) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 200 to 20000, more preferably 400 to 10000. The number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 100 to 5000, more preferably 200 to 1000. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure are values converted to standard polystyrene by gel permeation chromatography analysis.
本発明のキサントゲン化合物分散体中における、ポリオキシアルキレン構造を有しないアニオン系界面活性剤の含有量は、特に限定されないが、キサントゲン化合物100重量部に対して、好ましくは0.1~30重量部、より好ましくは1~20重量部、さらに好ましくは2~18重量部、特に好ましくは3~15重量部、最も好ましくは5~10重量部である。ポリオキシアルキレン構造を有しないアニオン系界面活性剤の含有量を上記範囲とすることにより、キサントゲン化合物分散体中における、キサントゲン化合物の分散性をより高めることができ、これにより、得られるディップ成形体などの膜成形体の、引張強度および引裂強度をより高めることができ、かつ、引張強度および引裂強度の安定性をより高めることができる。
The content of the anionic surfactant having no polyoxyalkylene structure in the xanthate compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the xanthate compound. , More preferably 1 to 20 parts by weight, still more preferably 2 to 18 parts by weight, particularly preferably 3 to 15 parts by weight, and most preferably 5 to 10 parts by weight. By setting the content of the anionic surfactant having no polyoxyalkylene structure in the above range, the dispersibility of the xanthogen compound in the xanthogen compound dispersion can be further enhanced, and thus the obtained dip molded product can be obtained. The tensile strength and tear strength of the film-molded product such as, etc. can be further increased, and the stability of the tensile strength and tear strength can be further enhanced.
本発明で用いるノニオン系界面活性剤は、その分子主鎖中に、非イオン性の界面活性剤として作用するセグメントを有するものである。このような非イオン性の界面活性剤として作用するセグメントとしては、ポリオキシアルキレン構造が好適に挙げられる。
The nonionic surfactant used in the present invention has a segment in its molecular main chain that acts as a nonionic surfactant. A polyoxyalkylene structure is preferably mentioned as a segment that acts as such a nonionic surfactant.
ノニオン系界面活性剤の具体例としては、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレン(硬化)ヒマシ油、ポリオキシエチレンアルキルアミン、脂肪酸アルカノールアミドなどが挙げられる。
Specific examples of nonionic surfactants include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene styrene phenyl ether, polyoxyethylene (hardened) castor oil, and polyoxyethylene alkyl. Examples include amines and fatty acid alkanolamides.
ポリオキシアルキレングリコールとしては、たとえば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコールなどのポリオキシプロピレングリコールエチレンオキサイド付加物等が挙げられる。
Examples of the polyoxyalkylene glycol include polyoxypropylene glycol ethylene oxide adducts such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene glycol.
ポリオキシアルキレンアルキルエーテルとしては、たとえば、プロピレンオキサイドおよび/またはエチレンオキサイドが1~50個(好ましくは、1~10個)付加した直鎖状もしくは分岐鎖状エーテルが挙げられる。これらの中でも、プロピレンオキサイドが1~50個(好ましくは、1~10個)付加した直鎖状もしくは分岐鎖状エーテル、エチレンオキサイドが1~50個(好ましくは、1~10個)付加した直鎖状もしくは分岐鎖状エーテル、エチレンオキサイドとプロピレンオキサイドが合計2~50個(好ましくは、2~10個)ブロックもしくはランダムに付加した直鎖状もしくは分岐鎖状エーテルなどが挙げられる。ポリオキシアルキレンアルキルエーテルとしては、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルドデシルエーテル、ポリオキシエチレンドデシルエーテル、ポリオキシエチレンラウリルエーテルなどが挙げられ、これらのなかでも、ポリオキシエチレンオレイルエーテルおよびポリオキシエチレンオクチルドデシルエーテルが好ましい。
Examples of the polyoxyalkylene alkyl ether include linear or branched chain ethers to which 1 to 50 (preferably 1 to 10) propylene oxide and / or ethylene oxide are added. Among these, linear or branched chain ethers to which 1 to 50 propylene oxides (preferably 1 to 10) are added, and direct ethylene oxides to which 1 to 50 (preferably 1 to 10) are added. Examples include chain-shaped or branched-chain ethers, and linear or branched-chain ethers in which a total of 2 to 50 (preferably 2 to 10) blocks of ethylene oxide and propylene oxide are added or randomly added. Examples of the polyoxyalkylene alkyl ether include polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene dodecyl ether, polyoxyethylene lauryl ether, and the like, among these, polyoxyethylene oleyl ether and polyoxy. Polyethylene octyldodecyl ether is preferred.
ポリオキシアルキレンアルキルフェニルエーテルとしては、アルキルフェノールに、プロピレンオキサイドおよび/またはエチレンオキサイドが1~50個(好ましくは、1~10個)付加した化合物などが挙げられる。
ポリオキシエチレンスチレン化フェニルエーテルとしては、(モノ、ジ、トリ)スチレン化フェノールのエチレンオキサイド付加物などが挙げられ、これらのなかでも、ジスチレン化フェノールのエチレンオキサイド付加物である、ポリオキシエチレンジスチレン化フェニルエーテルが好ましい。 Examples of the polyoxyalkylene alkyl phenyl ether include compounds in which 1 to 50 (preferably 1 to 10) of propylene oxide and / or ethylene oxide are added to the alkyl phenol.
Examples of the polyoxyethylene styrene phenyl ether include ethylene oxide adducts of (mono, di, tri) styrene phenol, and among these, polyoxyethylene di, which is an ethylene oxide adduct of distyrene phenol. Polyethylene phenyl ether is preferred.
ポリオキシエチレンスチレン化フェニルエーテルとしては、(モノ、ジ、トリ)スチレン化フェノールのエチレンオキサイド付加物などが挙げられ、これらのなかでも、ジスチレン化フェノールのエチレンオキサイド付加物である、ポリオキシエチレンジスチレン化フェニルエーテルが好ましい。 Examples of the polyoxyalkylene alkyl phenyl ether include compounds in which 1 to 50 (preferably 1 to 10) of propylene oxide and / or ethylene oxide are added to the alkyl phenol.
Examples of the polyoxyethylene styrene phenyl ether include ethylene oxide adducts of (mono, di, tri) styrene phenol, and among these, polyoxyethylene di, which is an ethylene oxide adduct of distyrene phenol. Polyethylene phenyl ether is preferred.
ポリオキシエチレン(硬化)ヒマシ油としては、ヒマシ油もしくは硬化ヒマシ油のエチレンオキサイド付加物が挙げられる。
Examples of polyoxyethylene (hardened) castor oil include castor oil and ethylene oxide adducts of hardened castor oil.
脂肪酸アルカノールアミドとしては、たとえば、ラウリン酸ジエタノールアミド、パルミチン酸ジエタノールアミド、ミリスチン酸ジエタノールアミド、ステアリン酸ジエタノールアミド、オレイン酸ジエタノールアミド、パーム油脂肪酸ジエタノールアミド、ヤシ油脂肪酸ジエタノールアミド等が挙げられる。
Examples of the fatty acid alkanolamide include lauric acid diethanolamide, palmitic acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, palm oil fatty acid diethanolamide, and coconut oil fatty acid diethanolamide.
ノニオン系界面活性剤の中でも、ポリオキシアルキレン構造を有するノニオン系界面活性剤が好ましく、ポリオキシエチレン構造を有するノニオン系界面活性剤がより好ましく、ポリオキシエチレンのヒドロカルビル化エーテルであることがより好ましく、ポリオキシエチレンアルキルエーテルおよびポリオキシエチレンジスチレン化フェニルエーテルがさらに好ましく、ポリオキシエチレンアルキルエーテルが特に好ましい。ノニオン系界面活性剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
Among the nonionic surfactants, a nonionic surfactant having a polyoxyalkylene structure is preferable, a nonionic surfactant having a polyoxyethylene structure is more preferable, and a hydrocarbylated ether of polyoxyethylene is more preferable. , Polyoxyethylene alkyl ethers and polyoxyethylene distyrene phenyl ethers are more preferred, and polyoxyethylene alkyl ethers are particularly preferred. The nonionic surfactant may be used alone or in combination of two or more.
また、本発明で用いるノニオン系界面活性剤は、非イオン性の界面活性剤として作用するセグメントに加えて、アニオン性の界面活性剤として作用するセグメントを有する、ノニオニックアニオン系界面活性剤であってもよい。本発明で用いるノニオン系界面活性剤は、アニオン性の界面活性剤として作用するセグメントを有しないものが好ましい。
The nonionic surfactant used in the present invention is a nonionic anionic surfactant having a segment acting as an anionic surfactant in addition to a segment acting as a nonionic surfactant. There may be. The nonionic surfactant used in the present invention preferably does not have a segment that acts as an anionic surfactant.
ノニオニックアニオン系界面活性剤としては、たとえば、下記一般式(3)で表される化合物などが挙げられる。
R4-O-(CR5R6CR7R8)n-SO3M (3)
(上記一般式(3)中、R4は、炭素数6~16のアルキル基、または炭素数1~25のアルキル基で置換されていてもよい炭素数6~14のアリール基、R5~R8は、水素およびメチル基よりなる群からそれぞれ独立して選ばれる基、Mは、アルカリ金属原子またはアンモニウムイオン、nは3~40である。) Examples of the nonionic anionic surfactant include compounds represented by the following general formula (3).
R 4- O- (CR 5 R 6 CR 7 R 8 ) n- SO 3 M (3)
(In the above general formula (3), R 4 is an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 6 to 16 carbon atoms or an alkyl group having 1 to 25 carbon atoms, R 5 to R 8 is a group independently selected from the group consisting of hydrogen and methyl groups, M is an alkali metal atom or ammonium ion, and n is 3 to 40.)
R4-O-(CR5R6CR7R8)n-SO3M (3)
(上記一般式(3)中、R4は、炭素数6~16のアルキル基、または炭素数1~25のアルキル基で置換されていてもよい炭素数6~14のアリール基、R5~R8は、水素およびメチル基よりなる群からそれぞれ独立して選ばれる基、Mは、アルカリ金属原子またはアンモニウムイオン、nは3~40である。) Examples of the nonionic anionic surfactant include compounds represented by the following general formula (3).
R 4- O- (CR 5 R 6 CR 7 R 8 ) n- SO 3 M (3)
(In the above general formula (3), R 4 is an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 6 to 16 carbon atoms or an alkyl group having 1 to 25 carbon atoms, R 5 to R 8 is a group independently selected from the group consisting of hydrogen and methyl groups, M is an alkali metal atom or ammonium ion, and n is 3 to 40.)
上記一般式(3)で表される化合物の具体例としては、ポリオキシエチレンラウリルエーテル硫酸塩、ポリオキシエチレンセチルエーテル硫酸塩、ポリオキシエチレンステアリルエーテル硫酸塩、ポリオキシエチレンオレイルエーテル硫酸塩などのポリオキシエチレンアルキルエーテル硫酸塩;ポリオキシエチレンノニルフェニルエーテル硫酸塩、ポリオキシエチレンオクチルフェニルエーテル硫酸塩、ポリオキシエチレンジスチリルエーテル硫酸塩などのポリオキシエチレンアリールエーテル硫酸塩;などが挙げられる。
Specific examples of the compound represented by the above general formula (3) include polyoxyethylene lauryl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, polyoxyethylene oleyl ether sulfate, and the like. Polyoxyethylene alkyl ether sulfate; polyoxyethylene aryl phenyl ether sulfate such as polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene octylphenyl ether sulfate, polyoxyethylene distyryl ether sulfate; and the like.
ノニオニックアニオン系界面活性剤の中でも、ポリオキシアルキレン構造を有するノニオニックアニオン系界面活性剤が好ましく、ポリオキシエチレン構造を有するノニオニックアニオン系界面活性剤がより好ましい。ノニオニックアニオン系界面活性剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
Among the nonionic anionic surfactants, the nonionic anionic surfactant having a polyoxyalkylene structure is preferable, and the nonionic anionic surfactant having a polyoxyethylene structure is more preferable. The nonionic anionic surfactant may be used alone or in combination of two or more.
本発明で用いるノニオン系界面活性剤の数平均分子量(Mn)は、好ましくは100~5000、より好ましくは150~3500、さらに好ましくは180~2500、特に好ましくは200~1000である。ノニオン系界面活性剤の数平均分子量は、たとえば、ノニオン系界面活性剤をテトラヒドロフランに溶解して、0.2重量%溶液とした後、0.45μmのメンブランフィルターで濾過したものを測定試料として、ゲルパーミエーションクロマトグラフィ(GPC)を用いて下記条件にて測定することにより、標準ポリスチレン換算の数平均分子量として求めることができる。
測定装置:HLC-8220GPC(東ソー社製)
カラム:TSKgel G1000H(東ソー社製)、TSKgel G2000H(東ソー社製)
溶離液:テトラヒドロフラン(THF)
溶離速度:0.3ml/分
検知器:RI(極性(+))
カラム温度:40℃ The number average molecular weight (Mn) of the nonionic surfactant used in the present invention is preferably 100 to 5000, more preferably 150 to 3500, still more preferably 180 to 2500, and particularly preferably 200 to 1000. The number average molecular weight of the nonionic surfactant is, for example, a measurement sample obtained by dissolving the nonionic surfactant in tetrahydrofuran to prepare a 0.2 wt% solution and then filtering with a 0.45 μm membrane filter. It can be determined as a standard polystyrene-equivalent number average molecular weight by measuring under the following conditions using gel permeation chromatography (GPC).
Measuring device: HLC-8220GPC (manufactured by Tosoh)
Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh)
Eluent: tetrahydrofuran (THF)
Elution rate: 0.3 ml / min Detector: RI (polarity (+))
Column temperature: 40 ° C
測定装置:HLC-8220GPC(東ソー社製)
カラム:TSKgel G1000H(東ソー社製)、TSKgel G2000H(東ソー社製)
溶離液:テトラヒドロフラン(THF)
溶離速度:0.3ml/分
検知器:RI(極性(+))
カラム温度:40℃ The number average molecular weight (Mn) of the nonionic surfactant used in the present invention is preferably 100 to 5000, more preferably 150 to 3500, still more preferably 180 to 2500, and particularly preferably 200 to 1000. The number average molecular weight of the nonionic surfactant is, for example, a measurement sample obtained by dissolving the nonionic surfactant in tetrahydrofuran to prepare a 0.2 wt% solution and then filtering with a 0.45 μm membrane filter. It can be determined as a standard polystyrene-equivalent number average molecular weight by measuring under the following conditions using gel permeation chromatography (GPC).
Measuring device: HLC-8220GPC (manufactured by Tosoh)
Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh)
Eluent: tetrahydrofuran (THF)
Elution rate: 0.3 ml / min Detector: RI (polarity (+))
Column temperature: 40 ° C
本発明のキサントゲン化合物分散体中における、ノニオン系界面活性剤の含有量は、特に限定されないが、キサントゲン化合物100重量部に対して、好ましくは0.1~30重量部、より好ましくは1~20重量部、さらに好ましくは1.2~15重量部、特に好ましくは1.5~10重量部、最も好ましくは2~5重量部である。
The content of the nonionic surfactant in the xanthogen compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the xanthogen compound. It is by weight, more preferably 1.2 to 15 parts by weight, particularly preferably 1.5 to 10 parts by weight, and most preferably 2 to 5 parts by weight.
本発明のキサントゲン化合物分散体中における、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、前記ノニオン系界面活性剤との比率は、「ポリオキシアルキレン構造を有しないアニオン系界面活性剤:ノニオン系界面活性剤」の重量比で、99:1~10:90であることが好ましく、97:3~15:85であることがより好ましく、95:5~55:45であることがさらに好ましく、90:10~55:45であることが特に好ましく、85:15~70:30であることが最も好ましい。ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、前記ノニオン系界面活性剤との比率を上記範囲とすることにより、キサントゲン化合物分散体中における、キサントゲン化合物の分散性をより高めることができ、これにより、得られるディップ成形体などの膜成形体の、引張強度および引裂強度をより高めることができ、かつ、引張強度および引裂強度の安定性をより高めることができる。
The ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant in the xanthogen compound dispersion of the present invention is "anionic surfactant having no polyoxyalkylene structure: nonionic. The weight ratio of the "surfactant" is preferably 99: 1 to 10:90, more preferably 97: 3 to 15:85, and even more preferably 95: 5 to 55:45. , 90:10 to 55:45, most preferably 85:15 to 70:30. By setting the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant in the above range, the dispersibility of the xanthogen compound in the xanthogen compound dispersion can be further enhanced. Thereby, the tensile strength and the tear strength of the obtained film molded product such as the dip molded product can be further increased, and the stability of the tensile strength and the tear strength can be further enhanced.
本発明で用いる水またはアルコールとしては、水、メタノール、エタノール、プロパノールおよびブタノールから選択される少なくとも一種であることが好ましく、水であることがより好ましい。すなわち、本発明のキサントゲン化合物分散体は、水性分散体であることが好ましい。
The water or alcohol used in the present invention is preferably at least one selected from water, methanol, ethanol, propanol and butanol, and more preferably water. That is, the xanthate compound dispersion of the present invention is preferably an aqueous dispersion.
本発明のキサントゲン化合物分散体の製造方法としては、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールとを混合し、次いで、得られた混合液について解砕処理を行う方法が好ましい。ここで、解砕処理としては、分散体中に含有される、キサントゲン化合物の破砕や凝集の緩和を可能とすることができる処理であればよく、特に限定されないが、たとえば、せん断作用や摩砕作用を利用した解砕装置を用いる方法、攪拌式の解砕装置を用いる方法など、公知の解砕装置を用いる方法が挙げられる。具体的には、ロールミル、ハンマーミル、振動ミル、ジェットミル、ボールミル、遊星型ボールミル、ビーズミル、サンドミル、三本ロールミル等の解砕装置を使用することができる。これらのなかでも、ボールミル、遊星型ボールミル、またはビーズミルを使用して解砕処理を行う方法が好適である。
As a method for producing a xanthate compound dispersion of the present invention, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, water or an alcohol are mixed, and then the obtained mixed solution is used. A method of performing a crushing treatment is preferable. Here, the crushing treatment may be any treatment that can alleviate the crushing and aggregation of the xanthate compound contained in the dispersion, and is not particularly limited, but for example, shearing action or grinding. Examples thereof include a method using a known crusher, such as a method using a crusher utilizing the action and a method using a stirring type crusher. Specifically, a crushing device such as a roll mill, a hammer mill, a vibration mill, a jet mill, a ball mill, a planetary ball mill, a bead mill, a sand mill, or a three-roll mill can be used. Among these, a method of performing the crushing treatment using a ball mill, a planetary ball mill, or a bead mill is preferable.
たとえば、ボールミルを用いて解砕処理を行う場合には、メディアとして、メディアサイズが、好ましくはφ5~φ50mm、より好ましくはφ10~φ35mmであるものを使用し、回転数が、好ましくは10~300rpm、より好ましくは10~100rpm、処理時間が、好ましくは24~120時間、より好ましくは24~72時間の条件にて、解砕処理を行うことが好適である。また、遊星型ボールミルを用いて解砕処理を行う場合には、メディアとして、メディアサイズが、好ましくはφ0.1~φ5mm、より好ましくはφ0.3~φ3mmであるものを使用し、回転数が、好ましくは100~1000rpm、より好ましくは100~500rpm、処理時間が、好ましくは0.25~5時間、より好ましくは0.25~3時間の条件にて、解砕処理を行うことが好適である。さらに、ビーズミルを用いて解砕処理を行う場合には、メディアとして、メディアサイズが、好ましくはφ0.1~φ3mm、より好ましくはφ0.1~φ1mmであるものを使用し、回転数が、好ましくは1000~10000rpm、より好ましくは1000~5000rpm、処理時間が、好ましくは0.25~5時間、より好ましくは0.25~3時間の条件にて、解砕処理を行うことが好適である。
For example, when the crushing process is performed using a ball mill, a medium having a media size of preferably φ5 to φ50 mm, more preferably φ10 to φ35 mm is used, and the rotation speed is preferably 10 to 300 rpm. It is preferable to carry out the crushing treatment under the conditions of more preferably 10 to 100 rpm and a treatment time of preferably 24 to 120 hours, more preferably 24 to 72 hours. When the crushing process is performed using a planetary ball mill, a medium having a media size of preferably φ0.1 to φ5 mm, more preferably φ0.3 to φ3 mm is used, and the rotation speed is high. The crushing treatment is preferably carried out under the conditions of preferably 100 to 1000 rpm, more preferably 100 to 500 rpm, and a treatment time of preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours. is there. Further, when the crushing treatment is performed using a bead mill, a medium having a media size of preferably φ0.1 to φ3 mm, more preferably φ0.1 to φ1 mm is used, and the rotation speed is preferably high. Is preferably 1000 to 10000 rpm, more preferably 1000 to 5000 rpm, and the treatment time is preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours.
<共役ジエン系重合体ラテックス組成物>
本発明の共役ジエン系重合体ラテックス組成物は、共役ジエン系重合体のラテックスと、加硫剤と、上述した本発明のキサントゲン化合物分散体とを含有する。 <Conjugated diene polymer latex composition>
The conjugated diene polymer latex composition of the present invention contains the latex of the conjugated diene polymer, a vulcanizing agent, and the above-mentioned xanthogen compound dispersion of the present invention.
