WO2023238748A1 - Polychloroprene latex adhesive - Google Patents
Polychloroprene latex adhesive Download PDFInfo
- Publication number
- WO2023238748A1 WO2023238748A1 PCT/JP2023/020265 JP2023020265W WO2023238748A1 WO 2023238748 A1 WO2023238748 A1 WO 2023238748A1 JP 2023020265 W JP2023020265 W JP 2023020265W WO 2023238748 A1 WO2023238748 A1 WO 2023238748A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- adhesive
- parts
- chloroprene
- chloroprene polymer
- Prior art date
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 138
- 239000004816 latex Substances 0.000 title claims abstract description 138
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 128
- 239000000853 adhesive Substances 0.000 title claims abstract description 125
- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 68
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims abstract description 114
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- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 44
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- 239000000178 monomer Substances 0.000 description 35
- 238000006116 polymerization reaction Methods 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- -1 nonionic Chemical group 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 13
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- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
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- 238000004108 freeze drying Methods 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
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- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-M 9,10-dioxoanthracene-1-sulfonate Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] JAJIPIAHCFBEPI-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
- C09J111/02—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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
Definitions
- the present invention relates to polychloroprene latex adhesives.
- Polychloroprene latex is used in civil engineering, construction, plywood, furniture, shoes, water-based adhesives such as wet suits, work gloves, laboratory gloves, medical gloves, dip molded products such as balloons, waterproof coatings for civil engineering, construction, etc. It is used in various fields.
- water-based adhesives polychloroprene latex adhesives
- polychloroprene latex adhesives are highly safe because they are water-based, and are being actively investigated for various uses due to their wide adaptability to adherends and well-balanced adhesive properties. There is.
- Polyolefin resin has water resistance, chemical resistance, light weight, and toughness, so it is widely used as a material for various molded products such as automobile interior materials, electrical insulation materials, and daily goods. It is extremely difficult to adhere to materials such as those that have no polar groups on their surfaces and have low polarizability. Furthermore, if polyolefin resin or the like cannot be bonded, there are problems such as the products and manufacturing processes to which polychloroprene latex adhesives can be applied are severely limited.
- a polychloroprene latex adhesive is applied to both adherends to be joined, and these adhesive layers are dried and then laminated together, thereby exhibiting high adhesiveness immediately after lamination. Due to these characteristics, it is expected to be used as a water-based contact adhesive, but since it requires drying time, it takes time to bond after applying the adhesive, and it is difficult to shorten the drying time. However, there were issues such as the need for special drying equipment, which led to increased costs.
- a chloroprene rubber latex adhesive composition in which a chlorinated polyolefin resin emulsion is added to a chloroprene polymer latex is known as a means for improving adhesiveness with a polyolefin resin (for example, see Patent Document 1).
- the present invention provides a polychloroprene latex adhesive that shortens the drying time of the adhesive layer when using the adhesive, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. The task is to do so.
- the chlorinated polyolefin resin emulsion (b) is 1 to 20 parts by mass in terms of solid content. 1 to 100 parts by mass of the tackifying resin emulsion (C) in terms of solid content, and 0.1 to 30 parts by mass of the pH adjuster (d) in terms of solid content, according to [1].
- Polychloroprene latex adhesive is 100 parts by mass in terms of solid content.
- the plasticizer (e) is contained in an amount of 0.1 to 100 parts by mass in terms of solid content [1] or [2] Polychloroprene latex adhesive as described in. [4] The polychloroprene latex adhesive according to any one of [1] to [3], wherein at least one of the adherends is a polyolefin resin.
- the polychloroprene latex adhesive when using an adhesive, shortens the drying time of the adhesive layer, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. is obtained.
- the polychloroprene latex adhesive of the present invention is particularly suitable for use as a spray type adhesive used for adhering polyolefin resins and polyurethane foams.
- the long drying time and heat drying that were conventionally required are not essential, so the work process can be shortened and energy and costs can be reduced. It is possible to simplify the equipment.
- the polychloroprene latex adhesive according to the present invention includes a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d).
- a chloroprene polymer latex a
- b chlorinated polyolefin resin emulsion
- c tackifier resin emulsion
- a pH adjuster a pH adjuster
- Chloroprene polymer latex includes a chloroprene polymer.
- the chloroprene polymer in the present invention means a polymer containing a monomer unit derived from 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene monomer), and includes a homopolymer of chloroprene monomer, It also includes a copolymer containing a monomer unit derived from a chloroprene monomer and another monomer copolymerizable with the chloroprene monomer.
- Other monomers include 1-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, sulfur, acrylic acid and its esters, methacrylic acid and Examples include esters thereof.
- the chloroprene polymer latex according to one embodiment of the present invention preferably contains 60 to 100% by mass of chloroprene monomer units when the chloroprene polymer contained in the chloroprene polymer latex is 100% by mass.
- the content of the chloroprene monomer unit is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 99, 100% by mass, and within the range between any two of the numerical values exemplified here. It may be.