本発明の共役ジエン系重合体ラテックス組成物は、共役ジエン系重合体のラテックスと、加硫剤と、上述した本発明のキサントゲン化合物分散体とを含有する。 <Conjugated diene polymer latex composition>
The conjugated diene polymer latex composition of the present invention contains the latex of the conjugated diene polymer, a vulcanizing agent, and the above-mentioned xanthogen compound dispersion of the present invention.
共役ジエン系重合体のラテックスを構成する共役ジエン系重合体としては、特に限定されず、たとえば、合成ポリイソプレン、スチレン-イソプレン-スチレンブロック共重合体(SIS)、蛋白質を除去した天然ゴム、ニトリル基含有共役ジエン系共重合体などが挙げられる。これらのなかでも、合成ポリイソプレン、SIS、蛋白質を除去した天然ゴムなどのイソプレン単位を含有するものが好ましく、合成ポリイソプレンが特に好ましい。なお、共役ジエン系重合体としては、酸性基を有する単量体により変性して得られる酸変性共役ジエン系重合体であってもよい。
The conjugated diene polymer constituting the latex of the conjugated diene polymer is not particularly limited, and for example, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile. Examples thereof include group-containing conjugated diene-based copolymers. Among these, those containing isoprene units such as synthetic polyisoprene, SIS, and natural rubber from which proteins have been removed are preferable, and synthetic polyisoprene is particularly preferable. The conjugated diene polymer may be an acid-modified conjugated diene polymer obtained by modifying with a monomer having an acidic group.
共役ジエン系重合体として合成ポリイソプレンを用いる場合には、合成ポリイソプレンは、イソプレンの単独重合体であってもよいし、イソプレンと共重合可能な他のエチレン性不飽和単量体とを共重合したものであってもよい。合成ポリイソプレン中のイソプレン単位の含有量は、柔軟で、引張強度に優れるディップ成形体などの膜成形体が得られやすいことから、全単量体単位に対して、好ましくは70重量%以上、より好ましくは90重量%以上、さらに好ましくは95重量%以上、特に好ましくは100重量%(イソプレンの単独重合体)である。
When synthetic polyisoprene is used as the conjugated diene polymer, the synthetic polyisoprene may be a homopolymer of isoprene, or may be a copolymer of isoprene and another ethylenically unsaturated monomer copolymerizable with isoprene. It may be a polymer. The content of the isoprene unit in the synthetic polyisoprene is preferably 70% by weight or more with respect to all the monomer units because it is easy to obtain a film molded product such as a dip molded product which is flexible and has excellent tensile strength. It is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 100% by weight (a homopolymer of isoprene).
イソプレンと共重合可能な他のエチレン性不飽和単量体としては、たとえば、ブタジエン、クロロプレン、1,3-ペンタジエン等のイソプレン以外の共役ジエン単量体;アクリロニトリル、メタクリロニトリル、フマロニトリル、α-クロロアクリロニトリル等のエチレン性不飽和ニトリル単量体;スチレン、アルキルスチレン等のビニル芳香族単量体;(メタ)アクリル酸メチル(「アクリル酸メチルおよび/またはメタクリル酸メチル」の意味であり、以下、(メタ)アクリル酸エチルなども同様。)、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸-2-エチルヘキシル等のエチレン性不飽和カルボン酸エステル単量体;などが挙げられる。これらのイソプレンと共重合可能な他のエチレン性不飽和単量体は、1種単独でも、複数種を併用してもよい。
Other ethylenically unsaturated monomers copolymerizable with isoprene include conjugated diene monomers other than isoprene such as butadiene, chloroprene, 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, α-. Ethylene unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate (meaning "methyl acrylate and / or methyl methacrylate" and below. , (Meta) ethyl acrylate, etc.), (Meta) ethyl acrylate, (meth) butyl acrylate, (meth) acrylate, ethylenically unsaturated carboxylic acid ester monomer, such as -2-ethylhexyl; etc. Can be mentioned. The other ethylenically unsaturated monomers copolymerizable with these isoprene may be used alone or in combination of two or more.
合成ポリイソプレンは、従来公知の方法、たとえばトリアルキルアルミニウム-四塩化チタンからなるチーグラー系重合触媒やn-ブチルリチウム、sec-ブチルリチウムなどのアルキルリチウム重合触媒を用いて、不活性重合溶媒中で、イソプレンと、必要に応じて用いられる共重合可能な他のエチレン性不飽和単量体とを溶液重合して得ることができる。溶液重合により得られた合成ポリイソプレンの重合体溶液は、そのまま、合成ポリイソプレンラテックスの製造に用いてもよいが、該重合体溶液から固形の合成ポリイソプレンを取り出した後、有機溶媒に溶解して、合成ポリイソプレンラテックスの製造に用いることもできる。また、上述した方法により合成ポリイソプレンの重合体溶液を得た場合には、重合体溶液中に残った重合触媒の残渣などの不純物を取り除いてもよい。また、重合中または重合後の溶液に、後述する老化防止剤を添加してもよい。また、市販の固形の合成ポリイソプレンを用いることもできる。
Synthetic polyisoprene is prepared in an inert polymerization solvent using a conventionally known method, for example, a Cheegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium. , Isoprene and other copolymerizable ethylenically unsaturated monomers used as needed can be obtained by solution polymerization. The polymer solution of synthetic polyisoprene obtained by solution polymerization may be used as it is for the production of synthetic polyisoprene latex, but after taking out solid synthetic polyisoprene from the polymer solution, it is dissolved in an organic solvent. It can also be used in the production of synthetic polyisoprene latex. Further, when a polymer solution of synthetic polyisoprene is obtained by the above-mentioned method, impurities such as the residue of the polymerization catalyst remaining in the polymer solution may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid synthetic polyisoprene can be used.
合成ポリイソプレン中のイソプレン単位としては、イソプレンの結合状態により、シス結合単位、トランス結合単位、1,2-ビニル結合単位、3,4-ビニル結合単位の4種類が存在する。得られるディップ成形体などの膜成形体の引張強度向上の観点から、合成ポリイソプレンに含まれるイソプレン単位中のシス結合単位の含有割合は、全イソプレン単位に対して、好ましくは70重量%以上、より好ましくは90重量%以上、さらに好ましくは95重量%以上である。
There are four types of isoprene units in synthetic polyisoprene, cis-binding units, trans-binding units, 1,2-vinyl-binding units, and 3,4-vinyl-binding units, depending on the isoprene binding state. From the viewpoint of improving the tensile strength of the obtained film molded product such as a dip molded product, the content ratio of the cis bond unit in the isoprene unit contained in the synthetic polyisoprene is preferably 70% by weight or more with respect to the total isoprene unit. It is more preferably 90% by weight or more, still more preferably 95% by weight or more.
合成ポリイソプレンの重量平均分子量は、ゲル・パーミーエーション・クロマトグラフィー分析による標準ポリスチレン換算で、好ましくは10,000~5,000,000、より好ましくは500,000~5,000,000、さらに好ましくは800,000~3,000,000である。合成ポリイソプレンの重量平均分子量を上記範囲とすることにより、ディップ成形体などの膜成形体の引張強度が向上するとともに、合成ポリイソプレンラテックスが製造しやすくなる傾向がある。
The weight average molecular weight of the synthetic polyisoprene is preferably 10,000 to 5,000,000, more preferably 500,000 to 5,000,000, more preferably 500,000 to 5,000,000, in terms of standard polystyrene by gel permeation chromatography analysis. Is between 800,000 and 3,000,000. By setting the weight average molecular weight of the synthetic polyisoprene in the above range, the tensile strength of the film molded product such as a dip molded product is improved, and the synthetic polyisoprene latex tends to be easily produced.
また、合成ポリイソプレンのポリマー・ムーニー粘度(ML1+4、100℃)は、好ましくは50~85、より好ましくは60~85、さらに好ましくは70~85である。
The polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the synthetic polyisoprene is preferably 50 to 85, more preferably 60 to 85, and even more preferably 70 to 85.
合成ポリイソプレンラテックスを得るための方法としては、たとえば、(1)有機溶媒に溶解または微分散した合成ポリイソプレンの溶液または微細懸濁液を、アニオン性界面活性剤の存在下に、水中で乳化し、必要により有機溶媒を除去して、合成ポリイソプレンラテックスを製造する方法、(2)イソプレン単独または、イソプレンとそれと共重合可能なエチレン性不飽和単量体との混合物を、アニオン性界面活性剤の存在下に、乳化重合もしくは懸濁重合して、直接、合成ポリイソプレンラテックスを製造する方法、が挙げられるが、イソプレン単位中のシス結合単位の割合が高い合成ポリイソプレンを用いることができ、引張強度等の機械的特性に優れるディップ成形体などの膜成形体が得られやすい点から、上記(1)の製造方法が好ましい。
As a method for obtaining a synthetic polyisoprene latex, for example, (1) a solution or a fine suspension of synthetic polyisoprene dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of an anionic surfactant. Then, if necessary, a method for producing a synthetic polyisoprene latex by removing an organic solvent, (2) isoprene alone or a mixture of isoprene and an ethylenically unsaturated monomer copolymerizable therewith, anionic surface activity. A method of directly producing a synthetic polyisoprene latex by emulsification polymerization or suspension polymerization in the presence of an agent can be mentioned, but synthetic polyisoprene having a high ratio of cis-bonding units in isoprene units can be used. The production method (1) above is preferable from the viewpoint that a film-formed body such as a dip-formed body having excellent mechanical properties such as tensile strength can be easily obtained.
上記(1)の製造方法で用いる有機溶媒としては、たとえば、ベンゼン、トルエン、キシレン等の芳香族炭化水素溶媒;シクロペンタン、シクロペンテン、シクロヘキサン、シクロヘキセン等の脂環族炭化水素溶媒;ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素溶媒;塩化メチレン、クロロホルム、二塩化エチレン等のハロゲン化炭化水素溶媒;等を挙げることができる。これらのうち、脂環族炭化水素溶媒が好ましく、シクロヘキサンが特に好ましい。
Examples of the organic solvent used in the production method (1) above include aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane and cyclohexene; pentane, hexane and the like. An aliphatic hydrocarbon solvent such as heptane; a halogenated hydrocarbon solvent such as methylene chloride, chloroform and ethylene dichloride; and the like can be mentioned. Of these, an alicyclic hydrocarbon solvent is preferable, and cyclohexane is particularly preferable.
なお、有機溶媒の使用量は、合成ポリイソプレン100重量部に対して、好ましくは2,000重量部以下、より好ましくは20~1,500重量部、更に好ましくは500~1,500である。
The amount of the organic solvent used is preferably 2,000 parts by weight or less, more preferably 20 to 1,500 parts by weight, and further preferably 500 to 1,500 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
上記(1)の製造方法で用いるアニオン性界面活性剤としては、たとえば、ラウリン酸ナトリウム、ミリスチン酸カリウム、パルミチン酸ナトリウム、オレイン酸カリウム、リノレン酸ナトリウム、ロジン酸ナトリウム等の脂肪酸塩;ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウム、デシルベンゼンスルホン酸ナトリウム、デシルベンゼンスルホン酸カリウム、セチルベンゼンスルホン酸ナトリウム、セチルベンゼンスルホン酸カリウム等のアルキルベンゼンスルホン酸塩;ジ(2-エチルヘキシル)スルホコハク酸ナトリウム、ジ(2-エチルヘキシル)スルホコハク酸カリウム、ジオクチルスルホコハク酸ナトリウム等のアルキルスルホコハク酸塩;ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等のアルキル硫酸エステル塩;ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸カリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩;ラウリルリン酸ナトリウム、ラウリルリン酸カリウム等のモノアルキルリン酸塩;等が挙げられる。
Examples of the anionic surfactant used in the production method (1) above include fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and sodium loginate; dodecylbenzene sulfonate. Alkylbenzene sulfonates such as sodium acid, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate, di (2-Ethylhexyl) Alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; sodium polyoxyethylene lauryl ether sulfate, potassium polyoxyethylene lauryl ether sulfate, etc. Polyoxyethylene alkyl ether sulfate ester salt; monoalkyl phosphate such as sodium lauryl phosphate and potassium lauryl phosphate; and the like.
これらアニオン性界面活性剤の中でも、脂肪酸塩、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩が好ましく、脂肪酸塩およびアルキルベンゼンスルホン酸塩が特に好ましい。
Among these anionic surfactants, fatty acid salts, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates are preferable, and fatty acid salts and alkylbenzene sulfonates are particularly preferable.
また、合成ポリイソプレン由来の、微量に残留する重合触媒(特に、アルミニウムとチタニウム)をより効率的に除去でき、共役ジエン系重合体ラテックス組成物を製造する際における、凝集物の発生が抑制されることから、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩からなる群から選ばれる少なくとも1種と、脂肪酸塩とを併用して用いることが好ましく、アルキルベンゼンスルホン酸塩と、脂肪酸塩とを併用して用いることが特に好ましい。ここで、脂肪酸塩としては、ロジン酸ナトリウムおよびロジン酸カリウムが好ましく、また、アルキルベンゼンスルホン酸塩としては、ドデシルベンゼンスルホン酸ナトリウムおよびドデシルベンゼンスルホン酸カリウムが好ましい。また、これらの界面活性剤は、1種単独でも2種以上を併用してもよい。
In addition, a trace amount of the polymerization catalyst (particularly aluminum and fatty acid) derived from synthetic polyisoprene can be removed more efficiently, and the generation of agglomerates in the production of the conjugated diene polymer latex composition is suppressed. Therefore, it is preferable to use at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates in combination with fatty acid salts. It is particularly preferable to use the alkylbenzene sulfonate in combination with the fatty acid salt. Here, as the fatty acid salt, sodium loginate and potassium loginate are preferable, and as the alkylbenzene sulfonate, sodium dodecylbenzene sulfonate and potassium dodecylbenzene sulfonate are preferable. In addition, these surfactants may be used alone or in combination of two or more.
なお、上述したように、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩からなる群から選ばれる少なくとも1種と、脂肪酸塩とを併用して用いることにより、得られるラテックスが、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩の中から選ばれた少なくとも1種と、脂肪酸塩とを含有するものとなる。
As described above, at least one selected from the group consisting of alkylbenzene sulfonates, alkylsulfosuccinates, alkylsulfate salts and polyoxyethylene alkylether sulfates should be used in combination with fatty acid salts. The resulting latex contains at least one selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates, and fatty acid salts. ..
また、上記(1)の製造方法においては、アニオン性界面活性剤以外の界面活性剤を併用してもよく、このようなアニオン性界面活性剤以外の界面活性剤としては、α,β-不飽和カルボン酸のスルホエステル、α,β-不飽和カルボン酸のサルフェートエステル、スルホアルキルアリールエーテル等の共重合性の界面活性剤が挙げられる。
Further, in the production method of (1) above, a surfactant other than the anionic surfactant may be used in combination, and the surfactant other than the anionic surfactant may be α, β-non. Examples thereof include copolymerizable surfactants such as sulfoesters of saturated carboxylic acids, sulfate esters of α, β-unsaturated carboxylic acids, and sulfoalkylaryl ethers.
上記(1)の製造方法で用いるアニオン性界面活性剤の使用量は、合成ポリイソプレン100重量部に対して、好ましくは0.1~50重量部、より好ましくは0.5~30重量部である。なお、2種類以上の界面活性剤を用いる場合においては、これらの合計の使用量を上記範囲とすることが好ましい。すなわち、たとえば、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩の中から選ばれた少なくとも1種と、脂肪酸塩とを併用する場合には、これらの使用量の合計を上記範囲とすることが好ましい。アニオン性界面活性剤の使用量が少なすぎると、乳化時に凝集物が多量に発生するおそれがあり、逆に多すぎると、発泡しやすくなり、得られるディップ成形体などの膜成形体にピンホールが発生する可能性がある。
The amount of the anionic surfactant used in the production method (1) is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the synthetic polyisoprene. is there. When two or more kinds of surfactants are used, it is preferable that the total amount of these surfactants used is in the above range. That is, for example, when at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkylsulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination with a fatty acid salt, these It is preferable that the total amount used is in the above range. If the amount of anionic surfactant used is too small, a large amount of agglomerates may be generated during emulsification. May occur.
また、アニオン性界面活性剤として、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩の中から選ばれた少なくとも1種と、脂肪酸塩とを併用する場合には、これらの使用割合を、「脂肪酸塩」:「アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩の中から選ばれた少なくとも1種の界面活性剤の合計」の重量比で、1:1~10:1の範囲とすることが好ましく、1:1~7:1の範囲とすることがより好ましい。アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキル硫酸エステル塩およびポリオキシエチレンアルキルエーテル硫酸エステル塩の中から選ばれた少なくとも1種の界面活性剤の使用割合が多すぎると、合成ポリイソプレンの取り扱い時に泡立ちが激しくなるおそれがあり、これにより、長時間の静置や、消泡剤の添加などの操作が必要になり、作業性の悪化およびコストアップに繋がるおそれがある。
In addition, when at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination as an anionic surfactant, and a fatty acid salt is used in combination. In the above, the ratio of these to be used is "fatty acid salt": "alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt". The weight ratio of "total of agents" is preferably in the range of 1: 1 to 10: 1, and more preferably in the range of 1: 1 to 7: 1. Too much of the surfactant selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates will result in the handling of synthetic polyisoprenes. Foaming may become intense, which requires operations such as standing for a long time and adding an antifoaming agent, which may lead to deterioration of workability and cost increase.
上記(1)の製造方法で使用する水の量は、合成ポリイソプレンの有機溶媒溶液100重量部に対して、好ましくは10~1,000重量部、より好ましくは30~500重量部、最も好ましくは50~100重量部である。使用する水の種類としては、硬水、軟水、イオン交換水、蒸留水、ゼオライトウォーターなどが挙げられ、軟水、イオン交換水および蒸留水が好ましい。
The amount of water used in the production method (1) is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, most preferably 30 parts by weight, based on 100 parts by weight of the organic solvent solution of synthetic polyisoprene. Is 50 to 100 parts by weight. Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, zeolite water and the like, and soft water, ion-exchanged water and distilled water are preferable.
有機溶媒に溶解または微分散した合成ポリイソプレンの溶液または微細懸濁液を、アニオン性界面活性剤の存在下、水中で乳化する装置は、一般に乳化機または分散機として市販されているものであれば特に限定されず使用できる。合成ポリイソプレンの溶液または微細懸濁液に、アニオン性界面活性剤を添加する方法としては、特に限定されず、予め、水もしくは合成ポリイソプレンの溶液または微細懸濁液のいずれか、あるいは両方に添加してもよいし、乳化操作を行っている最中に、乳化液に添加してもよく、一括添加しても、分割添加してもよい。
An apparatus for emulsifying a solution or microsuspension of synthetic polyisoprene dissolved or finely dispersed in an organic solvent in water in the presence of anionic surfactant, whichever is generally commercially available as an emulsifier or disperser. It can be used without particular limitation. The method of adding the anionic surfactant to the synthetic polyisoprene solution or microsuspension is not particularly limited, and it is previously added to water, the synthetic polyisoprene solution or the fine suspension, or both. It may be added, may be added to the emulsified solution during the emulsification operation, may be added all at once, or may be added in portions.
乳化装置としては、たとえば、商品名「ホモジナイザー」(IKA社製)、商品名「ポリトロン」(キネマティカ社製)、商品名「TKオートホモミキサー」(特殊機化工業社製)等のバッチ式乳化機;商品名「TKパイプラインホモミキサー」(特殊機化工業社製)、商品名「コロイドミル」(神鋼パンテック社製)、商品名「スラッシャー」(日本コークス工業社製)、商品名「トリゴナル湿式微粉砕機」(三井三池化工機社製)、商品名「キャビトロン」(ユーロテック社製)、商品名「マイルダー」(太平洋機工社製)、商品名「ファインフローミル」(太平洋機工社製)等の連続式乳化機;商品名「マイクロフルイダイザー」(みずほ工業社製)、商品名「ナノマイザー」(ナノマイザー社製)、商品名「APVガウリン」(ガウリン社製)等の高圧乳化機;商品名「膜乳化機」(冷化工業社製)等の膜乳化機;商品名「バイブロミキサー」(冷化工業社製)等の振動式乳化機;商品名「超音波ホモジナイザー」(ブランソン社製)等の超音波乳化機;等が挙げられる。なお、乳化装置による乳化操作の条件は、特に限定されず、所望の分散状態になるように、処理温度、処理時間などを適宜選定すればよい。
Examples of the emulsifying device include batch emulsification such as the product name "homogenizer" (manufactured by IKA), the product name "Polytron" (manufactured by Kinematica), and the product name "TK autohomo mixer" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). Machine; Product name "TK Pipeline Homo Mixer" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), Product name "Coloid Mill" (manufactured by Shinko Pantech Co., Ltd.), Product name "Slasher" (manufactured by Nippon Coke Industries Co., Ltd.), Product name " Trigonal wet pulverizer (manufactured by Mitsui Miike Kakoki Co., Ltd.), product name "Cavitron" (manufactured by Eurotech), product name "Milder" (manufactured by Pacific Kiko Co., Ltd.), product name "Fine Flow Mill" (manufactured by Pacific Kiko Co., Ltd.) Continuous emulsifiers such as (manufactured by); high-pressure emulsifiers such as the product name "Microfluidizer" (manufactured by Mizuho Kogyo Co., Ltd.), the product name "Nammizer" (manufactured by Nanomizer), and the product name "APV Gaulin" (manufactured by Gaulin). Membrane emulsifiers such as the product name "Membrane Emulsifier" (manufactured by Refrigeration Industry Co., Ltd.); Vibration type emulsifiers such as the product name "Vibro Mixer" (manufactured by Refrigeration Industry Co., Ltd.); Product name "Ultrasonic Homogenizer" (Branson) Ultrasonic emulsifiers such as (manufactured by the company); etc. The conditions for the emulsification operation by the emulsification device are not particularly limited, and the treatment temperature, treatment time, and the like may be appropriately selected so as to obtain a desired dispersed state.
上記(1)の製造方法においては、乳化操作を経て得られた乳化物から、有機溶媒を除去することが望ましい。乳化物から有機溶媒を除去する方法としては、得られる合成ポリイソプレンラテックス中における、有機溶媒(好ましくは脂環族炭化水素溶媒)の含有量を500重量ppm以下とすることのできる方法が好ましく、たとえば、減圧蒸留、常圧蒸留、水蒸気蒸留、遠心分離等の方法を採用することができる。
In the production method (1) above, it is desirable to remove the organic solvent from the emulsion obtained through the emulsification operation. As a method for removing the organic solvent from the emulsion, a method in which the content of the organic solvent (preferably alicyclic hydrocarbon solvent) in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less is preferable. For example, methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
上記(1)の方法においては、乳化操作を経て得られた乳化物から、有機溶媒を除去して、合成ポリイソプレンラテックスを得ることが望ましい。乳化物から有機溶媒を除去する方法は、得られる合成ポリイソプレンラテックス中における、有機溶媒としての脂環族炭化水素溶媒および芳香族炭化水素溶媒の合計含有量を500重量ppm以下とすることができるような方法であれば、特に限定されず、減圧蒸留、常圧蒸留、水蒸気蒸留、遠心分離等の方法を採用することができる。
In the method (1) above, it is desirable to remove the organic solvent from the emulsion obtained through the emulsification operation to obtain a synthetic polyisoprene latex. In the method for removing the organic solvent from the emulsion, the total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent as the organic solvent in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less. Such a method is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
また、有機溶媒を除去した後、必要に応じ、合成ポリイソプレンラテックスの固形分濃度を上げるために、減圧蒸留、常圧蒸留、遠心分離、膜濃縮等の方法で濃縮操作を施してもよく、特に、合成ポリイソプレンラテックスの固形分濃度を上げるとともに、合成ポリイソプレンラテックス中の界面活性剤の残留量を低減することができるという観点より、遠心分離を行うことが好ましい。
Further, after removing the organic solvent, if necessary, in order to increase the solid content concentration of the synthetic polyisoprene latex, a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration. In particular, it is preferable to carry out centrifugation from the viewpoint that the solid content concentration of the synthetic polyisoprene latex can be increased and the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
遠心分離は、たとえば、連続遠心分離機を用いて、遠心力を、好ましくは100~10,000G、遠心分離前の合成ポリイソプレンラテックスの固形分濃度を、好ましくは2~15重量%、遠心分離機に送り込む流速を、好ましくは500~1700Kg/hr、遠心分離機の背圧(ゲージ圧)を、好ましくは-0.05~1.6MPa、より好ましくは0.03~1.6MPaの条件にて実施することが好ましく、遠心分離後の軽液として、合成ポリイソプレンラテックスを得ることができる。そして、これにより、合成ポリイソプレンラテックス中における、界面活性剤の残留量を低減することができる。
Centrifugation uses, for example, a continuous centrifuge to centrifuge the centrifugal force, preferably 100 to 10,000 G, and the solid content concentration of the synthetic polyisoprene latex before centrifugation, preferably 2 to 15% by weight. The flow velocity to be sent to the machine is preferably 500 to 1700 kg / hr, and the back pressure (gauge pressure) of the centrifuge is preferably -0.05 to 1.6 MPa, more preferably 0.03 to 1.6 MPa. Synthetic polyisoprene latex can be obtained as a light liquid after centrifugation. As a result, the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
合成ポリイソプレンラテックスの固形分濃度は、好ましくは30~70重量%、より好ましくは40~70重量%である。固形分濃度が低すぎると、共役ジエン系重合体ラテックス組成物の固形分濃度が低くなるために、得られるディップ成形体などの膜成形体の膜厚が薄くなり破れ易くなる。逆に固形分濃度が高すぎると、合成ポリイソプレンラテックスの粘度が高くなり、配管での移送や調合タンク内での撹拌が困難になる場合がある。
The solid content concentration of the synthetic polyisoprene latex is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that the film-formed body such as the obtained dip-molded body becomes thin and easily torn. On the other hand, if the solid content concentration is too high, the viscosity of the synthetic polyisoprene latex becomes high, which may make it difficult to transfer the synthetic polyisoprene latex or stir it in the compounding tank.
合成ポリイソプレンラテックスの体積平均粒子径は、好ましくは0.1~10μm、より好ましくは0.5~3μm、さらに好ましくは0.5~2.0μmである。この体積平均粒子径を上記範囲とすることにより、ラテックス粘度が適度なものとなり取り扱いやすくなるとともに、合成ポリイソプレンラテックスを貯蔵した際に、ラテックス表面に皮膜が生成することを抑制できる。
The volume average particle size of the synthetic polyisoprene latex is preferably 0.1 to 10 μm, more preferably 0.5 to 3 μm, and even more preferably 0.5 to 2.0 μm. By setting the volume average particle size in the above range, the latex viscosity becomes appropriate and easy to handle, and it is possible to suppress the formation of a film on the latex surface when the synthetic polyisoprene latex is stored.
また、合成ポリイソプレンラテックスには、ラテックスの分野で通常配合される、pH調整剤、消泡剤、防腐剤、架橋剤、キレート剤、酸素捕捉剤、分散剤、老化防止剤等の添加剤を配合してもよい。pH調整剤としては、たとえば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の炭酸塩;炭酸水素ナトリウムなどのアルカリ金属の炭酸水素塩;アンモニア;トリメチルアミン、トリエタノールアミンなどの有機アミン化合物;等が挙げられるが、アルカリ金属の水酸化物またはアンモニアが好ましい。
In addition, synthetic polyisoprene latex contains additives such as pH adjusters, defoamers, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. May be blended. Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
また、共役ジエン系重合体としては、上述したように、スチレン-イソプレン-スチレンブロック共重合体(SIS)を用いることもできる。なお、SISにおいては、「S」はスチレンブロック、「I」はイソプレンブロックをそれぞれ表す。
Further, as the conjugated diene-based polymer, as described above, a styrene-isoprene-styrene block copolymer (SIS) can also be used. In SIS, "S" represents a styrene block and "I" represents an isoprene block.
SISは、従来公知の方法、たとえばn-ブチルリチウムなどの活性有機金属を開始剤として、不活性重合溶媒中で、イソプレンとスチレンとをブロック共重合して得ることができる。そして、得られたSISの重合体溶液は、SISラテックスの製造にそのまま用いてもよいが、該重合体溶液から固形のSISを取り出した後、その固形のSISを有機溶媒に溶解して、SISラテックスの製造に用いることもできる。SISラテックスの製造方法としては、特に限定されないが、有機溶媒に溶解または微分散したSISの溶液または微細懸濁液を、界面活性剤の存在下に、水中で乳化し、必要により有機溶媒を除去して、SISラテックスを製造する方法が好ましい。この際、合成した後に重合体溶液中に残った重合触媒の残渣などの不純物を取り除いてもよい。また、重合中または重合後の溶液に、後述する老化防止剤を添加してもよい。また、市販の固形のSISを用いることもできる。
SIS can be obtained by block copolymerization of isoprene and styrene in an inert polymerization solvent using a conventionally known method, for example, an active organometallic such as n-butyllithium as an initiator. The obtained SIS polymer solution may be used as it is in the production of SIS latex, but after taking out the solid SIS from the polymer solution, the solid SIS is dissolved in an organic solvent to SIS. It can also be used in the production of latex. The method for producing SIS latex is not particularly limited, but a SIS solution or fine suspension dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of a surfactant, and the organic solvent is removed if necessary. The method for producing the SIS latex is preferable. At this time, impurities such as the residue of the polymerization catalyst remaining in the polymer solution after the synthesis may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid SIS can be used.
有機溶媒としては、上記合成ポリイソプレンの場合と同様のものを使用することができ、芳香族炭化水素溶媒および脂環族炭化水素溶媒が好ましく、シクロヘキサンおよびトルエンが特に好ましい。なお、有機溶媒の使用量は、SIS100重量部に対して、通常50~2,000重量部、好ましくは80~1,000重量部、より好ましくは100~500重量部、さらに好ましくは150~300重量部である。
As the organic solvent, the same solvent as in the case of the synthetic polyisoprene can be used, and aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents are preferable, and cyclohexane and toluene are particularly preferable. The amount of the organic solvent used is usually 50 to 2,000 parts by weight, preferably 80 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, still more preferably 150 to 300 parts by weight, based on 100 parts by weight of SIS. It is a part by weight.
界面活性剤としては、上記合成ポリイソプレンの場合と同様のものを例示することができ、アニオン性界面活性剤が好適であり、ロジン酸ナトリウムおよびドデシルベンゼンスルホン酸ナトリウムが特に好ましい。
As the surfactant, the same ones as in the case of the above synthetic polyisoprene can be exemplified, anionic surfactant is preferable, and sodium loginate and sodium dodecylbenzenesulfonate are particularly preferable.
界面活性剤の使用量は、SIS100重量部に対して、好ましくは0.1~50重量部、より好ましくは0.5~30重量部である。この量が少なすぎると、ラテックスの安定性が劣る傾向にあり、逆に多すぎると、発泡しやすくなり、ディップ成形時に問題が起きる可能性がある。
The amount of the surfactant used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of SIS. If this amount is too small, the stability of the latex tends to be poor, and conversely, if it is too large, foaming tends to occur, which may cause problems during dip molding.
上述したSISラテックスの製造方法で使用する水の量は、SISの有機溶媒溶液100重量部に対して、好ましくは10~1,000重量部、より好ましくは30~500重量部、最も好ましくは50~100である。使用する水の種類としては、硬水、軟水、イオン交換水、蒸留水、ゼオライトウォーターなどが挙げられる。また、メタノールなどのアルコールに代表される極性溶媒を水と併用してもよい。
The amount of water used in the above-mentioned method for producing SIS latex is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 50 parts by weight with respect to 100 parts by weight of the organic solvent solution of SIS. ~ 100. Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, and zeolite water. Further, a polar solvent typified by alcohol such as methanol may be used in combination with water.
単量体の添加方法としては、上記合成ポリイソプレンの場合と同様のものを例示することができる。また、SISの有機溶媒溶液または微細懸濁液を、界面活性剤の存在下、水中で乳化する装置は、上記合成ポリイソプレンの場合と同様のものを例示することができる。そして、界面活性剤の添加方法は、特に限定されず、予め水もしくはSISの有機溶媒溶液または微細懸濁液のいずれか、あるいは両方に添加してもよいし、乳化操作を行っている最中に、乳化液に添加してもよく、一括添加しても、分割添加してもよい。
As a method for adding the monomer, the same method as in the case of the above synthetic polyisoprene can be exemplified. Further, an apparatus for emulsifying an organic solvent solution or a fine suspension of SIS in water in the presence of a surfactant can be exemplified as the same as in the case of the synthetic polyisoprene described above. The method of adding the surfactant is not particularly limited, and the surfactant may be added to water, an organic solvent solution of SIS, a fine suspension, or both in advance, or during the emulsification operation. In addition, it may be added to the emulsion, may be added all at once, or may be added separately.
上述したSISラテックスの製造方法においては、乳化操作を経て得られた乳化物から、有機溶媒を除去して、SISラテックスを得ることが好ましい。乳化物から有機溶媒を除去する方法は、特に限定されず、減圧蒸留、常圧蒸留、水蒸気蒸留、遠心分離等の方法を採用することができる。
In the above-mentioned method for producing SIS latex, it is preferable to remove the organic solvent from the emulsion obtained through the emulsification operation to obtain SIS latex. The method for removing the organic solvent from the emulsion is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
また、有機溶媒を除去した後、必要に応じ、SISラテックスの固形分濃度を上げるために、減圧蒸留、常圧蒸留、遠心分離、膜濃縮等の方法で濃縮操作を施してもよい。
Further, after removing the organic solvent, if necessary, in order to increase the solid content concentration of the SIS latex, a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
SISラテックスの固形分濃度は、好ましくは30~70重量%、より好ましくは50~70重量%である。固形分濃度が低すぎると、共役ジエン系重合体ラテックス組成物の固形分濃度が低くなるため、ディップ成形体などの膜成形体とした際に、膜厚が薄くなり破れ易くなる。逆に固形分濃度が高すぎると、SISラテックスの粘度が高くなり、配管での移送や調合タンク内での撹拌が難しくなる。
The solid content concentration of the SIS latex is preferably 30 to 70% by weight, more preferably 50 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that when a film molded product such as a dip molded product is formed, the film thickness becomes thin and it becomes easy to tear. On the contrary, if the solid content concentration is too high, the viscosity of the SIS latex becomes high, and it becomes difficult to transfer the SIS latex by piping or to stir it in the compounding tank.
また、SISラテックスには、ラテックスの分野で通常配合される、pH調整剤、消泡剤、防腐剤、架橋剤、キレート剤、酸素捕捉剤、分散剤、老化防止剤等の添加剤を配合してもよい。pH調整剤としては、上記合成ポリイソプレンの場合と同様のものを例示することができ、アルカリ金属の水酸化物またはアンモニアが好ましい。
In addition, SIS latex contains additives such as pH adjusters, antifoaming agents, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. You may. As the pH adjuster, the same as in the case of the above synthetic polyisoprene can be exemplified, and alkali metal hydroxide or ammonia is preferable.
このようにして得られるSISラテックスに含まれる、SIS中のスチレンブロックにおけるスチレン単位の含有量は、全単量体単位に対して、好ましくは70~100重量%、より好ましくは90~100重量%、さらに好ましくは100重量%である。また、SIS中のイソプレンブロックにおけるイソプレン単位の含有量は、全単量体単位に対して、好ましくは70~100重量%、より好ましくは90~100重量%、さらに好ましくは100重量%である。
The content of the styrene unit in the styrene block in the SIS contained in the SIS latex thus obtained is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, based on all the monomer units. , More preferably 100% by weight. The content of the isoprene unit in the isoprene block in SIS is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, still more preferably 100% by weight, based on all the monomer units.
なお、SIS中のスチレン単位とイソプレン単位の含有割合は、「スチレン単位:イソプレン単位」の重量比で、通常1:99~90:10、好ましくは3:97~70:30、より好ましくは5:95~50:50、さらに好ましくは10:90~30:70の範囲である。
The content ratio of the styrene unit and the isoprene unit in the SIS is a weight ratio of "styrene unit: isoprene unit", which is usually 1:99 to 90:10, preferably 3:97 to 70:30, and more preferably 5. : 95 to 50:50, more preferably 10:90 to 30:70.
SISの重量平均分子量は、ゲル・パーミーエーション・クロマトグラフィー分析による標準ポリスチレン換算で、好ましくは10,000~1,000,000、より好ましくは50,000~500,000、さらに好ましくは100,000~300,000である。SISの重量平均分子量を上記範囲とすることにより、ディップ成形体などの膜成形体の引張強度と柔軟性のバランスが向上するとともに、SISのラテックスが製造しやすくなる傾向がある。
The weight average molecular weight of SIS is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, still more preferably 100,000 in terms of standard polystyrene by gel permeation chromatography analysis. ~ 300,000. By setting the weight average molecular weight of SIS in the above range, the balance between the tensile strength and flexibility of a film molded product such as a dip molded product is improved, and the latex of SIS tends to be easily produced.
SISラテックス中のラテックス粒子(SIS粒子)の体積平均粒子径は、好ましくは0.1~10μm、より好ましくは0.5~3μm、さらに好ましくは0.5~2.0μmである。ラテックス粒子の体積平均粒子径を上記範囲とすることにより、ラテックス粘度が適度なものとなり取り扱いやすくなるとともに、SISラテックスを貯蔵した際に、ラテックス表面に皮膜が生成することを抑制できる。
The volume average particle size of the latex particles (SIS particles) in the SIS latex is preferably 0.1 to 10 μm, more preferably 0.5 to 3 μm, and even more preferably 0.5 to 2.0 μm. By setting the volume average particle size of the latex particles in the above range, the latex viscosity becomes appropriate and easy to handle, and it is possible to suppress the formation of a film on the latex surface when the SIS latex is stored.
また、共役ジエン系重合体としては、蛋白質を除去した天然ゴムを用いることもできる。蛋白質を除去した天然ゴムの原料となる天然ゴムとしては、天然ゴムの樹から得られたラテックスに含まれる天然ゴムおよび該ラテックスを処理したラテックスに含まれる天然ゴムを使用することができ、たとえば、天然ゴムの樹から採取されたフィールドラテックスに含まれる天然ゴムや、フィールドラテックスをアンモニア等で処理してなる市販の天然ゴムラテックスに含まれる天然ゴムなどを使用することができる。
Further, as the conjugated diene-based polymer, natural rubber from which proteins have been removed can also be used. As the natural rubber used as a raw material for the natural rubber from which the protein has been removed, natural rubber contained in latex obtained from a natural rubber tree and natural rubber contained in latex treated with the latex can be used, for example. Natural rubber contained in field latex collected from a natural rubber tree, natural rubber contained in commercially available natural rubber latex obtained by treating field latex with ammonia or the like can be used.
蛋白質を除去した天然ゴムを得る際における、天然ゴムから蛋白質を除去する方法としては、特に限定されないが、天然ゴムラテックスについて、界面活性剤の存在下で、尿素化合物を反応させることにより、天然ゴム中に含まれる蛋白質を変性させた後、このような変性蛋白質を含有する天然ゴムラテックスに対し、遠心分離、ゴム分の凝固、限外ろ過等の処理を施すことにより、天然ゴムと変性蛋白質とを分離し、この変性蛋白質を除去することにより、蛋白質を除去した天然ゴムのラテックスを得ることができる。
The method for removing the protein from the natural rubber in obtaining the natural rubber from which the protein has been removed is not particularly limited, but the natural rubber latex is reacted with a urea compound in the presence of a surfactant to obtain the natural rubber. After denaturing the protein contained therein, the natural rubber latex containing such a modified protein is subjected to treatments such as centrifugation, coagulation of rubber content, and ultrafiltration to obtain the natural rubber and the modified protein. By separating and removing this denatured protein, a natural rubber latex from which the protein has been removed can be obtained.
また、共役ジエン系重合体としては、上述したように、ニトリル基含有共役ジエン系共重合体を用いることもできる。
Further, as the conjugated diene-based polymer, as described above, a nitrile group-containing conjugated diene-based copolymer can also be used.
ニトリル基含有共役ジエン系共重合体は、共役ジエン単量体にエチレン性不飽和ニトリル単量体を共重合してなる共重合体であり、これらに加えて、必要に応じて用いられる、これらと共重合可能な他のエチレン性不飽和単量体を共重合してなる共重合体であってもよい。
The nitrile group-containing conjugated diene-based copolymer is a copolymer obtained by copolymerizing an ethylenically unsaturated nitrile monomer with a conjugated diene monomer, and in addition to these, these are used as needed. It may be a copolymer obtained by copolymerizing another ethylenically unsaturated monomer copolymerizable with.
共役ジエン単量体としては、たとえば、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、2-エチル-1,3-ブタジエン、1,3-ペンタジエンおよびクロロプレンなどが挙げられる。これらのなかでも、1,3-ブタジエンおよびイソプレンが好ましく、1,3-ブタジエンがより好ましい。これらの共役ジエン単量体は、単独で、または2種以上を組合せて用いることができる。ニトリル基含有共役ジエン系共重合体中における、共役ジエン単量体により形成される共役ジエン単量体単位の含有割合は、好ましくは56~78重量%であり、より好ましくは56~73重量%、さらに好ましくは56~68重量%である。共役ジエン単量体単位の含有量を上記範囲とすることにより、得られるディップ成形体などの膜成形体を、風合いおよび伸びに優れたものとすることができる。
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. Be done. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable. These conjugated diene monomers can be used alone or in combination of two or more. The content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 56 to 78% by weight, more preferably 56 to 73% by weight. , More preferably 56 to 68% by weight. By setting the content of the conjugated diene monomer unit in the above range, the obtained film molded product such as a dip molded product can be made excellent in texture and elongation.
エチレン性不飽和ニトリル単量体としては、ニトリル基を含有するエチレン性不飽和単量体であれば特に限定されないが、たとえば、アクリロニトリル、メタクリロニトリル、フマロニトリル、α-クロロアクリロニトリル、α-シアノエチルアクリロニトリルなどが挙げられる。なかでも、アクリロニトリルおよびメタクリロニトリルが好ましく、アクリロニトリルがより好ましい。これらのエチレン性不飽和ニトリル単量体は、単独で、または2種以上を組合せて用いることができる。ニトリル基含有共役ジエン系共重合体中における、エチレン性不飽和ニトリル単量体により形成されるエチレン性不飽和ニトリル単量体単位の含有割合は、好ましくは20~40重量%であり、より好ましくは25~40重量%、さらに好ましくは30~40重量%である。エチレン性不飽和ニトリル単量体単位の含有量を上記範囲とすることにより、得られるディップ成形体などの膜成形体を、風合いおよび伸びに優れたものとすることができる。
The ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a nitrile group, and for example, acrylonitrile, methacrylonitrile, fumaronitrile, α-chloroacrylonitrile, α-cyanoethylacrylonitrile. And so on. Of these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable. These ethylenically unsaturated nitrile monomers can be used alone or in combination of two or more. The content ratio of the ethylenically unsaturated nitrile monomer unit formed of the ethylenically unsaturated nitrile monomer in the nitrile group-containing conjugated diene copolymer is preferably 20 to 40% by weight, more preferably 20 to 40% by weight. Is 25 to 40% by weight, more preferably 30 to 40% by weight. By setting the content of the ethylenically unsaturated nitrile monomer unit in the above range, the obtained film molded product such as a dip molded product can be made excellent in texture and elongation.