- the chloroprene polymer latex according to one embodiment of the present invention may also contain a monomer unit derived from ethylenically unsaturated carboxylic acid, and when the chloroprene polymer contained in the chloroprene polymer latex is 100% by mass.
- the content of monomer units derived from ethylenically unsaturated carboxylic acid can be 0 parts by mass or more and less than 2.0 parts by mass.
- the content of monomer units derived from ethylenically unsaturated carboxylic acid is, for example, 0 parts by mass, 0.1 parts by mass, less than 0.2 parts by mass, 0.2 parts by mass, 0.3 parts by mass, 0 parts by mass, less than .4 parts by mass, 0.4 parts by mass, 0.5 parts by mass, 0.8 parts by mass, 1.0 parts by mass, 1.5 parts by mass, less than 2.0 parts by mass, and the numerical values exemplified here. It may be within the range between any two.
- the chloroprene polymer latex according to one embodiment of the present invention may not contain a chloroprene polymer containing monomer units derived from ethylenically unsaturated carboxylic acid.
- the chloroprene polymer latex according to one embodiment of the present invention may include one type of chloroprene polymer, or may include two or more types of chloroprene polymers.
- the chloroprene polymer latex according to an embodiment of the present invention contains two or more types of chloroprene polymers, the total content of each monomer unit contained in the two or more types of chloroprene polymers contained in the chloroprene polymer latex. It is preferable that the ratio is within the above numerical range.
- the chloroprene polymer latex according to one embodiment of the present invention preferably includes a homopolymer of chloroprene monomers.
- the chloroprene polymer latex according to one embodiment of the present invention has a solid content of a homopolymer of chloroprene monomer, based on 100% by mass of the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive.
- the content is preferably more than 50% by mass and 100% by mass or less, more preferably more than 80% by mass and 100% by mass or less, and preferably more than 90% by mass and 100% by mass or less.
- the content of the homopolymer of chloroprene monomer is, for example, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and is between any two of the values exemplified here. may be within the range of
- the chloroprene polymer latex according to an embodiment of the present invention may also contain a carboxy-modified chloroprene copolymer, and the chloroprene polymer latex based on the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive has a carboxy
- the modified chloroprene copolymer can be contained in an amount of 0 mass % or more and less than 50 mass %, and can be contained in a solid content of 0 mass % or more and less than 20 mass %, or 0 mass % or more and less than 10 parts by mass.
- the content of the carboxy-modified chloroprene copolymer is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45% by mass, less than 50% by mass, and any of the values exemplified here or within a range between the two.
- the chloroprene polymer latex according to one embodiment of the present invention may not contain a carboxy-modified chloroprene copolymer.
- the chloroprene polymer latex according to the present invention includes a chloroprene polymer, and the chloroprene polymer has a toluene insoluble content of 20% by mass or less. That is, the chloroprene polymer latex according to the present invention has a toluene insoluble content of 20% by mass or less.
- the toluene-insoluble content refers to the content of gel components insoluble in toluene solvent in the chloroprene polymer.
- sol refers to a component soluble in toluene solvent.
- the excellent initial adhesive strength in the present invention is achieved because the chloroprene polymer contains a large amount of sol having excellent molecular mobility. Therefore, fusion of the chloroprene polymer molecular chains at the adhesive interface occurs quickly, adhesive strength is instantaneously developed, and excellent initial adhesive strength can be developed.
- the toluene insoluble content is more preferably 10% by mass or less, for example, 0% by mass, 1% by mass, 2% by mass, 3% by mass, 4% by mass, 5% by mass, 6% by mass, 7% by mass, Less than 8% by mass, 8% by mass, 10% by mass, 12% by mass, 14% by mass, 16% by mass, 18% by mass, 20% by mass, and within the range between any two of the numerical values exemplified here. There may be. If the toluene-insoluble content of the chloroprene polymer exceeds 20% by mass, this initial adhesive strength will decrease, which is not preferable.
- the toluene insoluble content can be controlled by adjusting the polymerization conditions, such as the type and amount of the polymerization initiator and chain transfer agent, as well as the polymerization temperature, polymerization time, and polymerization rate, during the production of chloroprene polymer latex. can do.
- the polymerization conditions such as the type and amount of the polymerization initiator and chain transfer agent, as well as the polymerization temperature, polymerization time, and polymerization rate, during the production of chloroprene polymer latex. can do.
- the toluene-insoluble matter is the toluene-insoluble matter contained in the two or more kinds of chloroprene polymers (the toluene-insoluble matter contained in the two or more kinds of chloroprene polymers). It is preferable that the toluene-insoluble content of the mixture is within the above numerical range.
- the method for producing the chloroprene polymer latex according to the present invention is not particularly limited, it can be produced by the following method.
- the method for producing a chloroprene polymer latex according to an embodiment of the present invention may include an emulsion polymerization step, and in the emulsion polymerization step, a chloroprene monomer, or a chloroprene monomer and other materials copolymerizable therewith are used.
- These monomers are subjected to emulsion polymerization using appropriate emulsifiers, dispersants, polymerization initiators, chain transfer agents, etc., and when the desired polymerization rate is reached, a polymerization terminator is added to form a chloroprene-based polymer latex. can be obtained. Furthermore, unreacted monomers can be removed from the chloroprene polymer latex thus obtained by a steam flash method, a concentration method, or the like.
- the emulsifier is not particularly limited, and known anionic, nonionic, and cationic emulsifiers used in the polymerization of chloroprene polymers can be used.
- the emulsifier preferably contains one or more selected from rosin acid or an alkali metal salt thereof.
- rosin acid any of wood rosin acid, gum rosin acid, tall oil rosin acid, or disproportionated rosin acid obtained by disproportionation of these can be used.
- rosin acid or an alkali metal salt thereof is used as an emulsifier, the emulsion stability of the chloroprene polymer latex easily decreases when mechanical stimulation is applied. Therefore, when the chloroprene polymer latex is used as an adhesive, excellent initial adhesive strength can be exhibited.
- rosin acid When using rosin acid as an emulsifier, it is more preferable to add its alkali metal salt from the viewpoint of polymerization control and initial adhesive performance, particularly adhesive performance in a wet state.
- alkali metal salt examples include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
- sodium hydroxide and potassium hydroxide are preferred from the viewpoint of cost, water solubility, and the like.
- the amount of rosin acid added is preferably 0.5 to 10 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the total monomers used.
- anionic emulsifiers and dispersants other than rosin acid can also be used, and examples of anionic emulsifiers and dispersants other than rosin acid include alkyl sulfonates and alkylaryl sulfates having 8 to 20 carbon atoms. , a condensate of sodium naphthalene sulfonate and formaldehyde, and sodium alkyl diphenyl ether disulfonate.
- a nonionic emulsifier or dispersant may be used in combination.
- the combined use of a nonionic emulsifier can improve the low-temperature stability of the chloroprene polymer latex and its adhesive properties when used as an adhesive.
- Chain transfer agent During emulsion polymerization of chloroprene monomers, a chain transfer agent can be added to adjust the molecular weight, molecular weight distribution, and toluene-insoluble content of the chloroprene polymer.
- the chain transfer agent may be added at the beginning of the polymerization or during the polymerization.
- Chain transfer agents include long chain alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, and dialkyl xanthogen disulfides such as diisopropyl xanthogen disulfide and diethyl xanthogen disulfide.
- long-chain alkyl mercaptans From the viewpoint of easy control of molecular weight and gel content, it is preferable to use long-chain alkyl mercaptans.
- One type of these chain transfer agents may be used, or two or more types may be used in combination.
- the amount of the chain transfer agent added can be 0.001 to 1 part by weight based on 100 parts by weight of the total monomers.
- Polymerization initiator As the initiator for emulsion polymerization, ordinary radical polymerization initiators can be used, and specifically, organic or inorganic peroxides such as benzoyl peroxide, potassium persulfate, ammonium persulfate, azobisisobutylene, etc. Azo compounds such as lonitrile are used. A co-catalyst such as anthraquinone sulfonate, potassium sulfite, or sodium sulfite may be used in combination as appropriate.
- organic or inorganic peroxides such as benzoyl peroxide, potassium persulfate, ammonium persulfate, azobisisobutylene, etc. Azo compounds such as lonitrile are used.
- a co-catalyst such as anthraquinone sulfonate, potassium sulfite, or sodium sulfite may be used in combination as appropriate.
- sodium hydroxide and/or potassium hydroxide can be used in the emulsion polymerization step.
- the amount of sodium hydroxide and potassium hydroxide added can be 0.01 to 2.0 parts by weight per 100 parts by weight of the monomer.
- the polymerization conversion rate of the chloroprene monomer is preferably 50% by mass or more and less than 90% by mass, more preferably 60 to 85% by mass. If the polymerization conversion rate of the chloroprene monomer is less than 50%, the solid content of the chloroprene polymer latex will decrease, which will put a burden on the drying process after applying the adhesive and make it difficult to make the adhesive layer uniform. In addition, residual chloroprene monomers may cause problems such as odor and deterioration of adhesive strength.
- the polymerization conversion rate is 90% by mass or more, branching increases in the chloroprene polymer and the molecular weight increases, resulting in a broadened molecular weight distribution, which deteriorates contact properties and water resistance, which are important performances in the present invention. may occur.
- the polymerization conversion rate (mass %) is determined by [(polymer mass/total monomer mass) ⁇ 100].
- the chloroprene polymer can be polymerized at a temperature in the range of 0 to 45°C, but it is particularly preferable to polymerize at a low temperature of 5 to 15°C. It is known that trans-1,4-bonds account for 85% or more of a chloroprene homopolymer, and its molecular structure is relatively highly regular. Chloroprene homopolymer has typical crystalline polymer properties due to its highly regular molecular structure.
- the ratio of trans-1,4-bonds in the polychloroprene molecule is further increased, making it possible to obtain a chloroprene homopolymer with a higher crystallization rate. Sufficient adhesive strength is achieved when this is used as an adhesive.