共役ジエン単量体およびエチレン性不飽和ニトリル単量体と共重合可能なその他のエチレン性不飽和単量体としては、たとえば、カルボキシル基を含有するエチレン性不飽和単量体であるエチレン性不飽和カルボン酸単量体;スチレン、アルキルスチレン、ビニルナフタレン等のビニル芳香族単量体;フルオロエチルビニルエーテル等のフルオロアルキルビニルエーテル;(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N,N-ジメチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-プロポキシメチル(メタ)アクリルアミド等のエチレン性不飽和アミド単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸トリフルオロエチル、(メタ)アクリル酸テトラフルオロプロピル、マレイン酸ジブチル、フマル酸ジブチル、マレイン酸ジエチル、(メタ)アクリル酸メトキシメチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸メトキシエトキシエチル、(メタ)アクリル酸シアノメチル、(メタ)アクリル酸-2-シアノエチル、(メタ)アクリル酸-1-シアノプロピル、(メタ)アクリル酸-2-エチル-6-シアノヘキシル、(メタ)アクリル酸-3-シアノプロピル、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、グリシジル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート等のエチレン性不飽和カルボン酸エステル単量体;ジビニルベンゼン、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート等の架橋性単量体;などを挙げることができる。これらのエチレン性不飽和単量体は単独で、または2種以上を組み合わせて使用することができる。なお、共重合可能なその他のエチレン性不飽和単量体として、エチレン性不飽和カルボン酸単量体を使用することで、ニトリル基含有共役ジエン系共重合体を、カルボキシル基を備えるものとすることができる。
Other ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer and the ethylenically unsaturated nitrile monomer include, for example, ethylenically unsaturated, which is an ethylenically unsaturated monomer containing a carboxyl group. Saturated carboxylic acid monomer; Vinyl aromatic monomer such as styrene, alkylstyrene, vinylnaphthalene; Fluoroalkylvinyl ether such as fluoroethyl vinyl ether; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol Ethylene unsaturated amide monomers such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Butyl acrylate, -2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate, methoxy (meth) acrylate Methyl, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, -2-cyanoethyl (meth) acrylate, -1-cyanopropyl (meth) acrylate, (meth) -2-Acrylic acid-6-cyanohexyl, (meth) acrylate-3-cyanopropyl, (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) ) Ethylene unsaturated carboxylic acid ester monomer such as acrylate; divinylbenzene, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropanthry (meth) acrylate, pentaerythritol (meth) acrylate, etc. Crosslinkable monomer; and the like. These ethylenically unsaturated monomers can be used alone or in combination of two or more. By using an ethylenically unsaturated carboxylic acid monomer as another copolymerizable ethylenically unsaturated monomer, the nitrile group-containing conjugated diene copolymer is provided with a carboxyl group. be able to.
エチレン性不飽和カルボン酸単量体としては、カルボキシル基を含有するエチレン性不飽和単量体であれば特に限定されないが、たとえば、アクリル酸、メタクリル酸などのエチレン性不飽和モノカルボン酸単量体;イタコン酸、マレイン酸、フマル酸等のエチレン性不飽和多価カルボン酸単量体;無水マレイン酸、無水シトラコン酸等のエチレン性不飽和多価カルボン酸無水物;フマル酸モノブチル、マレイン酸モノブチル、マレイン酸モノ-2-ヒドロキシプロピル等のエチレン性不飽和多価カルボン酸部分エステル単量体;などが挙げられる。これらのなかでも、エチレン性不飽和モノカルボン酸が好ましく、メタクリル酸が特に好ましい。これらのエチレン性不飽和カルボン酸単量体はアルカリ金属塩またはアンモニウム塩として用いることもできる。また、エチレン性不飽和カルボン酸単量体は単独で、または2種以上を組合せて用いることができる。ニトリル基含有共役ジエン系共重合体中における、エチレン性不飽和カルボン酸単量体により形成されるエチレン性不飽和カルボン酸単量体単位の含有割合は、好ましくは2~5重量%であり、より好ましくは2~4.5重量%、さらに好ましくは2.5~4.5重量%である。エチレン性不飽和カルボン酸単量体単位の含有量を上記範囲とすることにより、得られるディップ成形体などの膜成形体を、風合いおよび伸びに優れたものとすることができる。
The ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group, but for example, a single amount of an ethylenically unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid. Body; Esterically unsaturated polycarboxylic acid monomer such as itaconic acid, maleic acid, fumaric acid; ethylenically unsaturated polycarboxylic acid anhydride such as maleic anhydride, citraconic anhydride; monobutyl fumarate, maleic acid Examples thereof include ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl and mono-2-hydroxypropyl maleate. Among these, ethylenically unsaturated monocarboxylic acid is preferable, and methacrylic acid is particularly preferable. These ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts. Further, the ethylenically unsaturated carboxylic acid monomer can be used alone or in combination of two or more. The content ratio of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 2 to 5% by weight. It is more preferably 2 to 4.5% by weight, still more preferably 2.5 to 4.5% by weight. By setting the content of the ethylenically unsaturated carboxylic acid monomer unit in the above range, the obtained film molded product such as a dip molded product can be made excellent in texture and elongation.
ニトリル基含有共役ジエン系共重合体中における、その他のエチレン性不飽和単量体により形成されるその他の単量体単位の含有割合は、好ましくは10重量%以下であり、より好ましくは5重量%以下、さらに好ましくは3重量%以下である。
The content ratio of the other monomer unit formed by the other ethylenically unsaturated monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 10% by weight or less, more preferably 5% by weight. % Or less, more preferably 3% by weight or less.
ニトリル基含有共役ジエン系共重合体は、上述した単量体を含有してなる単量体混合物を共重合することにより得られるが、乳化重合により共重合する方法が好ましい。乳化重合方法としては、従来公知の方法を採用することができる。
The nitrile group-containing conjugated diene-based copolymer can be obtained by copolymerizing a monomer mixture containing the above-mentioned monomer, and a method of copolymerizing by emulsion polymerization is preferable. As the emulsion polymerization method, a conventionally known method can be adopted.
ニトリル基含有共役ジエン系共重合体のラテックスの数平均粒子径は、好ましくは60~300nm、より好ましくは80~150nmである。粒子径は、乳化剤および重合開始剤の使用量を調節するなどの方法により、所望の値に調整することができる。
The number average particle size of the latex of the nitrile group-containing conjugated diene copolymer is preferably 60 to 300 nm, more preferably 80 to 150 nm. The particle size can be adjusted to a desired value by a method such as adjusting the amount of the emulsifier and the polymerization initiator used.
また、本発明で用いる共役ジエン系重合体としては、上述したように、合成ポリイソプレン、スチレン-イソプレン-スチレンブロック共重合体(SIS)、蛋白質を除去した天然ゴム、ニトリル基含有共役ジエン系共重合体などを用いることができるが、これらに限定されず、ブタジエン重合体、スチレン-ブタジエン共重合体などを用いてもよい。
Further, as the conjugated diene-based polymer used in the present invention, as described above, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile group-containing conjugated diene-based polymer are used. Polymers and the like can be used, but the present invention is not limited to these, and butadiene polymers, styrene-butadiene copolymers and the like may be used.
ブタジエン重合体は、共役ジエン単量体としての1,3-ブタジエンの単独重合体であってもよいし、共役ジエン単量体としての1,3-ブタジエンと共重合可能な他のエチレン性不飽和単量体とを共重合してなる共重合体であってもよい。
The butadiene polymer may be a homopolymer of 1,3-butadiene as a conjugated diene monomer, or another ethylenically non-polymerizable copolymer with 1,3-butadiene as a conjugated diene monomer. It may be a copolymer obtained by copolymerizing with a saturated monomer.
また、スチレン-ブタジエン共重合体は、共役ジエン単量体としての1,3-ブタジエンにスチレンを共重合してなる共重合体であり、これらに加えて、必要に応じて用いられる、これらと共重合可能な他のエチレン性不飽和単量体を共重合してなる共重合体であってもよい。
The styrene-butadiene copolymer is a copolymer obtained by copolymerizing 1,3-butadiene as a conjugated diene monomer with styrene, and in addition to these, it is used as needed. It may be a copolymer obtained by copolymerizing another copolymerizable ethylenically unsaturated monomer.
また、本発明で用いる共役ジエン系重合体は、酸性基を有する単量体により変性して得られる酸変性共役ジエン系重合体であってもよく、カルボキシ変性されたカルボキシ変性共役ジエン系重合体であることが好ましい。カルボキシ変性共役ジエン系重合体は、上述した共役ジエン系重合体を、カルボキシル基を有する単量体により変性することにより得ることができる。なお、ニトリル基含有共役ジエン系共重合体として、可能なその他のエチレン性不飽和単量体として、エチレン性不飽和カルボン酸単量体を使用した場合には、既にカルボキシ変性されているため、後述するカルボキシル基を有する単量体による変性は、必ずしも必要でない。
Further, the conjugated diene-based polymer used in the present invention may be an acid-modified conjugated diene-based polymer obtained by modifying with a monomer having an acidic group, or a carboxy-modified carboxy-modified conjugated diene-based polymer. Is preferable. The carboxy-modified conjugated diene-based polymer can be obtained by modifying the above-mentioned conjugated diene-based polymer with a monomer having a carboxyl group. When an ethylenically unsaturated carboxylic acid monomer is used as the other possible ethylenically unsaturated monomer as the nitrile group-containing conjugated diene copolymer, it has already been carboxy-modified. Modification with a monomer having a carboxyl group, which will be described later, is not always necessary.
共役ジエン系重合体を、カルボキシル基を有する単量体により変性する方法としては、特に限定されないが、たとえば、共役ジエン系重合体に、カルボキシル基を有する単量体を水相中でグラフト重合する方法が挙げられる。共役ジエン系重合体にカルボキシル基を有する単量体を水相中でグラフト重合する方法としては、特に限定されず、従来公知の方法を用いればよいが、たとえば、共役ジエン系重合体のラテックスに、カルボキシル基を有する単量体と、グラフト重合触媒とを添加した後、水相中で、共役ジエン系重合体にカルボキシル基を有する単量体を反応させる方法が好ましい。
The method for modifying the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but for example, a monomer having a carboxyl group is graft-polymerized on the conjugated diene polymer in an aqueous phase. The method can be mentioned. The method for graft-polymerizing a monomer having a carboxyl group in the conjugated diene polymer in the aqueous phase is not particularly limited, and a conventionally known method may be used. For example, in the latex of the conjugated diene polymer. , A method in which a monomer having a carboxyl group and a graft polymerization catalyst are added and then the conjugated diene polymer is reacted with the monomer having a carboxyl group in an aqueous phase is preferable.
グラフト重合触媒としては、特に限定されないが、たとえば、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、過リン酸カリウム、過酸化水素等の無機過酸化物;ジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイド、t-ブチルハイドロパーオキサイド、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、ジ-t-ブチルパーオキサイド、イソブチリルパーオキサイド、ベンゾイルパーオキサイド等の有機過酸化物;2,2’-アゾビスイソブチロニトリル、アゾビス-2,4-ジメチルバレロニトリル、アゾビスイソ酪酸メチル等のアゾ化合物;等を挙げることができるが、得られるディップ成形体などの膜成形体の引張強度がより向上するという観点から、有機過酸化物が好ましく、1,1,3,3-テトラメチルブチルハイドロパーオキサイドが特に好ましい。これらのグラフト重合触媒は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
The graft polymerization catalyst is not particularly limited, and for example, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc. Organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, isobutyryl peroxide, benzoyl peroxide; 2,2'- Azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azo compounds such as methyl azobisisobutyrate; and the like; From this point of view, organic peroxide is preferable, and 1,1,3,3-tetramethylbutylhydroperoxide is particularly preferable. These graft polymerization catalysts may be used alone or in combination of two or more.
上記グラフト重合触媒は、それぞれ単独で、あるいは2種類以上を組み合わせて使用することができる。グラフト重合触媒の使用量は、その種類によって異なるが、共役ジエン系重合体100重量部に対して、好ましくは0.1~10重量部、より好ましくは0.2~5重量部である。また、グラフト重合触媒を添加する方法としては、特に限定されず、一括添加、分割添加、連続添加等の公知の添加方法を採用することができる。
The above graft polymerization catalysts can be used alone or in combination of two or more. The amount of the graft polymerization catalyst used varies depending on the type, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the conjugated diene polymer. The method for adding the graft polymerization catalyst is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
また、有機過酸化物は、還元剤との組み合わせで、レドックス系重合開始剤として使用することができる。還元剤としては、特に限定されないが、たとえば、硫酸第一鉄、ナフテン酸第一銅等の還元状態にある金属イオンを含有する化合物;ヒドロキシメタンスルフィン酸ナトリウムなどのスルフィン酸塩;ジメチルアニリン等のアミン化合物;等が挙げられる。これらの還元剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
In addition, the organic peroxide can be used as a redox-based polymerization initiator in combination with a reducing agent. The reducing agent is not particularly limited, but for example, a compound containing a metal ion in a reduced state such as ferrous sulfate and ferrous naphthenate; a sulfinate such as sodium hydroxymethanesulfinate; a dimethylaniline and the like. Amine compounds; etc. These reducing agents may be used alone or in combination of two or more.
還元剤の添加量は、特に限定されないが、有機過酸化物1重量部に対して0.01~1重量部であることが好ましい。
The amount of the reducing agent added is not particularly limited, but is preferably 0.01 to 1 part by weight with respect to 1 part by weight of the organic peroxide.
有機過酸化物の添加方法は、特に限定されず、それぞれ、一括添加、分割添加、連続添加等の公知の添加方法を用いることができる。
The method for adding the organic peroxide is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be used, respectively.
共役ジエン系重合体にカルボキシル基を有する単量体を反応させる際の反応温度は、特に限定されないが、好ましくは15~80℃、より好ましくは30~50℃である。共役ジエン系重合体にカルボキシル基を有する単量体を反応させる際の反応時間は、上記反応温度に応じて適宜設定すればよいが、好ましくは30~300分間、より好ましくは60~120分間である。
The reaction temperature when reacting the conjugated diene polymer with the monomer having a carboxyl group is not particularly limited, but is preferably 15 to 80 ° C, more preferably 30 to 50 ° C. The reaction time for reacting the conjugated diene polymer with the monomer having a carboxyl group may be appropriately set according to the above reaction temperature, but is preferably 30 to 300 minutes, more preferably 60 to 120 minutes. is there.
共役ジエン系重合体にカルボキシル基を有する単量体を反応させる際における、共役ジエン系重合体のラテックスの固形分濃度は、特に限定されないが、好ましくは5~60重量%、より好ましくは10~40重量%である。
The solid content concentration of the latex of the conjugated diene polymer in reacting the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 10 to 60% by weight. It is 40% by weight.
カルボキシル基を有する単量体としては、たとえば、アクリル酸、メタクリル酸等のエチレン性不飽和モノカルボン酸単量体;イタコン酸、マレイン酸、フマル酸、ブテントリカルボン酸等のエチレン性不飽和多価カルボン酸単量体;フマル酸モノブチル、マレイン酸モノブチル、マレイン酸モノ2-ヒドロキシプロピル等のエチレン性不飽和多価カルボン酸の部分エステル単量体;無水マレイン酸、無水シトラコン酸等の多価カルボン酸無水物;などを挙げることができるが、カルボキシ変性による効果がより一層顕著になることから、エチレン性不飽和モノカルボン酸単量体が好ましく、アクリル酸およびメタクリル酸が特に好ましい。なお、これらの単量体は1種単独でも、2種以上を併用して用いてもよい。また、上記カルボキシル基は、アルカリ金属やアンモニア等との塩になっているものも含まれる。
Examples of the monomer having a carboxyl group include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; and ethylenically unsaturated polyvalents such as itaconic acid, maleic acid, fumaric acid, and butentricarboxylic acid. Carboxylic acid monomer; Partial ester monomer of ethylenically unsaturated polyvalent carboxylic acid such as monobutyl fumarate, monobutyl maleate, mono2-hydroxypropyl maleate; polyvalent carboxylic acid such as maleic anhydride and citraconic anhydride Acid anhydrides; and the like can be mentioned, but ethylenically unsaturated monocarboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are particularly preferable, because the effect of carboxy modification becomes even more remarkable. It should be noted that these monomers may be used alone or in combination of two or more. Further, the above-mentioned carboxyl group includes those which are salts with alkali metals, ammonia and the like.
カルボキシル基を有する単量体の使用量は、共役ジエン系重合体100重量部に対して、好ましくは0.01重量部~100重量部、より好ましくは0.01重量部~40重量部、さらに好ましくは0.5重量部~20重量部である。カルボキシル基を有する単量体の使用量を上記範囲とすることにより、得られる共役ジエン系重合体ラテックス組成物の粘度がより適度なものとなり、移送しやすくなるとともに、得られるディップ成形体などの膜成形体の引張強度がより向上する。
The amount of the monomer having a carboxyl group to be used is preferably 0.01 parts by weight to 100 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, and further, with respect to 100 parts by weight of the conjugated diene polymer. It is preferably 0.5 parts by weight to 20 parts by weight. By setting the amount of the monomer having a carboxyl group in the above range, the viscosity of the obtained conjugated diene-based polymer latex composition becomes more appropriate, the transfer becomes easier, and the obtained dip molded product or the like becomes available. The tensile strength of the film molded product is further improved.
カルボキシル基を有する単量体を共役ジエン系重合体のラテックスに添加する方法としては、特に限定されず、一括添加、分割添加、連続添加等の公知の添加方法を採用することができる。
The method of adding the monomer having a carboxyl group to the latex of the conjugated diene polymer is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
カルボキシ変性共役ジエン系重合体におけるカルボキシル基を有する単量体による変性率は、得られる共役ジエン系重合体ラテックス組成物の使用目的に応じて適宜制御すればよいが、好ましくは0.01~10重量%、より好ましくは0.2~5重量%であり、さらに好ましくは0.3~3重量%、特に好ましくは0.4~2重量%である。なお、変性率は、下記式で表される。
変性率(重量%)=(X/Y)×100
なお、上記式においては、Xは、カルボキシ変性共役ジエン系重合体中における、カルボキシル基を有する単量体の単位の重量を、Yは、カルボキシ変性共役ジエン系重合体の重量をそれぞれ表す。Xは、カルボキシ変性共役ジエン系重合体について、1H-NMR測定を行い、1H-NMR測定の結果から算出する方法、あるいは、中和滴定により酸量を求め、求めた酸量から算出する方法などにより求めることができる。 The modification rate of the carboxy-modified conjugated diene-based polymer by the monomer having a carboxyl group may be appropriately controlled according to the intended use of the obtained conjugated diene-based polymer latex composition, but is preferably 0.01 to 10. It is% by weight, more preferably 0.2 to 5% by weight, still more preferably 0.3 to 3% by weight, and particularly preferably 0.4 to 2% by weight. The denaturation rate is expressed by the following formula.
Degeneration rate (% by weight) = (X / Y) x 100
In the above formula, X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified conjugated diene-based polymer, and Y represents the weight of the carboxy-modified conjugated diene-based polymer. X is calculated from a method of performing 1 H-NMR measurement on a carboxy-modified conjugated diene polymer and calculating from the result of 1 H-NMR measurement, or obtaining an acid amount by neutralization titration and calculating from the obtained acid amount. It can be obtained by a method or the like.
変性率(重量%)=(X/Y)×100
なお、上記式においては、Xは、カルボキシ変性共役ジエン系重合体中における、カルボキシル基を有する単量体の単位の重量を、Yは、カルボキシ変性共役ジエン系重合体の重量をそれぞれ表す。Xは、カルボキシ変性共役ジエン系重合体について、1H-NMR測定を行い、1H-NMR測定の結果から算出する方法、あるいは、中和滴定により酸量を求め、求めた酸量から算出する方法などにより求めることができる。 The modification rate of the carboxy-modified conjugated diene-based polymer by the monomer having a carboxyl group may be appropriately controlled according to the intended use of the obtained conjugated diene-based polymer latex composition, but is preferably 0.01 to 10. It is% by weight, more preferably 0.2 to 5% by weight, still more preferably 0.3 to 3% by weight, and particularly preferably 0.4 to 2% by weight. The denaturation rate is expressed by the following formula.
Degeneration rate (% by weight) = (X / Y) x 100
In the above formula, X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified conjugated diene-based polymer, and Y represents the weight of the carboxy-modified conjugated diene-based polymer. X is calculated from a method of performing 1 H-NMR measurement on a carboxy-modified conjugated diene polymer and calculating from the result of 1 H-NMR measurement, or obtaining an acid amount by neutralization titration and calculating from the obtained acid amount. It can be obtained by a method or the like.