- Polymerization terminator In the production of a chloroprene polymer, a polymerization terminator is added to stop the reaction when a predetermined polymerization rate is reached, in order to obtain a polymer with a desired molecular weight and distribution.
- the polymerization terminator include phenothiazine, pt-butylcatechol, hydroquinone, hydroquinone monomethyl ether, and diethylhydroxylamine.
- the solid content concentration of the chloroprene polymer latex is not particularly limited, but is usually 40 to 65% by mass.
- Chlorinated polyolefin resin emulsion (b)
- the chlorinated polyolefin resin emulsion is a resin emulsion obtained by chlorinating a polyolefin resin.
- the chlorinated polyolefin resin emulsion is a component for imparting adhesive properties of the polychloroprene latex adhesive to the polyolefin resin.
- the amount of the chlorinated polyolefin resin emulsion added is not particularly limited, but from the viewpoint of adhesion to the polyolefin resin, the solid content of the chlorinated polyolefin resin emulsion should be set to 100 parts by mass in terms of solid content of the chloroprene polymer latex. It is preferable to use 1 to 20 parts by mass in terms of solid content, and more preferably 3 to 15 parts by mass in terms of solid content.
- the amount of the chlorinated polyolefin resin emulsion added is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 in terms of solid content. , 18, 19, and 20 parts by mass, and may be within a range between any two of the numerical values exemplified here.
- the polyolefin in the chlorinated polyolefin resin is not particularly limited, but includes polyethylene, polypropylene, ethylene-propylene copolymer resin, ethylene-butene copolymer resin, propylene-butene copolymer resin, ethylene-propylene-butene copolymer resin, and ethylene-propylene. -diene copolymer resins, etc., with propylene-butene copolymer resins and ethylene-propylene-butene copolymer resins being preferred.
- the chlorine content of the chlorinated polyolefin resin emulsion is not particularly limited, but is preferably 10 to 40% by mass. By setting the chlorine content to 10% by mass or more, the compatibility with the chloroprene polymer latex can be improved. Further, by setting the chlorine content to 40% by mass or less, it is possible to prevent a decrease in adhesiveness with an adherend such as a polyolefin resin.
- the chlorine content is, for example, 10, 15, 20, 25, 30, 35, 39, 40% by mass, and may be within a range between any two of the numerical values exemplified here.
- the chlorinated polyolefin resin is preferably chlorinated and acid-modified, more preferably maleic anhydride-modified.
- Surfactants may be added to the chlorinated polyolefin resin emulsion within a range that does not impair the effects of the present invention, such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Examples include agents.
- a nonionic surfactant may be used from the viewpoint of improving the storage stability of the resulting polychloroprene latex adhesive.
- chlorinated polyolefin resin emulsions include EW-5303 and EH-801 manufactured by Toyobo Co., Ltd.
- Tackifying resin emulsion (c) The tackifying resin emulsion is added to improve the initial adhesive strength of the chloroprene polymer latex adhesive. In particular, the adhesiveness can be improved when a polyolefin resin is used as the adherend.
- the amount of the tackifier resin emulsion added is not particularly limited, but from the viewpoint of adhesion to the adherend, it is 1 to 100 parts by weight in terms of solid content per 100 parts by mass in terms of solid content of the chloroprene polymer latex. It is preferable to use parts by mass, and more preferably 20 to 70 parts by mass in terms of solid content.
- the amount of the tackifying resin emulsion added is, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 parts by mass, and is in the range between any two of the numerical values exemplified here. It may be within.
- the type of tackifier resin is not particularly limited, but includes rosin-based resins such as gum rosin, tall rosin, wood rosin, symmetrical rosin, polymerized rosin, glycerin esters and pentaerythritol esters of these rosins, and hydrogenated products thereof; Terpene phenol resins such as hydrogenated products of terpene phenol resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, dicyclopentadiene petroleum resins Pure monomer petroleum resins , these hydrogenated products include petroleum resins, styrene resins, coumaron indene resins, alkylphenol resins, xylene resins, dammar, copal, shellac, etc., and phenols such as terpene phenol resins and alkylphenol resins. It is preferable that a resin is included, and it is more preferable that a terpen
- tackifying resin emulsions include Tamanol E-100 and Tamanol E-200NT manufactured by Arakawa Chemical Industries, Ltd., which are terpene phenol resin emulsions.
- the pH adjuster is added to improve the initial adhesive strength and storage stability of the chloroprene polymer latex.
- weak acids and buffers can be used, and examples thereof include hydroxy acids such as citric acid and glycolic acid, boric acid, and amino acids, and it is desirable to include at least one compound selected from amino acids.
- amino acids include glycine, alanine, threonine, and proline. It is more preferable to use glycine, which is a type of amino acid, in terms of cost, adhesive performance, ease of handling, etc.
- the amount of the pH adjuster added is not particularly limited, but it is preferable to use an amount that can adjust the pH of the chloroprene rubber latex adhesive composition to a range of 7 to 10. More preferably, the pH range is adjusted to 8-10.
- glycine When using glycine as a pH adjuster, it is preferably 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 2 to 16 parts by weight, based on 100 parts by weight of the chloroprene polymer latex. %, more preferably from 3 to 13 parts by weight, sufficient adhesive strength can be developed at an advantageous cost.
- the amount of the pH adjuster added is, for example, 0.1, 1, 2, 3, 5, 10, 15, 20, 25, 30 parts by mass, and within the range between any two of the numerical values exemplified here. It may be.
- Plasticizer (e) Polychloroprene latex adhesives may also contain plasticizers.
- the amount of the plasticizer added can be 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the solid content of the chloroprene polymer latex. It is.
- the amount of plasticizer added is, for example, 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 parts by mass, and is between any two of the numerical values exemplified here. may be within the range of By adding a plasticizer, the initial strength of the resulting polychloroprene latex adhesive can be improved, and the texture of the adhesive film after drying can be softened.
- the plasticizer is preferably one that has good compatibility with the chloroprene polymer, and is not particularly limited, but examples include dibutyl sebacate, dibutyl phthalate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, dioctyl phthalate, and Examples include cresyl phosphate and cresyl diphenyl phosphate.
- Polychloroprene latex adhesives are generally susceptible to oxygen degradation.
- stabilizers such as antioxidants can be used as appropriate within a range that does not impair the effects of the invention.
- the amount of antioxidant added to the polychloroprene latex adhesive is preferably 0.1 to 3 parts by mass in terms of solid content per 100 parts by mass of solid content of the chloroprene polymer latex. By setting it within this range, the stability over time of the flexibility of the resulting adhesive can be improved.
- the antioxidant is insoluble in water or destabilizes the emulsified state of the chloroprene polymer latex, it is preferable to prepare an aqueous dispersion in advance and then add it.
- the polychloroprene latex adhesive according to one embodiment of the invention may be antioxidant-free.
- a polychloroprene latex adhesive according to one embodiment of the invention may include polyvinyl alcohol.
- the content of polyvinyl alcohol can be 2% by mass or less, and can be less than 2% by mass, based on 100% by mass of the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive.
- the content of polyvinyl alcohol is, for example, 0, 0.5, 1.0, 1.5, 1.9, 2.0 parts by mass, and within the range between any two of the numerical values exemplified here. There may be.
- the polychloroprene latex adhesive according to one embodiment of the present invention is obtained by controlling the content of polyvinyl alcohol to a certain value or less, or by not containing polyvinyl alcohol. It is also possible to improve initial adhesion.
- the polychloroprene latex adhesive according to an embodiment of the present invention may include other resin emulsions ( latex) may be added as an adjunct.
- resin emulsions (latex) include resin emulsions such as (modified) vinyl acetate, vinyl acetate/acrylic mixture, acrylic/styrene mixture, and urethane.
- the amount of the other resin emulsion (latex) can be 30% by mass or less (in terms of solid content) based on 100% by mass of the solid content of the polychloroprene latex adhesive, for example, 0, 5, 10, The content may be 15, 20, 25, or 30% by mass, and may be within a range between any two of the numerical values exemplified here.
- the polychloroprene latex adhesive contains a resin emulsion (latex) other than the chloroprene polymer latex (a), the chlorinated polyolefin resin emulsion (b), and the tackifier resin emulsion (c). You don't have to.
- the polychloroprene latex adhesive according to one embodiment of the present invention has initial adhesive strengths 1 and 2 measured by the following procedure that satisfy the following. ⁇ Method for measuring initial adhesive strength> Urethane foam (thickness 20 mm x length 50 mm x width 50 mm) with a density of 30 kg/ m3 and polypropylene sheet (thickness 1 mm x length 50 mm x width 25 mm) were used as adherends, and adhesive was applied in an atmosphere of 23 °C. Spray coat onto each adherend so that the amount is 70 g/m 2 .
- the polychloroprene latex adhesive preferably has an initial adhesive strength 1 of 1.0 N/cm 2 or more, preferably 2.0 N/cm 2 or more, as measured by the above procedure. It is more preferable.
- the initial adhesive strength 1 is, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6. 0, 6.5, 7.0 N/cm 2 , and may be within the range between any two of the numerical values exemplified here.
- the polychloroprene latex adhesive according to an embodiment of the present invention preferably has an initial adhesive strength 2 of 3.5 N/cm 2 or more, preferably 4.0 N/cm 2 or more, as measured by the above procedure. It is more preferable.
- the initial adhesive strength 1 is, for example, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0 N/cm 2 , and the numerical values exemplified here It may be within the range between any two.
- the polychloroprene latex adhesive of the present invention described above can be used for various types of adherends, but it can be particularly suitably used when the adherend is a polyolefin resin.
- the polychloroprene latex adhesive according to the present invention shortens the drying time of the adhesive layer when used as an adhesive, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. Therefore, a polychloroprene latex adhesive for adhering to a polyolefin resin can be used, in which at least one of the adherends is made of a polyolefin resin.