本発明で用いる共役ジエン系重合体(酸変性された共役ジエン系重合体を含む)のラテックスには、ラテックスの分野で通常配合される、pH調整剤、消泡剤、防腐剤、キレート化剤、酸素捕捉剤、分散剤、老化防止剤等の添加剤を配合してもよい。
The latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention contains a pH adjuster, an antifoaming agent, an antiseptic, and a chelating agent, which are usually blended in the field of latex. , Oxygen trapping agent, dispersant, antiaging agent and other additives may be blended.
pH調整剤としては、たとえば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の炭酸塩;炭酸水素ナトリウムなどのアルカリ金属の炭酸水素塩;アンモニア;トリメチルアミン、トリエタノールアミンなどの有機アミン化合物;等が挙げられるが、アルカリ金属の水酸化物またはアンモニアが好ましい。
Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
本発明で用いる共役ジエン系重合体(酸変性された共役ジエン系重合体を含む)のラテックスの固形分濃度は、好ましくは30~70重量%、より好ましくは40~70重量%である。固形分濃度を上記範囲とすることにより、ラテックス中における凝集物の発生をより有効に抑制することができるとともに、ラテックスを貯蔵した際における重合体粒子の分離をより有効に抑制することができる。
The solid content concentration of the latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. By setting the solid content concentration in the above range, the generation of agglomerates in the latex can be more effectively suppressed, and the separation of polymer particles when the latex is stored can be more effectively suppressed.
本発明の共役ジエン系重合体ラテックス組成物は、上述した共役ジエン系重合体のラテックスに加えて、上述した本発明のキサントゲン化合物分散体、および加硫剤を含有する。
The conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention and a vulcanizing agent in addition to the above-mentioned latex of the conjugated diene polymer.
本発明の共役ジエン系重合体ラテックス組成物中における、キサントゲン化合物分散体の配合量は、特に限定されないが、共役ジエン系重合体100重量部に対する、キサントゲン化合物の含有量が、好ましくは0.01~10重量部となる量、より好ましくは0.1~7重量部となる量、さらに好ましくは0.5~5重量部となる量である。キサントゲン化合物分散体の配合量を上記範囲とすることにより、得られるディップ成形体などの膜成形体について、引張強度および引裂強度をより高めることができ、かつ、引張強度および引裂強度の安定性をより高めることができる。
The blending amount of the xanthogen compound dispersion in the conjugated diene polymer latex composition of the present invention is not particularly limited, but the content of the xanthogen compound with respect to 100 parts by weight of the conjugated diene polymer is preferably 0.01. The amount is up to 10 parts by weight, more preferably 0.1 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the blending amount of the xanthogen compound dispersion in the above range, the tensile strength and tear strength of the obtained film-molded product such as a dip-molded product can be further increased, and the tensile strength and the stability of the tear strength can be improved. Can be enhanced.
なお、キサントゲン化合物分散体中に含まれるキサントゲン化合物は、本発明の共役ジエン系重合体ラテックス組成物に含まれる活性化剤の作用により、キサントゲン酸塩の形態で存在することで、結果として、共役ジエン系重合体ラテックス組成物中に2種以上のキサントゲン化合物が含まれることになってもよい。あるいは、共役ジエン系重合体ラテックス組成物に硫黄系加硫剤等として硫黄が含まれる場合には、共役ジエン系重合体ラテックス組成物中において、キサントゲン化合物は、硫黄の作用により、その一部が、キサントゲン二硫化物やキサントゲン多硫化物の形態で存在してもよい。
The xanthogen compound contained in the xanthogen compound dispersion exists in the form of a xanthate salt due to the action of the activator contained in the conjugated diene polymer latex composition of the present invention, and as a result, it is conjugated. Two or more kinds of xanthogen compounds may be contained in the diene polymer latex composition. Alternatively, when the conjugated diene polymer latex composition contains sulfur as a sulfur-based vulcanizing agent or the like, a part of the xanthogen compound is contained in the conjugated diene polymer latex composition due to the action of sulfur. , Xantogen disulfide or xanthogen polysulfide may be present in the form.
加硫剤としては、硫黄系加硫剤が好適に用いられる。硫黄系加硫剤としては、たとえば、粉末硫黄、硫黄華、沈降硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄等の硫黄;塩化硫黄、二塩化硫黄、モルホリン・ジスルフィド、アルキルフェノールジスルフィド、カプロラクタムジスルフィド(N,N’-ジチオ-ビス(ヘキサヒドロ-2H-アゼピノン-2))、含りんポリスルフィド、高分子多硫化物、2-(4’-モルホリノジチオ)ベンゾチアゾール等の硫黄含有化合物が挙げられる。これらのなかでも、硫黄が好ましく使用できる。硫黄系加硫剤は、1種単独で、あるいは2種以上を組み合わせて用いることができる。
As the vulcanizing agent, a sulfur-based vulcanizing agent is preferably used. Examples of the sulfur-based sulfurizing agent include sulfur powder, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur; sulfur chloride, sulfur dichloride, morpholin disulfide, alkylphenol disulfide, and caprolactam disulfide (N). , N'-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfide, high molecular weight polysulfide, 2- (4'-morpholinodithio) benzothiazole and other sulfur-containing compounds. Of these, sulfur can be preferably used. The sulfur-based vulcanizing agent may be used alone or in combination of two or more.
本発明のラテックス組成物中における、加硫剤の含有量は、特に限定されないが、共役ジエン系重合体100重量部に対して、好ましくは0.1~10重量部、より好ましくは0.2~5重量部、さらに好ましくは0.5~3重量部である。加硫剤の含有量を上記範囲とすることにより、得られるディップ成形体などの膜成形体において、硬さの上昇を抑えながら、引張強度をより高めることができる。
The content of the vulcanizing agent in the latex composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 parts by weight, based on 100 parts by weight of the conjugated diene polymer. It is up to 5 parts by weight, more preferably 0.5 to 3 parts by weight. By setting the content of the vulcanizing agent in the above range, it is possible to further increase the tensile strength of the obtained film molded product such as a dip molded product while suppressing an increase in hardness.
また、本発明の共役ジエン系重合体ラテックス組成物は、金属酸化物および/または典型金属化合物をさらに含有するものであることが好ましく、少なくとも金属酸化物を含むことがより好ましい。
Further, the conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound, and more preferably at least a metal oxide.
金属酸化物および典型金属化合物は、キサントゲン化合物分散体に含まれるキサントゲン化合物とともに用いられることで、活性化剤として作用する。また、金属酸化物および典型金属化合物は、共役ジエン系重合体として酸変性共役ジエン系重合体を使用した場合に、酸性基を架橋する架橋剤としても作用し、これにより、得られるディップ成形体などの膜成形体の引張強度および引裂強度をより高めることができる。
The metal oxide and the main group metal compound act as an activator when used together with the xanthate compound contained in the xanthate compound dispersion. Further, the metal oxide and the typical metal compound also act as a cross-linking agent for cross-linking an acidic group when an acid-modified conjugated diene-based polymer is used as the conjugated diene-based polymer, whereby a dip molded product obtained by the above. It is possible to further increase the tensile strength and tear strength of the film-molded article such as.
金属酸化物としては、特に限定されないが、酸化亜鉛、酸化マグネシウム、酸化チタン、酸化カルシウム、鉛酸化物、酸化鉄、酸化銅、酸化錫、酸化ニッケル、酸化クロム、酸化コバルト、および酸化アルミニウムなどが挙げられる。これらのなかでも、得られるディップ成形体などの膜成形体の引張強度および引裂強度がより向上するという観点より、酸化亜鉛が好ましい。これらの金属酸化物は、1種単独でも、複数種を併用してもよい。
The metal oxide is not particularly limited, but includes zinc oxide, magnesium oxide, titanium oxide, calcium oxide, lead oxide, iron oxide, copper oxide, tin oxide, nickel oxide, chromium oxide, cobalt oxide, and aluminum oxide. Can be mentioned. Among these, zinc oxide is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These metal oxides may be used alone or in combination of two or more.
典型金属化合物としては、酸化物以外の典型金属化合物であればよく、特に限定されないが、典型金属の水酸化物、炭酸化物、硫酸化物、硝酸化物、リン酸化物、塩化物、臭化物、ヨウ化物などが挙げられ、なかでも、典型金属の炭酸化物が好ましい。また、典型金属化合物としては、亜鉛、マグネシウム、カルシウム、鉛、錫、およびアルミニウムなどの化合物が挙げられ、なかでも、亜鉛の化合物が好ましい。これらのなかでも、得られるディップ成形体などの膜成形体の引張強度および引裂強度がより向上するという観点より、炭酸亜鉛が好ましい。これらの典型金属化合物は、1種単独でも、複数種を併用してもよい。
The typical metal compound may be a typical metal compound other than an oxide, and is not particularly limited, but is not particularly limited, but is a typical metal hydroxide, carbon oxide, sulfate, glass oxide, phosphor oxide, chloride, bromide, or iodide. Of these, carbon oxides, which are typical metals, are preferable. In addition, typical metal compounds include compounds such as zinc, magnesium, calcium, lead, tin, and aluminum, and among them, zinc compounds are preferable. Among these, zinc carbonate is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These typical metal compounds may be used alone or in combination of two or more.
本発明の共役ジエン系重合体ラテックス組成物中における、金属酸化物および/または典型金属化合物の含有量の合計は、特に限定されないが、共役ジエン系重合体100重量部に対して、好ましくは0.01~30重量部、より好ましくは0.1~10重量部、さらに好ましくは0.5~5重量部である。金属酸化物および/または典型金属化合物の含有量の合計を上記範囲とすることにより、得られるディップ成形体などの膜成形体の引張強度および引裂強度をより向上させることができる。
The total content of the metal oxide and / or the typical metal compound in the conjugated diene polymer latex composition of the present invention is not particularly limited, but is preferably 0 with respect to 100 parts by weight of the conjugated diene polymer. It is 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.5 to 5 parts by weight. By setting the total content of the metal oxide and / or the main group metal compound in the above range, the tensile strength and the tear strength of the obtained film molded product such as the dip molded product can be further improved.
また、本発明の共役ジエン系重合体ラテックス組成物は、得られるディップ成形体などの膜成形体における、遅延型アレルギー(Type IV)の症状の発生を抑制可能な範囲であれば、さらにキサントゲン化合物以外の加硫促進剤を含有してもよい。キサントゲン化合物以外の加硫促進剤の含有量は、キサントゲン化合物の含有量とキサントゲン化合物以外の加硫促進剤の含有量の合計量に対して、20重量%以下であることが好ましく、10重量%以下であることがより好ましく、0重量%であること(すなわち、キサントゲン化合物以外の加硫促進剤を含有しないこと)がさらに好ましい。
Further, the conjugated diene polymer latex composition of the present invention is further provided with a xanthogen compound as long as it can suppress the occurrence of delayed type allergy (Type IV) symptoms in the obtained film molded product such as a dip molded product. A vulcanization accelerator other than the above may be contained. The content of the vulcanization accelerator other than the xanthate compound is preferably 20% by weight or less, preferably 10% by weight, based on the total content of the xanthate compound and the vulcanization accelerator other than the xanthate compound. It is more preferably 0% by weight (that is, it does not contain a vulcanization accelerator other than the xanthate compound).
キサントゲン化合物以外の加硫促進剤としては、ディップ成形などの膜成形において通常用いられるものが使用でき、たとえば、ジエチルジチオカルバミン酸、ジブチルジチオカルバミン酸、ジ-2-エチルヘキシルジチオカルバミン酸、ジシクロヘキシルジチオカルバミン酸、ジフェニルジチオカルバミン酸、ジベンジルジチオカルバミン酸などのジチオカルバミン酸類およびそれらの亜鉛塩;2-メルカプトベンゾチアゾール、2-メルカプトベンゾチアゾール亜鉛、2-メルカプトチアゾリン、ジベンゾチアジル・ジスルフィド、2-(2,4-ジニトロフェニルチオ)ベンゾチアゾール、2-(N,N-ジエチルチオ・カルバモイルチオ)ベンゾチアゾール、2-(2,6-ジメチル-4-モルホリノチオ)ベンゾチアゾール、2-(4′-モルホリノ・ジチオ)ベンゾチアゾール、4-モルホリニル-2-ベンゾチアジル・ジスルフィド、1,3-ビス(2-ベンゾチアジル・メルカプトメチル)ユリアなどが挙げられる。ただし、遅延型アレルギー(Type IV)の症状の発生を適切に抑制するという観点より、チウラム系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤、チアゾール系加硫促進剤以外の加硫促進剤を使用することが好ましい。なお、キサントゲン化合物以外の加硫促進剤は、1種単独で、あるいは2種以上を組み合わせて用いることができる。
As the sulfide accelerator other than the xanthogen compound, those usually used in film molding such as dip molding can be used, and for example, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, dicyclohexyldithiocarbamic acid, diphenyldithiocarbamine. Dithiocarbamic acids such as acids, dibenzyldithiocarbamic acid and their zinc salts; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazolin, dibenzothiazyl disulfide, 2- (2,4-dinitrophenylthio) ) Benzothiazole, 2- (N, N-diethylthio carbamoylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, 2- (4'-morpholino dithio) benzothiazole, 4 -Morphorinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea and the like can be mentioned. However, from the viewpoint of appropriately suppressing the occurrence of delayed allergy (Type IV) symptoms, vulcanization accelerators other than thiuram-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators, and thiazole-based vulcanization accelerators. It is preferable to use. The vulcanization accelerator other than the xanthate compound can be used alone or in combination of two or more.
本発明の共役ジエン系重合体ラテックス組成物には、さらに、老化防止剤;分散剤;カーボンブラック、シリカ、タルク等の補強剤;炭酸カルシウム、クレー等の充填剤;紫外線吸収剤;可塑剤;等の配合剤を必要に応じて配合することができる。
The conjugated diene polymer latex composition of the present invention further includes an antiaging agent; a dispersant; a reinforcing agent such as carbon black, silica and talc; a filler such as calcium carbonate and clay; an ultraviolet absorber; a plasticizer; Etc. can be blended as needed.
老化防止剤としては、2,6-ジ-4-メチルフェノール、2,6-ジ-t-ブチルフェノール、ブチルヒドロキシアニソール、2,6-ジ-t-ブチル-α-ジメチルアミノ-p-クレゾール、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、スチレン化フェノール、2,2’-メチレン-ビス(6-α-メチル-ベンジル-p-クレゾール)、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)、2,2’-メチレン-ビス(4-メチル-6-t-ブチルフェノール)、アルキル化ビスフェノール、p-クレゾールとジシクロペンタジエンのブチル化反応生成物、などの硫黄原子を含有しないフェノール系老化防止剤;2,2’-チオビス-(4-メチル-6-t-ブチルフェノール)、4,4’-チオビス-(6-t-ブチル-o-クレゾール)、2,6-ジ-t-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミノ)フェノールなどのチオビスフェノール系老化防止剤;トリス(ノニルフェニル)ホスファイト、ジフェニルイソデシルホスファイト、テトラフェニルジプロピレングリコール・ジホスファイトなどの亜燐酸エステル系老化防止剤;チオジプロピオン酸ジラウリルなどの硫黄エステル系老化防止剤;フェニル-α-ナフチルアミン、フェニル-β-ナフチルアミン、p-(p-トルエンスルホニルアミド)-ジフェニルアミン、4,4’―(α,α-ジメチルベンジル)ジフェニルアミン、N,N-ジフェニル-p-フェニレンジアミン、N-イソプロピル-N’-フェニル-p-フェニレンジアミン、ブチルアルデヒド-アニリン縮合物などのアミン系老化防止剤;6-エトキシ-2,2,4-トリメチル-1,2-ジヒドロキノリンなどのキノリン系老化防止剤;2,5-ジ-(t-アミル)ハイドロキノンなどのハイドロキノン系老化防止剤;などが挙げられる。これらの老化防止剤は、1種単独で、または2種以上を併用することができる。
Anti-aging agents include 2,6-di-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl-α-dimethylamino-p-cresol, Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2'-methylene-bis (6-α-methyl-benzyl-p-cresol), 4, Butylation of 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), alkylated bisphenol, p-cresol and dicyclopentadiene Phenolic antioxidants that do not contain sulfur atoms such as reaction products; 2,2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (6-t-butyl-) O-cresol), 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamino) phenol and other thiobisphenolic antioxidants; Tris (Nonylphenyl) phosphite, diphenylisodecylphosphite, tetraphenyldipropylene glycol / diphosphite and other phosphite-based anti-aging agents; sulfur ester-based anti-aging agents such as dilauryl thiodipropionate; phenyl-α-naphthylamine, Phenyl-β-naphthylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4'-(α, α-dimethylbenzyl) diphenylamine, N, N-diphenyl-p-phenylenediamine, N-isopropyl-N' -Amine-based anti-aging agents such as phenyl-p-phenylenediamine, butylaldehyde-aniline condensate; Hydroquinone-based anti-aging agents such as 5-di (t-amyl) hydroquinone; and the like. These antioxidants can be used alone or in combination of two or more.
本発明の共役ジエン系重合体ラテックス組成物中における、老化防止剤の含有量は、カルボキシ変性共役ジエン系重合体100重量部に対して、好ましくは0.05~10重量部、より好ましくは0.1~5重量部である。
The content of the antioxidant in the conjugated diene polymer latex composition of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0, based on 100 parts by weight of the carboxy-modified conjugated diene polymer. .1 to 5 parts by weight.
本発明の共役ジエン系重合体ラテックス組成物を調製する方法としては、特に限定されないが、たとえば、上述した共役ジエン系重合体のラテックスに、加硫剤、およびキサントゲン化合物分散体、ならびに必要に応じて用いられる各種配合剤を混合する方法などが挙げられる。この際においては、共役ジエン系重合体のラテックス以外の配合成分の水性分散液を調製した後、該水性分散液を、共役ジエン系重合体のラテックスに混合する方法などを採用することもできる。
The method for preparing the conjugated diene polymer latex composition of the present invention is not particularly limited, but for example, the latex of the conjugated diene polymer described above, a vulcanizing agent, a xanthogen compound dispersion, and if necessary. Examples thereof include a method of mixing various compounding agents used in the above. In this case, a method of preparing an aqueous dispersion of a compounding component other than the latex of the conjugated diene polymer and then mixing the aqueous dispersion with the latex of the conjugated diene polymer can also be adopted.
なお、本発明の共役ジエン系重合体ラテックス組成物の固形分濃度は、好ましくは10~60重量%、より好ましくは10~55重量%である。
The solid content concentration of the conjugated diene polymer latex composition of the present invention is preferably 10 to 60% by weight, more preferably 10 to 55% by weight.
また、本発明においては、得られるディップ成形体などの膜成形体の機械的特性を十分なものとするという観点より、ディップ成形などの膜成形に供する前に、本発明の共役ジエン系重合体ラテックス組成物について、熟成(前加硫)を行うことが好ましい。熟成(前加硫)時間は、特に限定されないが、好ましくは8~120時間、より好ましくは24~72時間である。熟成(前加硫)の温度は、特に限定されないが、好ましくは20~40℃である。また、本発明の共役ジエン系重合体ラテックス組成物を使用する際には、熟成(前加硫)を所定時間行った後、熟成(前加硫)条件を保ったまま(熟成(前加硫)を継続したまま)、ディップ成形などの膜成形を連続的に行ってもよく、この場合における熟成(前加硫)時間および熟成(前加硫)温度は、上記範囲とすればよい。特に、本発明の共役ジエン系重合体ラテックス組成物は、上述した本発明のキサントゲン化合物分散体を含むものであるため、熟成(前加硫)時間を上記のように比較的長くした場合でも、引張強度および引裂強度に優れる膜成形体を得ることができるものであり、熟成(前加硫)条件を保ったまま、多数のディップ成形体などの膜成形体を連続的に製造した場合でも、引張強度および引裂強度に優れる膜成形体を安定して製造できる(引張強度および引裂強度を大きく低下させることなく、安定して製造できる)ものである。そして、その結果として、本発明の共役ジエン系重合体ラテックス組成物によれば、引張強度および引裂強度に優れたディップ成形体などの膜成形体を高い生産性にて製造することが可能となる。
Further, in the present invention, from the viewpoint of making the mechanical properties of the obtained film-molded article such as a dip-molded article sufficient, the conjugated diene-based polymer of the present invention may be prepared before being subjected to film-molding such as dip molding. The latex composition is preferably aged (pre-vulcanized). The aging (pre-vulcanization) time is not particularly limited, but is preferably 8 to 120 hours, more preferably 24-72 hours. The temperature of aging (pre-vulcanization) is not particularly limited, but is preferably 20 to 40 ° C. Further, when using the conjugated diene polymer latex composition of the present invention, after aging (pre-vulcanization) for a predetermined time, the aging (pre-vulcanization) conditions are maintained (aging (pre-vulcanization)). ), Film molding such as dip molding may be continuously performed, and the aging (pre-vulcanization) time and aging (pre-vulcanization) temperature in this case may be within the above ranges. In particular, since the conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention, the tensile strength even when the aging (pre-vulcanization) time is relatively long as described above. It is possible to obtain a film-molded article having excellent tear strength, and even when a large number of dip-molded articles and other film-molded articles are continuously manufactured while maintaining the aging (pre-vulcanization) conditions, the tensile strength is obtained. In addition, a film molded product having excellent tear strength can be stably produced (stable production can be performed without significantly reducing the tensile strength and the tear strength). As a result, according to the conjugated diene polymer latex composition of the present invention, it becomes possible to produce a film molded product such as a dip molded product having excellent tensile strength and tear strength with high productivity. ..
<膜成形体>
本発明の膜成形体は、上述した本発明の共役ジエン系重合体ラテックス組成物からなる膜状の成形体である。本発明の膜成形体の膜厚は、好ましくは0.03~0.50mm、より好ましくは0.05~0.40mm、特に好ましくは0.08~0.30mmである。 <Membrane molded product>
The film-molded article of the present invention is a film-shaped molded article composed of the above-mentioned conjugated diene-based polymer latex composition of the present invention. The film thickness of the film molded product of the present invention is preferably 0.03 to 0.50 mm, more preferably 0.05 to 0.40 mm, and particularly preferably 0.08 to 0.30 mm.
本発明の膜成形体は、上述した本発明の共役ジエン系重合体ラテックス組成物からなる膜状の成形体である。本発明の膜成形体の膜厚は、好ましくは0.03~0.50mm、より好ましくは0.05~0.40mm、特に好ましくは0.08~0.30mmである。 <Membrane molded product>
The film-molded article of the present invention is a film-shaped molded article composed of the above-mentioned conjugated diene-based polymer latex composition of the present invention. The film thickness of the film molded product of the present invention is preferably 0.03 to 0.50 mm, more preferably 0.05 to 0.40 mm, and particularly preferably 0.08 to 0.30 mm.
本発明の膜成形体としては、特に限定されないが、本発明の共役ジエン系重合体ラテックス組成物をディップ成形して得られるディップ成形体であることが好適である。ディップ成形は、共役ジエン系重合体ラテックス組成物に型を浸漬し、型の表面に当該組成物を沈着させ、次に型を当該組成物から引き上げ、その後、型の表面に沈着した当該組成物を乾燥させる方法である。なお、共役ジエン系重合体ラテックス組成物に浸漬される前の型は予熱しておいてもよい。また、型を共役ジエン系重合体ラテックス組成物に浸漬する前、または、型を共役ジエン系重合体ラテックス組成物から引き上げた後、必要に応じて凝固剤を使用できる。
The film molded product of the present invention is not particularly limited, but a dip molded product obtained by dip molding the conjugated diene polymer latex composition of the present invention is preferable. Dip molding involves immersing a mold in a conjugated diene polymer latex composition, depositing the composition on the surface of the mold, then pulling the mold out of the composition, and then depositing the composition on the surface of the mold. Is a method of drying. The mold before being immersed in the conjugated diene polymer latex composition may be preheated. Further, a coagulant can be used as needed before immersing the mold in the conjugated diene polymer latex composition or after pulling the mold out of the conjugated diene polymer latex composition.
凝固剤の使用方法の具体例としては、共役ジエン系重合体ラテックス組成物に浸漬する前の型を凝固剤の溶液に浸漬して型に凝固剤を付着させる方法(アノード凝着浸漬法)、共役ジエン系重合体ラテックス組成物を沈着させた型を凝固剤溶液に浸漬する方法(ティーグ凝着浸漬法)などがあるが、厚みムラの少ないディップ成形体が得られる点で、アノード凝着浸漬法が好ましい。
Specific examples of the method of using the coagulant include a method of immersing the mold before being immersed in the conjugated diene polymer latex composition in a solution of the coagulant to attach the coagulant to the mold (anode adhesion immersion method). There is a method of immersing a mold in which a conjugated diene polymer latex composition is deposited in a coagulant solution (Teeg adhesion immersion method), but it is possible to obtain a dip molded body with less uneven thickness, so that it is immersed in an anode adhesion. The method is preferred.
凝固剤の具体例としては、塩化バリウム、塩化カルシウム、塩化マグネシウム、塩化亜鉛、塩化アルミニウムなどのハロゲン化金属;硝酸バリウム、硝酸カルシウム、硝酸亜鉛などの硝酸塩;酢酸バリウム、酢酸カルシウム、酢酸亜鉛など酢酸塩;硫酸カルシウム、硫酸マグネシウム、硫酸アルミニウムなどの硫酸塩;などの水溶性多価金属塩である。なかでも、カルシウム塩が好ましく、硝酸カルシウムがより好ましい。これらの水溶性多価金属塩は、1種単独で、または2種以上を併用することができる。
Specific examples of the coagulant include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; nitrates such as barium nitrate, calcium nitrate and zinc nitrate; acetic acid such as barium acetate, calcium acetate and zinc acetate. Salts; water-soluble polyvalent metal salts such as calcium sulfate, magnesium sulfate, sulfates such as aluminum sulfate; Of these, calcium salts are preferable, and calcium nitrate is more preferable. These water-soluble polyvalent metal salts can be used alone or in combination of two or more.
凝固剤は、通常、水、アルコール、またはそれらの混合物の溶液として使用することができ、好ましくは水溶液の状態で使用する。この水溶液は、さらにメタノール、エタノールなどの水溶性有機溶媒やノニオン性界面活性剤を含有していてもよい。凝固剤の濃度は、水溶性多価金属塩の種類によっても異なるが、好ましくは5~50重量%、より好ましくは10~30重量%である。
The coagulant can usually be used as a solution of water, alcohol, or a mixture thereof, and is preferably used in the state of an aqueous solution. This aqueous solution may further contain a water-soluble organic solvent such as methanol or ethanol or a nonionic surfactant. The concentration of the coagulant varies depending on the type of the water-soluble polyvalent metal salt, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
型を共役ジエン系重合体ラテックス組成物から引き上げた後、通常、加熱して型上に形成された沈着物を乾燥させる。乾燥条件は適宜選択すればよい。
After the mold is pulled up from the conjugated diene polymer latex composition, it is usually heated to dry the deposits formed on the mold. The drying conditions may be appropriately selected.
次いで、得られたディップ成形層に対し、加熱処理を施し加硫を行う。また、この際には、加熱処理を施す前に、水、好ましくは30~70℃の温水に、1~60分程度浸漬し、水溶性不純物(たとえば、余剰の乳化剤や凝固剤等)を除去してもよい。水溶性不純物の除去操作は、ディップ成形層を加熱処理した後に行なってもよいが、より効率的に水溶性不純物を除去できる点から、加熱処理前に行なうことが好ましい。
Next, the obtained dip molded layer is heat-treated and vulcanized. In this case, before the heat treatment, the mixture is immersed in water, preferably warm water at 30 to 70 ° C. for about 1 to 60 minutes to remove water-soluble impurities (for example, excess emulsifier, coagulant, etc.). You may. The operation for removing water-soluble impurities may be performed after the dip molding layer has been heat-treated, but it is preferably performed before the heat treatment because the water-soluble impurities can be removed more efficiently.
ディップ成形層の加硫は、通常、80~150℃の温度で、好ましくは10~130分の加熱処理を施すことにより行われる。加熱の方法としては、赤外線や加熱空気による外部加熱または高周波による内部加熱による方法が採用できる。なかでも、加熱空気による外部加熱が好ましい。
Vulcanization of the dip molded layer is usually carried out by heat treatment at a temperature of 80 to 150 ° C., preferably for 10 to 130 minutes. As the heating method, a method of external heating by infrared rays or heated air or internal heating by high frequency can be adopted. Of these, external heating with heated air is preferable.
そして、ディップ成形層をディップ成形用型から脱着することによって、ディップ成形体が、膜状の膜成形体として得られる。脱着方法としては、手で成形用型から剥したり、水圧や圧縮空気の圧力により剥したりする方法を採用することができる。なお、脱着後、さらに60~120℃の温度で、10~120分の加熱処理を行なってもよい。
Then, by detaching the dip molding layer from the dip molding mold, the dip molded body can be obtained as a film-shaped film molded body. As a desorption method, a method of manually peeling from the molding mold or a method of peeling by water pressure or compressed air pressure can be adopted. After desorption, heat treatment may be further performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
なお、本発明の膜成形体は、上述した本発明の共役ジエン系重合体ラテックス組成物を、ディップ成形する方法以外にも、上述した本発明の共役ジエン系重合体ラテックス組成物を、膜状に成形できる方法(たとえば、塗布法等)であれば、いずれの方法で得られるものであってもよい。
In addition to the method of dip molding the conjugated diene-based polymer latex composition of the present invention described above, the film-molded product of the present invention is a film-like conjugated diene-based polymer latex composition of the present invention described above. Any method may be used as long as it can be molded into (for example, a coating method).
本発明のディップ成形体を含む本発明の膜成形体は、即時型アレルギー(Type I)に加えて遅延型アレルギー(Type IV)の症状の発生を抑制可能であり、しかも、引張強度および引裂強度に優れ、かつ、引張強度および引裂強度の安定性に優れるものであり、たとえば、手袋として特に好適に用いることができる。膜成形体が手袋である場合、膜成形体同士の接触面における密着を防止し、着脱の際の滑りをよくするために、タルク、炭酸カルシウムなどの無機微粒子または澱粉粒子などの有機微粒子を手袋表面に散布したり、微粒子を含有するエラストマー層を手袋表面に形成したり、手袋の表面層を塩素化したりしてもよい。
The film molded product of the present invention, including the dip molded product of the present invention, can suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I), and also has tensile strength and tear strength. It is excellent in stability of tensile strength and tear strength, and can be particularly preferably used as a glove, for example. When the film-molded body is a glove, in order to prevent adhesion between the film-molded bodies on the contact surface and to improve slippage during attachment / detachment, gloves are made of inorganic fine particles such as talc and calcium carbonate or organic fine particles such as starch particles. It may be sprayed on the surface, an elastomer layer containing fine particles may be formed on the surface of the glove, or the surface layer of the glove may be chlorinated.
また、本発明のディップ成形体を含む本発明の膜成形体は、上記手袋の他にも、哺乳瓶用乳首、スポイト、チューブ、水枕、バルーンサック、カテーテル、コンドームなどの医療用品;風船、人形、ボールなどの玩具;加圧成形用バック、ガス貯蔵用バックなどの工業用品;指サックなどにも用いることができる。
In addition to the above gloves, the film molded product of the present invention including the dip molded product of the present invention includes medical supplies such as baby bottle nipples, droppers, tubes, water pillows, balloon sack, catheters, condoms; balloons, dolls, etc. , Balls and other toys; industrial products such as pressure molding bags and gas storage bags; can also be used for finger cots and the like.
<接着剤組成物>
また、本発明においては、上述した本発明の共役ジエン系重合体ラテックス組成物を、接着剤組成物として用いることができる。 <Adhesive composition>
Further, in the present invention, the above-mentioned conjugated diene polymer latex composition of the present invention can be used as the adhesive composition.
また、本発明においては、上述した本発明の共役ジエン系重合体ラテックス組成物を、接着剤組成物として用いることができる。 <Adhesive composition>
Further, in the present invention, the above-mentioned conjugated diene polymer latex composition of the present invention can be used as the adhesive composition.
接着剤組成物中における、本発明の共役ジエン系重合体ラテックス組成物の含有量(固形分量)は、好ましくは5~60重量%、より好ましくは10~30重量%である。
The content (solid content) of the conjugated diene-based polymer latex composition of the present invention in the adhesive composition is preferably 5 to 60% by weight, more preferably 10 to 30% by weight.
接着剤組成物は、本発明の共役ジエン系重合体ラテックス組成物に加えて、接着剤樹脂を含有してなることが好ましい。接着剤樹脂としては、特に限定されないが、たとえば、レゾルシン-ホルムアルデヒド樹脂、メラミン樹脂、エポキシ樹脂及びイソシアネート樹脂を好適に使用することができ、これらのなかでも、レゾルシン-ホルムアルデヒド樹脂が好ましい。レゾルシン-ホルムアルデヒド樹脂は、公知のもの(例えば、特開昭55-142635号公報に開示のもの)が使用できる。レゾルシンとホルムアルデヒドとの反応比率は、「レゾルシン:ホルムアルデヒド」のモル比で、通常、1:1~1:5、好ましくは1:1~1:3である。
The adhesive composition preferably contains an adhesive resin in addition to the conjugated diene polymer latex composition of the present invention. The adhesive resin is not particularly limited, but for example, resorcin-formaldehyde resin, melamine resin, epoxy resin and isocyanate resin can be preferably used, and among these, resorcin-formaldehyde resin is preferable. As the resorcin-formaldehyde resin, known ones (for example, those disclosed in JP-A-55-142635) can be used. The reaction ratio of resorcin to formaldehyde is a molar ratio of "resorcin: formaldehyde", usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3.
また、接着剤組成物の接着力をさらに高めるために、接着剤組成物には、従来から使用されている2,6-ビス(2,4-ジヒドロキシフェニルメチル)-4-クロロフェノールまたは類似の化合物、イソシアネート、ブロックイソシアネート、エチレン尿素、ポリエポキシド、変性ポリ塩化ビニル樹脂等を含有させることができる。
In addition, in order to further enhance the adhesive strength of the adhesive composition, the adhesive composition contains 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or the like conventionally used. Compounds, isocyanates, blocked isocyanates, ethylene ureas, polyepoxides, modified polyvinyl chloride resins and the like can be contained.
さらに、接着剤組成物には、架橋助剤を含有させることができる。架橋助剤を含有させることにより、接着剤組成物を用いて得られる後述する複合体の機械的強度を向上させることができる。架橋助剤としては、p-キノンジオキシム等のキノンジオキシム;ラウリルメタクリレートやメチルメタクリレート等のメタクリル酸エステル;DAF(ジアリルフマレート)、DAP(ジアリルフタレート)、TAC(トリアリルシアヌレート)、TAIC(トリアリルイソシアヌレート)等のアリル化合物;ビスマレイミド、フェニルマレイミド、N,N-m-フェニレンジマレイミド等のマレイミド化合物;硫黄;等を挙げることができる。
Further, the adhesive composition can contain a cross-linking aid. By containing the cross-linking aid, the mechanical strength of the complex described later obtained by using the adhesive composition can be improved. Examples of the cross-linking aid include quinone dioximes such as p-quinone dioxime; methacrylate esters such as lauryl methacrylate and methyl methacrylate; DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (triallyl cyanurate), and TAIC. Allyl compounds such as (triallyl isocyanurate); maleimide compounds such as bismaleimide, phenylmaleimide, N, Nm-phenylenedi maleimide; sulfur; and the like can be mentioned.
以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。なお、以下の「部」は、特に断りのない限り、重量基準である。なお、各種の物性は以下のように測定した。
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. Unless otherwise specified, the following "parts" are based on weight. Various physical properties were measured as follows.
<固形分濃度>
アルミ皿(重量:X1)に試料2gを精秤し(重量:X2)、これを105℃の熱風乾燥器内で2時間乾燥させた。次いで、デシケーター内で冷却した後、アルミ皿ごと重量を測定し(重量:X3)、下記の計算式にしたがって、固形分濃度を算出した。
固形分濃度(重量%)=(X3-X1)×100/X2 <Solid content concentration>
2 g of the sample was precisely weighed on an aluminum plate (weight: X1) (weight: X2), and this was dried in a hot air dryer at 105 ° C. for 2 hours. Then, after cooling in the desiccator, the weight of the aluminum dish was measured (weight: X3), and the solid content concentration was calculated according to the following formula.
Solid content concentration (% by weight) = (X3-X1) x 100 / X2
アルミ皿(重量:X1)に試料2gを精秤し(重量:X2)、これを105℃の熱風乾燥器内で2時間乾燥させた。次いで、デシケーター内で冷却した後、アルミ皿ごと重量を測定し(重量:X3)、下記の計算式にしたがって、固形分濃度を算出した。
固形分濃度(重量%)=(X3-X1)×100/X2 <Solid content concentration>
2 g of the sample was precisely weighed on an aluminum plate (weight: X1) (weight: X2), and this was dried in a hot air dryer at 105 ° C. for 2 hours. Then, after cooling in the desiccator, the weight of the aluminum dish was measured (weight: X3), and the solid content concentration was calculated according to the following formula.
Solid content concentration (% by weight) = (X3-X1) x 100 / X2
<カルボキシ変性合成ポリイソプレンの変性率>
カルボキシ変性合成ポリイソプレンのラテックスを構成するカルボキシ変性合成ポリイソプレンについて、水酸化ナトリウム水溶液を用いた中和滴定により、カルボキシ変性合成ポリイソプレン中におけるカルボキシル基の数を求めた。次いで、求めたカルボキシル基の数に基づいて、下記式にしたがって、カルボキシル基を有する単量体による変性率を求めた。
変性率(重量%)=(X/Y)×100
なお、上記式においては、Xは、カルボキシ変性合成ポリイソプレン中における、カルボキシル基を有する単量体の単位の重量を、Yは、カルボキシ変性合成ポリイソプレンの重量をそれぞれ表す。 <Modification rate of carboxy-modified synthetic polyisoprene>
The number of carboxyl groups in the carboxy-modified synthetic polyisoprene was determined by neutralization titration using an aqueous sodium hydroxide solution for the carboxy-modified synthetic polyisoprene constituting the latex of the carboxy-modified synthetic polyisoprene. Then, based on the obtained number of carboxyl groups, the modification rate of the monomer having a carboxyl group was determined according to the following formula.
Degeneration rate (% by weight) = (X / Y) x 100
In the above formula, X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified synthetic polyisoprene, and Y represents the weight of the carboxy-modified synthetic polyisoprene.
カルボキシ変性合成ポリイソプレンのラテックスを構成するカルボキシ変性合成ポリイソプレンについて、水酸化ナトリウム水溶液を用いた中和滴定により、カルボキシ変性合成ポリイソプレン中におけるカルボキシル基の数を求めた。次いで、求めたカルボキシル基の数に基づいて、下記式にしたがって、カルボキシル基を有する単量体による変性率を求めた。
変性率(重量%)=(X/Y)×100
なお、上記式においては、Xは、カルボキシ変性合成ポリイソプレン中における、カルボキシル基を有する単量体の単位の重量を、Yは、カルボキシ変性合成ポリイソプレンの重量をそれぞれ表す。 <Modification rate of carboxy-modified synthetic polyisoprene>
The number of carboxyl groups in the carboxy-modified synthetic polyisoprene was determined by neutralization titration using an aqueous sodium hydroxide solution for the carboxy-modified synthetic polyisoprene constituting the latex of the carboxy-modified synthetic polyisoprene. Then, based on the obtained number of carboxyl groups, the modification rate of the monomer having a carboxyl group was determined according to the following formula.
Degeneration rate (% by weight) = (X / Y) x 100
In the above formula, X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified synthetic polyisoprene, and Y represents the weight of the carboxy-modified synthetic polyisoprene.
<ノニオン系界面活性剤の数平均分子量(Mn)>
ノニオン系界面活性剤をテトラヒドロフランに溶解して、0.2重量%溶液とした後、0.45μmのメンブランフィルターで濾過したものを測定試料として、ゲルパーミエーションクロマトグラフィ(GPC)を用いて下記条件にて測定することにより、標準ポリスチレン換算のノニオン系界面活性剤の数平均分子量(Mn)を求めた。
測定装置:HLC-8220GPC(東ソー社製)
カラム:TSKgel G1000H(東ソー社製)、TSKgel G2000H(東ソー社製)
溶離液:テトラヒドロフラン(THF)
溶離速度:0.3ml/分
検知器:RI(極性(+))
カラム温度:40℃ <Number average molecular weight (Mn) of nonionic surfactant>
A nonionic surfactant was dissolved in tetrahydrofuran to prepare a 0.2 wt% solution, and then filtered through a 0.45 μm membrane filter as a measurement sample, which was subjected to gel permeation chromatography (GPC) under the following conditions. The number average molecular weight (Mn) of the nonionic surfactant in terms of standard polystyrene was determined by the measurement.
Measuring device: HLC-8220GPC (manufactured by Tosoh)
Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh)
Eluent: tetrahydrofuran (THF)
Elution rate: 0.3 ml / min Detector: RI (polarity (+))
Column temperature: 40 ° C
ノニオン系界面活性剤をテトラヒドロフランに溶解して、0.2重量%溶液とした後、0.45μmのメンブランフィルターで濾過したものを測定試料として、ゲルパーミエーションクロマトグラフィ(GPC)を用いて下記条件にて測定することにより、標準ポリスチレン換算のノニオン系界面活性剤の数平均分子量(Mn)を求めた。
測定装置:HLC-8220GPC(東ソー社製)
カラム:TSKgel G1000H(東ソー社製)、TSKgel G2000H(東ソー社製)
溶離液:テトラヒドロフラン(THF)
溶離速度:0.3ml/分
検知器:RI(極性(+))
カラム温度:40℃ <Number average molecular weight (Mn) of nonionic surfactant>
A nonionic surfactant was dissolved in tetrahydrofuran to prepare a 0.2 wt% solution, and then filtered through a 0.45 μm membrane filter as a measurement sample, which was subjected to gel permeation chromatography (GPC) under the following conditions. The number average molecular weight (Mn) of the nonionic surfactant in terms of standard polystyrene was determined by the measurement.
Measuring device: HLC-8220GPC (manufactured by Tosoh)
Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh)
Eluent: tetrahydrofuran (THF)
Elution rate: 0.3 ml / min Detector: RI (polarity (+))
Column temperature: 40 ° C
<ディップ成形体の引張強度および引張強度の安定性>
ディップ成形体(24時間熟成品および72時間熟成品)を、ASTM D412に基づいて、ダンベル(商品名「スーパーダンベル(型式:SDMK-100C)」、ダンベル社製)で打ち抜き、引張強度測定用試験片を作製した。当該試験片をテンシロン万能試験機(商品名「RTG-1210」、オリエンテック社製)で引張速度500mm/minで引っ張り、破断直前の引張強度(単位:MPa)を測定した。なお、測定は、5個の試験片について行い、5個の試験片の測定値のうち、中央値(すなわち、5個の試験片のうち、3番目に大きい値を示した試験片の引張強度の値)を、引張強度の値として採用した。
引張強度が高いほど、引張強度に優れると判断できる。
また、24時間熟成品の引張強度と、72時間熟成品の引張強度との差が小さいほど、引張強度の安定性に優れると判断できる。 <Tensile strength of dip molded product and stability of tensile strength>
Dip molded products (24-hour aged product and 72-hour aged product) are punched with a dumbbell (trade name "Super Dumbbell (model: SDKM-100C)", manufactured by Dumbbell) based on ASTM D412, and a test for measuring tensile strength. Pieces were made. The test piece was pulled by a Tencilon universal testing machine (trade name "RTG-1210", manufactured by Orientec Co., Ltd.) at a tensile speed of 500 mm / min, and the tensile strength (unit: MPa) immediately before breaking was measured. The measurement was performed on 5 test pieces, and the tensile strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tensile strength.