- the polychloroprene latex adhesive according to one embodiment of the present invention is useful for adhering, for example, polyolefin resin and polyurethane foam used as automobile interior materials, polyolefin resin and fabric, and the like.
- ⁇ Adjustment example 1> "Manufacture of chloroprene polymer latex a-1" Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C.
- ⁇ Adjustment example 2 "Manufacture of chloroprene polymer latex a-2" Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C.
- the toluene insoluble content of the obtained chloroprene polymer was measured according to the following method.
- Example 1 As the chloroprene polymer latex (a), 100 parts by mass of the chloroprene polymer latex a-1 obtained above was used in terms of solid content, and as the chlorinated polyolefin resin emulsion (b), EW-5303 (manufactured by Toyobo Co., Ltd., maleic anhydride) was added. Modified chlorinated ethylene-propylene-butene copolymer resin emulsion, chlorine content 17% by mass) was 5 parts by mass in terms of solid content, and Tamanol E-100 (manufactured by Arakawa Chemical Industries) was used as the tackifying resin emulsion (c) in solid content.
- EW-5303 manufactured by Toyobo Co., Ltd., maleic anhydride
- Example 2 As shown in Table 1, a polychloroprene latex adhesive of Example 2 was obtained under the same conditions as Example 1 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
- Example 3 As shown in Table 1, EH-801 (manufactured by Toyobo, chlorine content 16% by mass) was added instead of EW-5303 (manufactured by Toyobo, chlorine content 17% by mass) as the chlorinated polyolefin resin emulsion (b).
- a polychloroprene latex adhesive of Example 3 was obtained under the same conditions as Example 1 except for the following.
- Example 4 As shown in Table 1, a polychloroprene latex adhesive of Example 4 was obtained under the same conditions as Example 3 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
- Example 5 and 6 As shown in Table 1, polychloroprene latex adhesives of Examples 5 and 6 were obtained under the same conditions as in Example 1, except that the amount of tackifier resin emulsion (c) added was changed.
- Example 7 As shown in Table 1, a polychloroprene latex adhesive of Example 7 was obtained under the same conditions as Example 1 except that no plasticizer was added.
- Example 8 and 9 As shown in Table 1, polychloroprene latex adhesives of Examples 8 and 9 were obtained under the same conditions as in Example 1, except that the amount of the pH adjuster (d) added was changed.
- Comparative example 1 As shown in Table 1, the polychloroprene latex adhesive of Comparative Example 1 was prepared under the same conditions as Example 1, except that the chlorinated polyolefin resin emulsion (b) and tackifying resin emulsion (c) were not added. Obtained.
- Comparative Example 2 As shown in Table 1, Comparative Example 2 was prepared under the same conditions as Example 1, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifier resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
- Comparative Example 3 As shown in Table 1, Comparative Example 3 was prepared under the same conditions as Example 3, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifying resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
- Comparative Example 4 As shown in Table 1, Comparative Example 4 was carried out under the same conditions as Example 1, except that chloroprene polymer latex a-2 was added as chloroprene polymer latex (a) instead of chloroprene polymer latex a-1. A polychloroprene latex adhesive was obtained.
- Comparative example 5 As shown in Table 1, a polychloroprene latex adhesive of Comparative Example 5 was obtained under the same conditions as in Example 1 except that the chlorinated polyolefin resin emulsion (b) was not added.
- the adherend (laminate) was compressed to 2 mm and held for 10 seconds. Immediately thereafter, a tensile test was conducted in a direction perpendicular to the adhesive surface using a tensile tester (Tensilon manufactured by A&D; tensile speed: 200 mm/min) to measure adhesive strength.
- a tensile tester Teensilon manufactured by A&D; tensile speed: 200 mm/min
- the polychloroprene latex adhesive according to the present invention has improved initial adhesive strength, especially adhesive strength in a wet state, and is suitable for applications requiring excellent initial adhesive strength, especially for polyolefin resins. It has been confirmed that it can be suitably used as a spray-type adhesive for adhering polyurethane foams and polyurethane foams.
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Abstract
The present invention provides a polychloroprene latex adhesive which, when used, reduces the drying time of an adhesive layer, the drying temperature of which is normal temperature, and which has excellent initial adhesive force with a polyolefin resin even in a wet state. The polychloroprene latex adhesive comprises a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifying resin emulsion (c), and a pH adjuster (d), wherein the chloroprene polymer latex (a) includes a chloroprene polymer, the toluene-insoluble fraction of which is not more than 20 mass%.
Description
本発明は、ポリクロロプレンラテックス接着剤に関する。
The present invention relates to polychloroprene latex adhesives.