It can be judged that the higher the tensile strength, the better the tensile strength.
Further, it can be judged that the smaller the difference between the tensile strength of the 24-hour aged product and the tensile strength of the 72-hour aged product, the better the stability of the tensile strength.
ディップ成形体(24時間熟成品および72時間熟成品)を、ASTM D412に基づいて、ダンベル(商品名「スーパーダンベル(型式:SDMK-100C)」、ダンベル社製)で打ち抜き、引張強度測定用試験片を作製した。当該試験片をテンシロン万能試験機(商品名「RTG-1210」、オリエンテック社製)で引張速度500mm/minで引っ張り、破断直前の引張強度(単位:MPa)を測定した。なお、測定は、5個の試験片について行い、5個の試験片の測定値のうち、中央値(すなわち、5個の試験片のうち、3番目に大きい値を示した試験片の引張強度の値)を、引張強度の値として採用した。
引張強度が高いほど、引張強度に優れると判断できる。
また、24時間熟成品の引張強度と、72時間熟成品の引張強度との差が小さいほど、引張強度の安定性に優れると判断できる。 <Tensile strength of dip molded product and stability of tensile strength>
Dip molded products (24-hour aged product and 72-hour aged product) are punched with a dumbbell (trade name "Super Dumbbell (model: SDKM-100C)", manufactured by Dumbbell) based on ASTM D412, and a test for measuring tensile strength. Pieces were made. The test piece was pulled by a Tencilon universal testing machine (trade name "RTG-1210", manufactured by Orientec Co., Ltd.) at a tensile speed of 500 mm / min, and the tensile strength (unit: MPa) immediately before breaking was measured. The measurement was performed on 5 test pieces, and the tensile strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tensile strength.
It can be judged that the higher the tensile strength, the better the tensile strength.
Further, it can be judged that the smaller the difference between the tensile strength of the 24-hour aged product and the tensile strength of the 72-hour aged product, the better the stability of the tensile strength.
<ディップ成形体の引裂強度および引裂強度の安定性>
ディップ成形体(24時間熟成品および72時間熟成品)を、ASTM D624-00に基づいて、23℃、相対湿度50%の恒温恒湿室で24時間以上放置した後、ダンベル(商品名「Die C」、ダンベル社製)で打ち抜き、引裂強度測定用の試験片を作製した。当該試験片をテンシロン万能試験機(商品名「RTG-1210」、A&D社製)で引張速度500mm/minで引っ張り、引裂強度(単位:N/mm)を測定した。なお、測定は、5個の試験片について行い、5個の試験片の測定値のうち、中央値(すなわち、5個の試験片のうち、3番目に大きい値を示した試験片の引裂強度の値)を、引裂強度の値として採用した。
引裂強度が高いほど、引裂強度に優れると判断できる。
また、24時間熟成品の引裂強度と、72時間熟成品の引裂強度との差が小さいほど、引裂強度の安定性に優れると判断できる。 <Tear strength and stability of tear strength of dip molded product>
Dip molded products (24-hour aged product and 72-hour aged product) are left to stand in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity for 24 hours or more based on ASTM D624-00, and then dumbbells (trade name "Die"). C ”, manufactured by Dumbbell Co., Ltd.) to prepare a test piece for measuring tear strength. The test piece was pulled by a Tencilon universal testing machine (trade name "RTG-1210", manufactured by A & D Co., Ltd.) at a tensile speed of 500 mm / min, and the tear strength (unit: N / mm) was measured. The measurement was performed on 5 test pieces, and the tear strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tear strength.
It can be judged that the higher the tear strength, the better the tear strength.
Further, it can be judged that the smaller the difference between the tear strength of the 24-hour aged product and the tear strength of the 72-hour aged product, the better the stability of the tear strength.
ディップ成形体(24時間熟成品および72時間熟成品)を、ASTM D624-00に基づいて、23℃、相対湿度50%の恒温恒湿室で24時間以上放置した後、ダンベル(商品名「Die C」、ダンベル社製)で打ち抜き、引裂強度測定用の試験片を作製した。当該試験片をテンシロン万能試験機(商品名「RTG-1210」、A&D社製)で引張速度500mm/minで引っ張り、引裂強度(単位:N/mm)を測定した。なお、測定は、5個の試験片について行い、5個の試験片の測定値のうち、中央値(すなわち、5個の試験片のうち、3番目に大きい値を示した試験片の引裂強度の値)を、引裂強度の値として採用した。
引裂強度が高いほど、引裂強度に優れると判断できる。
また、24時間熟成品の引裂強度と、72時間熟成品の引裂強度との差が小さいほど、引裂強度の安定性に優れると判断できる。 <Tear strength and stability of tear strength of dip molded product>
Dip molded products (24-hour aged product and 72-hour aged product) are left to stand in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity for 24 hours or more based on ASTM D624-00, and then dumbbells (trade name "Die"). C ”, manufactured by Dumbbell Co., Ltd.) to prepare a test piece for measuring tear strength. The test piece was pulled by a Tencilon universal testing machine (trade name "RTG-1210", manufactured by A & D Co., Ltd.) at a tensile speed of 500 mm / min, and the tear strength (unit: N / mm) was measured. The measurement was performed on 5 test pieces, and the tear strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tear strength.
It can be judged that the higher the tear strength, the better the tear strength.
Further, it can be judged that the smaller the difference between the tear strength of the 24-hour aged product and the tear strength of the 72-hour aged product, the better the stability of the tear strength.
<製造例1>
(カルボキシ変性合成ポリイソプレンのラテックスの製造)
重量平均分子量が1,300,000である合成ポリイソプレン(商品名「NIPOL IR2200L」、日本ゼオン社製、イソプレンの単独重合体、シス結合単位量98%)をシクロヘキサンと混合し、攪拌しながら温度を60℃に昇温して溶解し、B形粘度計で測定した粘度が12,000mPa・sの合成ポリイソプレンのシクロヘキサン溶液(a)を調製した(固形分濃度8重量%)。 <Manufacturing example 1>
(Manufacture of latex of carboxy-modified synthetic polyisoprene)
Synthetic polyisoprene having a weight average molecular weight of 1,300,000 (trade name "NIPOL IR2200L", manufactured by Nippon Zeon Co., Ltd., isoprene homopolymer, cis bond unit amount 98%) is mixed with cyclohexane and heated while stirring. Was dissolved by raising the temperature to 60 ° C. to prepare a cyclohexane solution (a) of synthetic polyisoprene having a viscosity of 12,000 mPa · s measured by a B-type viscosity meter (solid content concentration: 8% by weight).
(カルボキシ変性合成ポリイソプレンのラテックスの製造)
重量平均分子量が1,300,000である合成ポリイソプレン(商品名「NIPOL IR2200L」、日本ゼオン社製、イソプレンの単独重合体、シス結合単位量98%)をシクロヘキサンと混合し、攪拌しながら温度を60℃に昇温して溶解し、B形粘度計で測定した粘度が12,000mPa・sの合成ポリイソプレンのシクロヘキサン溶液(a)を調製した(固形分濃度8重量%)。 <Manufacturing example 1>
(Manufacture of latex of carboxy-modified synthetic polyisoprene)
Synthetic polyisoprene having a weight average molecular weight of 1,300,000 (trade name "NIPOL IR2200L", manufactured by Nippon Zeon Co., Ltd., isoprene homopolymer, cis bond unit amount 98%) is mixed with cyclohexane and heated while stirring. Was dissolved by raising the temperature to 60 ° C. to prepare a cyclohexane solution (a) of synthetic polyisoprene having a viscosity of 12,000 mPa · s measured by a B-type viscosity meter (solid content concentration: 8% by weight).
一方、ロジン酸ナトリウム20部を水に添加し、温度を60℃に昇温して溶解し、濃度1.5重量%のアニオン性界面活性剤水溶液(b)を調整した。
On the other hand, 20 parts of sodium rosinate was added to water, the temperature was raised to 60 ° C. and dissolved to prepare an aqueous anionic surfactant solution (b) having a concentration of 1.5% by weight.
次に、上記シクロヘキサン溶液(a)と、上記アニオン性界面活性剤水溶液(b)とを、重量比で1:1.5となるように、ミキサー(商品名「マルチラインミキサーMS26-MMR-5.5L」、佐竹化学機械工業社製)を用いて混合し、続いて、乳化装置(商品名「マイルダーMDN310」、太平洋機工社製)を用いて、回転数4100rpmで混合及び乳化して、乳化液(c)を得た。なお、その際、シクロヘキサン溶液(a)とアニオン性界面活性剤水溶液(b)の合計のフィード流速は2,000kg/hr、温度は60℃、背圧(ゲージ圧)は0.5MPaとした。
Next, the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) are mixed in a mixer (trade name “Multiline Mixer MS26-MMR-5” so as to have a weight ratio of 1: 1.5. .5L ”, manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.), and then mixed and emulsified using an emulsifying device (trade name“ Milder MDN310 ”, manufactured by Pacific Kiko Co., Ltd.) at a rotation speed of 4100 rpm to emulsify. Liquid (c) was obtained. At that time, the total feed flow velocity of the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) was 2,000 kg / hr, the temperature was 60 ° C., and the back pressure (gauge pressure) was 0.5 MPa.
次いで、乳化液(c)を、-0.01~-0.09MPa(ゲージ圧)の減圧下で80℃に加温し、シクロヘキサンを留去し、合成ポリイソプレンの水分散液(d)を得た。その際、消泡剤(商品名「SM5515」、東レ・ダウコーニング社製)を、乳化液(c)中の合成ポリイソプレンに対して300重量ppmの量になるよう、噴霧しながら連続添加した。なお、シクロヘキサンを留去する際には、乳化液(c)がタンクの容積の70体積%以下になるように調整し、かつ、攪拌翼として3段の傾斜パドル翼を用い、60rpmでゆっくり攪拌を実施した。
Next, the emulsion (c) was heated to 80 ° C. under a reduced pressure of −0.01 to −0.09 MPa (gauge pressure), cyclohexane was distilled off, and an aqueous dispersion (d) of synthetic polyisoprene was added. Obtained. At that time, an antifoaming agent (trade name "SM5515", manufactured by Toray Dow Corning Co., Ltd.) was continuously added while spraying so as to have an amount of 300 ppm by weight based on the synthetic polyisoprene in the emulsion (c). .. When distilling off cyclohexane, the emulsion (c) is adjusted to be 70% by volume or less of the volume of the tank, and a three-stage inclined paddle blade is used as the stirring blade, and the mixture is slowly stirred at 60 rpm. Was carried out.
そして、シクロヘキサンの留去が完了した後、得られた合成ポリイソプレンの水分散液(d)を、連続遠心分離機(商品名「SRG510」、アルファラバル社製)を用いて、4,000~5,000Gで遠心分離し、軽液としての合成ポリイソプレンのラテックス(e)を得た。なお、遠心分離の条件は、遠心分離前の水分散液(d)の固形分濃度10重量%、連続遠心分離時の流速は1300kg/hr、遠心分離機の背圧(ゲージ圧)は1.5MPaとした。得られた合成ポリイソプレンのラテックス(e)は、固形分濃度が60重量%であった。
Then, after the distillation of cyclohexane is completed, the obtained aqueous dispersion (d) of synthetic polyisoprene is used in a continuous centrifuge (trade name "SRG510", manufactured by Alfa Laval) from 4,000 to Centrifugation at 5,000 G gave a latex (e) of synthetic polyisoprene as a light liquid. The conditions for centrifugation are as follows: the solid content concentration of the aqueous dispersion (d) before centrifugation is 10% by weight, the flow velocity during continuous centrifugation is 1300 kg / hr, and the back pressure (gauge pressure) of the centrifuge is 1. It was set to 5 MPa. The obtained synthetic polyisoprene latex (e) had a solid content concentration of 60% by weight.
次いで、得られた合成ポリイソプレンのラテックス(e)中の合成ポリイソプレン100部に対して、蒸留水130部を添加して希釈した。そして、合成ポリイソプレンのラテックス(e)に、合成ポリイソプレン100部に対して、分散剤としてのβ-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩(商品名「デモールT-45」、花王社製)0.8部を合成ポリイソプレン100部に対し4部の蒸留水で希釈したものを5分間かけて添加した。次いで、分散剤を添加した合成ポリイソプレンのラテックス(e)を、窒素置換された攪拌機付き反応容器に仕込み、撹拌しながら温度を30℃にまで加温した。また、別の容器を用い、カルボキシル基を有する単量体としてのメタクリル酸3部と蒸留水16部とを混合してメタクリル酸希釈液を調整した。このメタクリル酸希釈液を、30℃にまで加温した反応容器内に、30分間かけて添加した。
Next, 130 parts of distilled water was added to 100 parts of the synthetic polyisoprene in the latex (e) of the obtained synthetic polyisoprene to dilute it. Then, in the latex (e) of synthetic polyisoprene, a sodium salt of β-naphthalene sulfonic acid formalin condensate as a dispersant with respect to 100 parts of synthetic polyisoprene (trade name "Demor T-45", manufactured by Kao Co., Ltd.). 0.8 part was diluted with 4 parts of distilled water to 100 parts of synthetic polyisoprene and added over 5 minutes. Next, the latex (e) of synthetic polyisoprene to which a dispersant was added was charged into a reaction vessel equipped with a stirrer substituted with nitrogen, and the temperature was heated to 30 ° C. while stirring. Further, using another container, 3 parts of methacrylic acid as a monomer having a carboxyl group and 16 parts of distilled water were mixed to prepare a diluted methacrylic acid solution. This diluted methacrylic acid solution was added to a reaction vessel heated to 30 ° C. over 30 minutes.
さらに、別の容器を用い、蒸留水7部、ナトリウムホルムアルデヒドスルホキシレート(商品名「SFS」、三菱ガス化学社製)0.32部、硫酸第一鉄(商品名「フロストFe」、中部キレスト社製)0.01部からなる溶液(f)を調製した。この溶液(f)を反応容器内に移した後、1,1,3,3-テトラメチルブチルハイドロパーオキサイド(商品名「パーオクタH」、日本油脂社製)0.5部を添加して30℃で1時間反応させることで、カルボキシ変性合成ポリイソプレンのラテックスを得た。次いでカルボキシ変性合成ポリイソプレンを遠心分離機にて濃縮して固形分濃度55%の軽液を得た。そして、得られたカルボキシ変性合成ポリイソプレンのラテックスについて、上記方法にしたがってカルボキシル基を有する単量体による変性率を測定したところ、変性率は0.5重量%であった。
Furthermore, using another container, 7 parts of distilled water, 0.32 parts of sodium formaldehyde sulfoxylate (trade name "SFS", manufactured by Mitsubishi Gas Chemical Company), ferrous sulfate (trade name "Frost Fe", Chubu Killest) A solution (f) consisting of 0.01 parts was prepared. After transferring this solution (f) into a reaction vessel, 0.5 part of 1,1,3,3-tetramethylbutylhydroperoxide (trade name "Perocta H", manufactured by Nippon Oil & Fats Co., Ltd.) is added to 30 parts. By reacting at ° C. for 1 hour, a latex of carboxy-modified synthetic polyisoprene was obtained. Next, the carboxy-modified synthetic polyisoprene was concentrated with a centrifuge to obtain a light liquid having a solid content concentration of 55%. Then, with respect to the obtained latex of the carboxy-modified synthetic polyisoprene, the modification rate of the obtained monomer having a carboxyl group was measured according to the above method, and the modification rate was 0.5% by weight.
<製造例2>
(SISのラテックスの製造)
重量平均分子量が1,300,000である合成ポリイソプレンに代えて、SIS(商品名「Quintac 3620」、日本ゼオン社製)を使用した以外は、製造例1と同様にして、乳化液(c)としてのSISのラテックスを得た。得られたSISのラテックスの固形分濃度は60重量%であった。 <Manufacturing example 2>
(Manufacturing of SIS latex)
An emulsion (c) in the same manner as in Production Example 1 except that SIS (trade name "Quintac 3620", manufactured by Nippon Zeon Co., Ltd.) was used instead of synthetic polyisoprene having a weight average molecular weight of 1,300,000. ) As a latex of SIS. The solid content concentration of the obtained SIS latex was 60% by weight.
(SISのラテックスの製造)
重量平均分子量が1,300,000である合成ポリイソプレンに代えて、SIS(商品名「Quintac 3620」、日本ゼオン社製)を使用した以外は、製造例1と同様にして、乳化液(c)としてのSISのラテックスを得た。得られたSISのラテックスの固形分濃度は60重量%であった。 <Manufacturing example 2>
(Manufacturing of SIS latex)
An emulsion (c) in the same manner as in Production Example 1 except that SIS (trade name "Quintac 3620", manufactured by Nippon Zeon Co., Ltd.) was used instead of synthetic polyisoprene having a weight average molecular weight of 1,300,000. ) As a latex of SIS. The solid content concentration of the obtained SIS latex was 60% by weight.
<実施例1>
(キサントゲン化合物分散体の調製)
キサントゲン化合物としてのジイソプロピルキサントゲン酸亜鉛(商品名「ノクセラーZIX」、大内新興化学工業株式会社製、体積平均粒子径:14μm、95%体積累積径(D95):55μm)2.5部、ポリオキシアルキレン構造を有しないアニオン系界面活性剤としてのβ-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩(商品名「デモールT-45」、花王社製、重量平均分子量:7,000)0.22部、ノニオン系界面活性剤としてのポリオキシエチレンオレイルエーテル(商品名「エマルゲン404」、花王社製、数平均分子量(Mn):421)0.06部、および水4.5部を、ボールミル(商品名「磁製ボールミル」、日陶科学社製)により混合することで解砕処理を行うことで、キサントゲン化合物分散体を得た。なお、ボールミルによる、混合条件としては、φ15mmとφ20mmのセラミック磁製ボールを使用し、50rpmで72時間以上回転させた。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、レーザー回折散乱式粒度分布計(商品名「SALD-2300」、株式会社 島津製作所製)を使用して測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.1μmであり、95%体積累積径(D95)は3.8μmであった。 <Example 1>
(Preparation of xanthate compound dispersion)
Zinc diisopropylxanthogenate as a xanthogen compound (trade name "Noxeller ZIX", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., volume average particle size: 14 μm, 95% volume cumulative diameter (D95): 55 μm) 2.5 parts, polyoxy Sodium salt of β-naphthalene sulfonic acid formalin condensate as an anionic surfactant having no alkylene structure (trade name "Demor T-45", manufactured by Kao, weight average molecular weight: 7,000) 0.22 parts, 0.06 parts of polyoxyethylene oleyl ether as a nonionic surfactant (trade name "Emargen 404", manufactured by Kao, number average molecular weight (Mn): 421), and 4.5 parts of water, ball mill (trade name) A xanthate compound dispersion was obtained by crushing by mixing with a "porcelain ball mill" (manufactured by Nikko Kagaku Co., Ltd.). As the mixing conditions by the ball mill, ceramic porcelain balls of φ15 mm and φ20 mm were used, and the balls were rotated at 50 rpm for 72 hours or more. The volume average particle diameter and 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured by a laser diffraction scattering type particle size distribution meter (trade name "SALD-2300", manufactured by Shimadzu Corporation). ), The volume average particle size of zinc diisopropylxanthogenate was 2.1 μm, and the 95% volume cumulative diameter (D95) was 3.8 μm.
(キサントゲン化合物分散体の調製)
キサントゲン化合物としてのジイソプロピルキサントゲン酸亜鉛(商品名「ノクセラーZIX」、大内新興化学工業株式会社製、体積平均粒子径:14μm、95%体積累積径(D95):55μm)2.5部、ポリオキシアルキレン構造を有しないアニオン系界面活性剤としてのβ-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩(商品名「デモールT-45」、花王社製、重量平均分子量:7,000)0.22部、ノニオン系界面活性剤としてのポリオキシエチレンオレイルエーテル(商品名「エマルゲン404」、花王社製、数平均分子量(Mn):421)0.06部、および水4.5部を、ボールミル(商品名「磁製ボールミル」、日陶科学社製)により混合することで解砕処理を行うことで、キサントゲン化合物分散体を得た。なお、ボールミルによる、混合条件としては、φ15mmとφ20mmのセラミック磁製ボールを使用し、50rpmで72時間以上回転させた。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、レーザー回折散乱式粒度分布計(商品名「SALD-2300」、株式会社 島津製作所製)を使用して測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.1μmであり、95%体積累積径(D95)は3.8μmであった。 <Example 1>
(Preparation of xanthate compound dispersion)
Zinc diisopropylxanthogenate as a xanthogen compound (trade name "Noxeller ZIX", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., volume average particle size: 14 μm, 95% volume cumulative diameter (D95): 55 μm) 2.5 parts, polyoxy Sodium salt of β-naphthalene sulfonic acid formalin condensate as an anionic surfactant having no alkylene structure (trade name "Demor T-45", manufactured by Kao, weight average molecular weight: 7,000) 0.22 parts, 0.06 parts of polyoxyethylene oleyl ether as a nonionic surfactant (trade name "Emargen 404", manufactured by Kao, number average molecular weight (Mn): 421), and 4.5 parts of water, ball mill (trade name) A xanthate compound dispersion was obtained by crushing by mixing with a "porcelain ball mill" (manufactured by Nikko Kagaku Co., Ltd.). As the mixing conditions by the ball mill, ceramic porcelain balls of φ15 mm and φ20 mm were used, and the balls were rotated at 50 rpm for 72 hours or more. The volume average particle diameter and 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured by a laser diffraction scattering type particle size distribution meter (trade name "SALD-2300", manufactured by Shimadzu Corporation). ), The volume average particle size of zinc diisopropylxanthogenate was 2.1 μm, and the 95% volume cumulative diameter (D95) was 3.8 μm.