ポリクロロプレンラテックスは土木建築、合板、家具、靴、ウェットスーツなどの水系接着剤、作業用手袋、実験用手袋、医療用手袋、風船などの浸漬成型品、土木、建築などの防水塗膜など、様々な分野で利用されている。このうち水系接着剤（ポリクロロプレンラテックス接着剤）は、水系であるため安全性が高く、被着体適応性の広さや接着性のバランスの良さから種々の用途への検討が盛んに行われている。
Polychloroprene latex is used in civil engineering, construction, plywood, furniture, shoes, water-based adhesives such as wet suits, work gloves, laboratory gloves, medical gloves, dip molded products such as balloons, waterproof coatings for civil engineering, construction, etc. It is used in various fields. Among these, water-based adhesives (polychloroprene latex adhesives) are highly safe because they are water-based, and are being actively investigated for various uses due to their wide adaptability to adherends and well-balanced adhesive properties. There is.
ポリオレフィン樹脂は耐水性、耐薬品性を有し、軽量かつ強靭であることから、自動車内装材料や電気絶縁材料、日用雑貨などの各種成型品の材料として幅広く用いられているが、ポリオレフィン樹脂のような、表面に極性基が存在せず分極性の小さい物質に対しては、極めて接着が困難である。また、ポリオレフィン樹脂等の接着ができないと、ポリクロロプレンラテックス接着剤を適用可能な製品や製造工程が非常に制限されるなどの課題がある。
Polyolefin resin has water resistance, chemical resistance, light weight, and toughness, so it is widely used as a material for various molded products such as automobile interior materials, electrical insulation materials, and daily goods. It is extremely difficult to adhere to materials such as those that have no polar groups on their surfaces and have low polarizability. Furthermore, if polyolefin resin or the like cannot be bonded, there are problems such as the products and manufacturing processes to which polychloroprene latex adhesives can be applied are severely limited.
また、一般に、ポリクロロプレンラテックス接着剤は、接合する被着体の双方に塗布し、これら接着層を乾燥した後に貼り合わせることにより、貼り合わせ直後から高い接着性を発現する。こうした特徴から、水系コンタクト型接着剤として利用が期待されている反面、乾燥時間が必要となるために、接着剤を塗布してから接着するのに時間を要すること、また乾燥時間を短縮するには特殊な乾燥設備が必要となりコストアップにつながるなどの課題があった。
Furthermore, in general, a polychloroprene latex adhesive is applied to both adherends to be joined, and these adhesive layers are dried and then laminated together, thereby exhibiting high adhesiveness immediately after lamination. Due to these characteristics, it is expected to be used as a water-based contact adhesive, but since it requires drying time, it takes time to bond after applying the adhesive, and it is difficult to shorten the drying time. However, there were issues such as the need for special drying equipment, which led to increased costs.
ポリオレフィン樹脂との接着性を向上させる手段として、クロロプレン重合体ラテックスに塩素化ポリオレフィン樹脂エマルジョンを添加したクロロプレンゴムラテックス接着剤組成物が知られている（例えば、特許文献１参照）。
A chloroprene rubber latex adhesive composition in which a chlorinated polyolefin resin emulsion is added to a chloroprene polymer latex is known as a means for improving adhesiveness with a polyolefin resin (for example, see Patent Document 1).
本発明は、接着剤使用時に、接着層の乾燥時間を短くし、かつ、乾燥温度を常温とし、湿潤状態であっても、ポリオレフィン樹脂と優れた初期接着力を有するポリクロロプレンラテックス接着剤を提供することを課題とする。
The present invention provides a polychloroprene latex adhesive that shortens the drying time of the adhesive layer when using the adhesive, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. The task is to do so.
本発明者らは、鋭意検討を重ねた結果、特定のクロロプレン重合体ラテックス（ａ）に塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）、及びｐＨ調整剤（ｄ）を加えたポリクロロプレンラテックス接着剤により、前記課題が達成されることを見出した。
As a result of extensive studies, the present inventors added a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d) to a specific chloroprene polymer latex (a). It has been found that a polychloroprene latex adhesive achieves this objective.
以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
［１］クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）、及びｐＨ調整剤（ｄ）を含有するポリクロロプレンラテックス接着剤であって、前記クロロプレン重合体ラテックス（ａ）が、トルエン不溶分が２０質量％以下であるクロロプレン重合体を含む、ポリクロロプレンラテックス接着剤。
［２］前記ポリクロロプレンラテックス接着剤に含まれる前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、前記塩素化ポリオレフィン樹脂エマルジョン（ｂ）を固形分換算で１～２０質量部、前記粘着付与樹脂エマルジョン（Ｃ）を固形分換算で１～１００質量部、前記ｐＨ調整剤（ｄ）を固形分換算で０．１～３０質量部、含有する、［１］に記載のポリクロロプレンラテックス接着剤。
［３］前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、可塑剤（ｅ）を固形分換算で０．１～１００質量部、含有する［１］又は［２］に記載のポリクロロプレンラテックス接着剤。
［４］［１］～［３］のいずれかに記載のポリクロロプレンラテックス接着剤であって、被着体の少なくとも一方をポリオレフィン樹脂とする、ポリオレフィン樹脂接着用ポリクロロプレンラテックス接着剤。 Various embodiments of the present invention will be illustrated below. The embodiments shown below can be combined with each other.
[1] A polychloroprene latex adhesive containing a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d), A polychloroprene latex adhesive, wherein the combined latex (a) contains a chloroprene polymer having a toluene insoluble content of 20% by mass or less.