(ラテックス組成物の調製)
まず、スチレン-マレイン酸モノ-sec-ブチルエステル-マレイン酸モノメチルエステル重合体(商品名「Scripset550」、Hercules社製)を準備し、水酸化ナトリウムを用い、重合体中のカルボキシル基を100%中和することで、ナトリウム塩水溶液(濃度10重量%)を調製した。そして、このナトリウム塩水溶液を、製造例1で得られたカルボキシ変性合成ポリイソプレンのラテックスに、ラテックス中のカルボキシ変性合成ポリイソプレン100部に対して固形分換算で0.8部になるようにして添加し、混合物を得た。 (Preparation of latex composition)
First, a styrene-maleic acid mono-sec-butyl ester-maleic acid monomethyl ester polymer (trade name "Scripest550", manufactured by Hercules) was prepared, and sodium hydroxide was used to contain 100% of the carboxyl groups in the polymer. By adding, an aqueous sodium salt solution (concentration: 10% by weight) was prepared. Then, this aqueous sodium salt solution was added to the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1 so that the solid content was 0.8 parts with respect to 100 parts of the carboxy-modified synthetic polyisoprene in the latex. Addition gave a mixture.
まず、スチレン-マレイン酸モノ-sec-ブチルエステル-マレイン酸モノメチルエステル重合体(商品名「Scripset550」、Hercules社製)を準備し、水酸化ナトリウムを用い、重合体中のカルボキシル基を100%中和することで、ナトリウム塩水溶液(濃度10重量%)を調製した。そして、このナトリウム塩水溶液を、製造例1で得られたカルボキシ変性合成ポリイソプレンのラテックスに、ラテックス中のカルボキシ変性合成ポリイソプレン100部に対して固形分換算で0.8部になるようにして添加し、混合物を得た。 (Preparation of latex composition)
First, a styrene-maleic acid mono-sec-butyl ester-maleic acid monomethyl ester polymer (trade name "Scripest550", manufactured by Hercules) was prepared, and sodium hydroxide was used to contain 100% of the carboxyl groups in the polymer. By adding, an aqueous sodium salt solution (concentration: 10% by weight) was prepared. Then, this aqueous sodium salt solution was added to the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1 so that the solid content was 0.8 parts with respect to 100 parts of the carboxy-modified synthetic polyisoprene in the latex. Addition gave a mixture.
そして、得られた混合物を攪拌しながら、混合物中のカルボキシ変性合成ポリイソプレン100部に対して、ジイソプロピルキサントゲン酸亜鉛の添加量が2.5部となるように、上記にて調製したキサントゲン化合物分散体を添加した。
Then, while stirring the obtained mixture, the xanthogen compound dispersion prepared above so that the amount of zinc diisopropylxanthate added is 2.5 parts with respect to 100 parts of the carboxy-modified synthetic polyisoprene in the mixture. The body was added.
次いで、固形分換算で、酸化亜鉛1.5部、硫黄1.5部、老化防止剤(商品名「Wingstay L」、グッドイヤー社製)2部となるように、各配合剤の水分散液を添加して、ラテックス組成物を得た。そして、得られたラテックス組成物を、2分割し、一方については、25℃に調整された恒温水槽で24時間熟成(前加硫)を行い、他方については、25℃に調整された恒温水槽で72時間熟成(前加硫)を行うことで、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物を得た。
Next, the aqueous dispersion of each compounding agent was added so as to have 1.5 parts of zinc oxide, 1.5 parts of sulfur, and 2 parts of an antiaging agent (trade name "Wingstay L", manufactured by Goodyear Tire and Rubber Co., Ltd.) in terms of solid content. Addition gave a latex composition. Then, the obtained latex composition was divided into two, one of which was aged for 24 hours (pre-vulcanization) in a constant temperature water bath adjusted to 25 ° C., and the other was a constant temperature water tank adjusted to 25 ° C. By carrying out aging (pre-vulcanization) for 72 hours in the above, a 24-hour aged latex composition and a 72-hour aged latex composition were obtained.
(ディップ成形体の製造)
市販のセラミック製手型(シンコー社製)を洗浄し、70℃のオーブン内で予備加熱した後、18重量%の硝酸カルシウムおよび0.05重量%のポリオキシエチレンラウリルエーテル(商品名「エマルゲン109P」、花王社製)を含有する凝固剤水溶液に5秒間浸漬し、凝固剤水溶液から取り出した。次いで、手型を70℃のオーブン内で30分以上乾燥させることで、手型に凝固剤を付着させて、手型を凝固剤により被覆した。 (Manufacturing of dip molded body)
After washing a commercially available ceramic hand mold (manufactured by Shinko Co., Ltd.) and preheating it in an oven at 70 ° C., 18% by weight of calcium nitrate and 0.05% by weight of polyoxyethylene lauryl ether (trade name "Emargen 109P"). , Manufactured by Kao Corporation), immersed in a coagulant aqueous solution for 5 seconds, and removed from the coagulant aqueous solution. Next, the hand mold was dried in an oven at 70 ° C. for 30 minutes or more to attach a coagulant to the hand mold, and the hand mold was covered with the coagulant.
市販のセラミック製手型(シンコー社製)を洗浄し、70℃のオーブン内で予備加熱した後、18重量%の硝酸カルシウムおよび0.05重量%のポリオキシエチレンラウリルエーテル(商品名「エマルゲン109P」、花王社製)を含有する凝固剤水溶液に5秒間浸漬し、凝固剤水溶液から取り出した。次いで、手型を70℃のオーブン内で30分以上乾燥させることで、手型に凝固剤を付着させて、手型を凝固剤により被覆した。 (Manufacturing of dip molded body)
After washing a commercially available ceramic hand mold (manufactured by Shinko Co., Ltd.) and preheating it in an oven at 70 ° C., 18% by weight of calcium nitrate and 0.05% by weight of polyoxyethylene lauryl ether (trade name "Emargen 109P"). , Manufactured by Kao Corporation), immersed in a coagulant aqueous solution for 5 seconds, and removed from the coagulant aqueous solution. Next, the hand mold was dried in an oven at 70 ° C. for 30 minutes or more to attach a coagulant to the hand mold, and the hand mold was covered with the coagulant.
その後、凝固剤で被覆された手型を、オーブンから取り出し、上記にて得られた24時間熟成ラテックス組成物に10秒間浸漬した。次いで、この手型を、室温で10分間風乾してから、60℃の温水中に5分間浸漬して水溶性不純物を溶出させて、手型にディップ成形層を形成した。その後、手型に形成したディップ成形層を、オーブンにより温度130℃、30分間の条件で加熱することにより加硫させた後、室温まで冷却し、タルクを散布してから手型から剥離して、手袋形状のディップ成形体(24時間熟成品)を得た。また、24時間熟成ラテックス組成物に代えて、72時間熟成ラテックス組成物を使用した以外は、上記と同様にして、手袋形状のディップ成形体(72時間熟成品)を得た。そして、得られたディップ成形体(24時間熟成品および72時間熟成品)を用いて、上記方法にしたがって、引張強度および引裂強度の測定を行った。結果を表1に示す。
Then, the hand mold coated with the coagulant was taken out from the oven and immersed in the 24-hour aged latex composition obtained above for 10 seconds. Next, the hand mold was air-dried at room temperature for 10 minutes and then immersed in warm water at 60 ° C. for 5 minutes to elute water-soluble impurities to form a dip molding layer on the hand mold. Then, the dip-molded layer formed in the hand mold is vulcanized by heating it in an oven at a temperature of 130 ° C. for 30 minutes, cooled to room temperature, sprayed with talc, and then peeled off from the hand mold. , A glove-shaped dip molded product (aged for 24 hours) was obtained. Further, a glove-shaped dip molded product (72-hour aged product) was obtained in the same manner as above except that the 72-hour aged latex composition was used instead of the 24-hour aged latex composition. Then, using the obtained dip molded products (24-hour aged product and 72-hour aged product), the tensile strength and the tear strength were measured according to the above method. The results are shown in Table 1.
<実施例2>
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.14部とし、ポリオキシエチレンオレイルエーテルの使用量を0.14部とした以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.3μmであり、95%体積累積径(D95)は3.9μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 2>
Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the β-naphthalene sulfonic acid formalin condensate was 0.14 parts and the amount of the polyoxyethylene oleyl ether was 0.14 parts. I got a body. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 μm, and the 95% cumulative volume diameter (D95) was 3.9 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.14部とし、ポリオキシエチレンオレイルエーテルの使用量を0.14部とした以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.3μmであり、95%体積累積径(D95)は3.9μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 2>
Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the β-naphthalene sulfonic acid formalin condensate was 0.14 parts and the amount of the polyoxyethylene oleyl ether was 0.14 parts. I got a body. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 μm, and the 95% cumulative volume diameter (D95) was 3.9 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
<実施例3>
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.06部とし、ポリオキシエチレンオレイルエーテルの使用量を0.22部とした以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.8μmであり、95%体積累積径(D95)は4.4μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 3>
Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the β-naphthalene sulfonic acid formalin condensate was 0.06 part and the amount of the polyoxyethylene oleyl ether was 0.22 part. I got a body. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.8 μm, and the 95% cumulative volume diameter (D95) was 4.4 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.06部とし、ポリオキシエチレンオレイルエーテルの使用量を0.22部とした以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.8μmであり、95%体積累積径(D95)は4.4μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 3>
Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the β-naphthalene sulfonic acid formalin condensate was 0.06 part and the amount of the polyoxyethylene oleyl ether was 0.22 part. I got a body. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.8 μm, and the 95% cumulative volume diameter (D95) was 4.4 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
<実施例4>
ポリオキシエチレンオレイルエーテル0.06部に代えて、ポリオキシエチレンオクチルドデシルエーテル(商品名「エマルゲン2025G」、花王社製、数平均分子量(Mn):2450)0.06部を使用した以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.3μmであり、95%体積累積径(D95)は3.8μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 4>
Except for using 0.06 parts of polyoxyethylene octyldodecyl ether (trade name "Emargen 2025G", manufactured by Kao Corporation, number average molecular weight (Mn): 2450) instead of 0.06 parts of polyoxyethylene oleyl ether. A xanthogen compound dispersion was obtained in the same manner as in Example 1. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 μm, and the 95% cumulative volume diameter (D95) was 3.8 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
ポリオキシエチレンオレイルエーテル0.06部に代えて、ポリオキシエチレンオクチルドデシルエーテル(商品名「エマルゲン2025G」、花王社製、数平均分子量(Mn):2450)0.06部を使用した以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.3μmであり、95%体積累積径(D95)は3.8μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 4>
Except for using 0.06 parts of polyoxyethylene octyldodecyl ether (trade name "Emargen 2025G", manufactured by Kao Corporation, number average molecular weight (Mn): 2450) instead of 0.06 parts of polyoxyethylene oleyl ether. A xanthogen compound dispersion was obtained in the same manner as in Example 1. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 μm, and the 95% cumulative volume diameter (D95) was 3.8 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
<実施例5>
製造例1で得られたカルボキシ変性合成ポリイソプレンのラテックスに代えて、製造例2で得られたSISのラテックスを使用した以外は、実施例4と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 5>
The 24-hour aged latex composition and the latex aged in the same manner as in Example 4 except that the latex of SIS obtained in Production Example 2 was used instead of the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1. A 72-hour aged latex composition and a dip molded product (24-hour aged product and 72-hour aged product) were obtained and measured in the same manner. The results are shown in Table 1.
製造例1で得られたカルボキシ変性合成ポリイソプレンのラテックスに代えて、製造例2で得られたSISのラテックスを使用した以外は、実施例4と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Example 5>
The 24-hour aged latex composition and the latex aged in the same manner as in Example 4 except that the latex of SIS obtained in Production Example 2 was used instead of the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1. A 72-hour aged latex composition and a dip molded product (24-hour aged product and 72-hour aged product) were obtained and measured in the same manner. The results are shown in Table 1.
<比較例1>
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.28部とし、ポリオキシエチレンオレイルエーテルを使用しない以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.1μmであり、95%体積累積径(D95)は3.8μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Comparative example 1>
A xanthogen compound dispersion was obtained in the same manner as in Example 1 except that the sodium salt of the β-naphthalene sulfonic acid formalin condensate was used in an amount of 0.28 parts and polyoxyethylene oleyl ether was not used. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.1 μm and the 95% cumulative volume diameter (D95) was 3.8 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩の使用量を0.28部とし、ポリオキシエチレンオレイルエーテルを使用しない以外は、実施例1と同様にして、キサントゲン化合物分散体を得た。得られたキサントゲン化合物分散体中のジイソプロピルキサントゲン酸亜鉛の体積平均粒子径および95%体積累積径(D95)を、実施例1と同様にして測定したところ、ジイソプロピルキサントゲン酸亜鉛の体積平均粒子径は2.1μmであり、95%体積累積径(D95)は3.8μmであった。
そして、得られたキサントゲン化合物分散体を使用した以外は、実施例1と同様にして、24時間熟成ラテックス組成物、および72時間熟成ラテックス組成物、ならびにディップ成形体(24時間熟成品および72時間熟成品)を得て、同様に測定を行った。結果を表1に示す。 <Comparative example 1>
A xanthogen compound dispersion was obtained in the same manner as in Example 1 except that the sodium salt of the β-naphthalene sulfonic acid formalin condensate was used in an amount of 0.28 parts and polyoxyethylene oleyl ether was not used. When the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.1 μm and the 95% cumulative volume diameter (D95) was 3.8 μm.
Then, in the same manner as in Example 1, a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
表1に示すように、キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有するキサントゲン化合物分散体を加硫促進剤として用いることにより、遅延型アレルギー(Type IV)の症状の発生原因となる加硫促進剤(たとえば、チウラム系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤、チアゾール系加硫促進剤など)を使用することなく、加硫物を得ることができ、即時型アレルギー(Type I)に加えて遅延型アレルギー(Type IV)の症状の発生を抑制可能であった。さらに、得られるディップ成形体は、引張強度および引裂強度に優れ、かつ、引張強度および引裂強度の安定性に優れたものであった。
また、上記のキサントゲン化合物分散体によれば、得られるラテックス組成物を24時間熟成してからディップ成形体の生産を開始し、熟成条件を保ったまま、さらに48時間以上、ディップ成形体の生産を継続して行った場合であっても、引張強度および引裂強度に優れるディップ成形体を安定して生産することができるものであった。すなわち、得られるラテックス組成物は熟成安定性に優れるものであった(実施例1~5)。 As shown in Table 1, a xanthate compound dispersion containing a xanthogen compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol is used as a vulcanization accelerator. By using, a vulcanization accelerator (for example, thiuram-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator, thiazole-based vulcanization accelerator, etc.) that causes the occurrence of delayed allergy (Type IV) symptoms can be used. A vulcanized product could be obtained without use, and it was possible to suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I). Further, the obtained dip molded product was excellent in tensile strength and tear strength, and was also excellent in stability of tensile strength and tear strength.
Further, according to the above-mentioned xanthogen compound dispersion, the obtained latex composition is aged for 24 hours before the production of the dip molded product is started, and the production of the dip molded product is continued for 48 hours or more while maintaining the aging conditions. Even when the above was continuously performed, it was possible to stably produce a dip molded product having excellent tensile strength and tear strength. That is, the obtained latex composition was excellent in aging stability (Examples 1 to 5).
また、上記のキサントゲン化合物分散体によれば、得られるラテックス組成物を24時間熟成してからディップ成形体の生産を開始し、熟成条件を保ったまま、さらに48時間以上、ディップ成形体の生産を継続して行った場合であっても、引張強度および引裂強度に優れるディップ成形体を安定して生産することができるものであった。すなわち、得られるラテックス組成物は熟成安定性に優れるものであった(実施例1~5)。 As shown in Table 1, a xanthate compound dispersion containing a xanthogen compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol is used as a vulcanization accelerator. By using, a vulcanization accelerator (for example, thiuram-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator, thiazole-based vulcanization accelerator, etc.) that causes the occurrence of delayed allergy (Type IV) symptoms can be used. A vulcanized product could be obtained without use, and it was possible to suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I). Further, the obtained dip molded product was excellent in tensile strength and tear strength, and was also excellent in stability of tensile strength and tear strength.
Further, according to the above-mentioned xanthogen compound dispersion, the obtained latex composition is aged for 24 hours before the production of the dip molded product is started, and the production of the dip molded product is continued for 48 hours or more while maintaining the aging conditions. Even when the above was continuously performed, it was possible to stably produce a dip molded product having excellent tensile strength and tear strength. That is, the obtained latex composition was excellent in aging stability (Examples 1 to 5).
一方、ノニオン系界面活性剤を含有しないキサントゲン化合物分散体を使用した場合には、得られるディップ成形体は、引張強度および引裂強度の安定性に劣るものであった(比較例1)。
On the other hand, when a xanthate compound dispersion containing no nonionic surfactant was used, the obtained dip molded product was inferior in stability of tensile strength and tear strength (Comparative Example 1).
Claims (10)
- キサントゲン化合物と、ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、ノニオン系界面活性剤と、水またはアルコールと、を含有するキサントゲン化合物分散体。 A xanthate compound dispersion containing a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
- 前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤と、前記ノニオン系界面活性剤との比率が、「ポリオキシアルキレン構造を有しないアニオン系界面活性剤:ノニオン系界面活性剤」の重量比で、99:1~10:90である請求項1に記載のキサントゲン化合物分散体。 The ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant is the weight ratio of "anionic surfactant having no polyoxyalkylene structure: nonionic surfactant". , 99: 1-10: 90. The xanthogen compound dispersion according to claim 1.
- 前記ポリオキシアルキレン構造を有しないアニオン系界面活性剤が、芳香族化合物である請求項1または2に記載のキサントゲン化合物分散体。 The xanthate compound dispersion according to claim 1 or 2, wherein the anionic surfactant having no polyoxyalkylene structure is an aromatic compound.
- 前記ノニオン系界面活性剤の数平均分子量が、100~5,000である請求項1~3のいずれかに記載のキサントゲン化合物分散体。 The xanthate compound dispersion according to any one of claims 1 to 3, wherein the nonionic surfactant has a number average molecular weight of 100 to 5,000.
- 共役ジエン系重合体のラテックスと、加硫剤と、請求項1~4のいずれかに記載のキサントゲン化合物分散と、を含有する共役ジエン系重合体ラテックス組成物。 A conjugated diene polymer latex composition containing a latex of a conjugated diene polymer, a vulcanizing agent, and the xanthogen compound dispersion according to any one of claims 1 to 4.
- さらに、金属酸化物および/または典型金属化合物を含む請求項5に記載の共役ジエン系重合体ラテックス組成物。 The conjugated diene polymer latex composition according to claim 5, further comprising a metal oxide and / or a typical metal compound.
- 前記共役ジエン系重合体が、合成ポリイソプレン、スチレン-イソプレン-スチレンブロック共重合体、または蛋白質を除去した天然ゴムである請求項5または6に記載の共役ジエン系重合体ラテックス組成物。 The conjugated diene polymer latex composition according to claim 5 or 6, wherein the conjugated diene polymer is a synthetic polyisoprene, a styrene-isoprene-styrene block copolymer, or a natural rubber from which a protein has been removed.
- 請求項5~7のいずれかに記載の共役ジエン系重合体ラテックス組成物からなる膜成形体。 A film molded product made of the conjugated diene polymer latex composition according to any one of claims 5 to 7.
- 請求項5~7のいずれかに記載の共役ジエン系重合体ラテックス組成物からなるディップ成形体。 A dip molded product made of the conjugated diene polymer latex composition according to any one of claims 5 to 7.
- 請求項5~7のいずれかに記載の共役ジエン系重合体ラテックス組成物からなる接着剤組成物。 An adhesive composition comprising the conjugated diene polymer latex composition according to any one of claims 5 to 7.
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WO2018155243A1 (en) * | 2017-02-22 | 2018-08-30 | 日本ゼオン株式会社 | Latex composition |
WO2019003744A1 (en) * | 2017-06-30 | 2019-01-03 | 日本ゼオン株式会社 | Film molded body |
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WO2018143159A1 (en) * | 2017-02-01 | 2018-08-09 | デンカ株式会社 | Chloroprene-based polymer latex composition, mixed latex composition using same, and use thereof |
WO2018155243A1 (en) * | 2017-02-22 | 2018-08-30 | 日本ゼオン株式会社 | Latex composition |
WO2019003744A1 (en) * | 2017-06-30 | 2019-01-03 | 日本ゼオン株式会社 | Film molded body |
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