[2] When the chloroprene polymer latex (a) contained in the polychloroprene latex adhesive is 100 parts by mass in terms of solid content, the chlorinated polyolefin resin emulsion (b) is 1 to 20 parts by mass in terms of solid content. 1 to 100 parts by mass of the tackifying resin emulsion (C) in terms of solid content, and 0.1 to 30 parts by mass of the pH adjuster (d) in terms of solid content, according to [1]. Polychloroprene latex adhesive.
[3] When the chloroprene polymer latex (a) is 100 parts by mass in terms of solid content, the plasticizer (e) is contained in an amount of 0.1 to 100 parts by mass in terms of solid content [1] or [2] Polychloroprene latex adhesive as described in.
[4] The polychloroprene latex adhesive according to any one of [1] to [3], wherein at least one of the adherends is a polyolefin resin.
［１］クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）、及びｐＨ調整剤（ｄ）を含有するポリクロロプレンラテックス接着剤であって、前記クロロプレン重合体ラテックス（ａ）が、トルエン不溶分が２０質量％以下であるクロロプレン重合体を含む、ポリクロロプレンラテックス接着剤。
［２］前記ポリクロロプレンラテックス接着剤に含まれる前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、前記塩素化ポリオレフィン樹脂エマルジョン（ｂ）を固形分換算で１～２０質量部、前記粘着付与樹脂エマルジョン（Ｃ）を固形分換算で１～１００質量部、前記ｐＨ調整剤（ｄ）を固形分換算で０．１～３０質量部、含有する、［１］に記載のポリクロロプレンラテックス接着剤。
［３］前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、可塑剤（ｅ）を固形分換算で０．１～１００質量部、含有する［１］又は［２］に記載のポリクロロプレンラテックス接着剤。
［４］［１］～［３］のいずれかに記載のポリクロロプレンラテックス接着剤であって、被着体の少なくとも一方をポリオレフィン樹脂とする、ポリオレフィン樹脂接着用ポリクロロプレンラテックス接着剤。 Various embodiments of the present invention will be illustrated below. The embodiments shown below can be combined with each other.
[1] A polychloroprene latex adhesive containing a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d), A polychloroprene latex adhesive, wherein the combined latex (a) contains a chloroprene polymer having a toluene insoluble content of 20% by mass or less.
[2] When the chloroprene polymer latex (a) contained in the polychloroprene latex adhesive is 100 parts by mass in terms of solid content, the chlorinated polyolefin resin emulsion (b) is 1 to 20 parts by mass in terms of solid content. 1 to 100 parts by mass of the tackifying resin emulsion (C) in terms of solid content, and 0.1 to 30 parts by mass of the pH adjuster (d) in terms of solid content, according to [1]. Polychloroprene latex adhesive.
[3] When the chloroprene polymer latex (a) is 100 parts by mass in terms of solid content, the plasticizer (e) is contained in an amount of 0.1 to 100 parts by mass in terms of solid content [1] or [2] Polychloroprene latex adhesive as described in.
[4] The polychloroprene latex adhesive according to any one of [1] to [3], wherein at least one of the adherends is a polyolefin resin.
本発明によれば、接着剤使用時に、接着層の乾燥時間を短くし、かつ、乾燥温度を常温とし、湿潤状態であっても、ポリオレフィン樹脂と優れた初期接着力を有するポリクロロプレンラテックス接着剤が得られる。本発明のポリクロロプレンラテックス接着剤は、特にポリオレフィン樹脂やポリウレタンフォームの接着に使用されるスプレータイプの接着剤として好適に用いられるものである。本発明に係るポリクロロプレンラテックス接着剤による接着工程では、従来必要であった、長時間の乾燥や加熱乾燥が必須ではないため、作業工程を短縮することができ、エネルギー及びコストを削減することができ、設備を簡略化することができる。
According to the present invention, when using an adhesive, the polychloroprene latex adhesive shortens the drying time of the adhesive layer, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. is obtained. The polychloroprene latex adhesive of the present invention is particularly suitable for use as a spray type adhesive used for adhering polyolefin resins and polyurethane foams. In the bonding process using the polychloroprene latex adhesive according to the present invention, the long drying time and heat drying that were conventionally required are not essential, so the work process can be shortened and energy and costs can be reduced. It is possible to simplify the equipment.
以下、本発明について詳細に説明する。なお、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示したものであり、これにより本発明を限定するものではない。
The present invention will be explained in detail below. Note that the embodiment described below shows an example of a typical embodiment of the present invention, and the present invention is not limited thereby.
本発明に係るポリクロロプレンラテックス接着剤は、クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）、及びｐＨ調整剤（ｄ）を含む。以下、本発明に係るポリクロロプレンラテックス接着剤が含み得る成分について説明する。
The polychloroprene latex adhesive according to the present invention includes a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d). Hereinafter, components that may be included in the polychloroprene latex adhesive according to the present invention will be explained.
１．クロロプレン重合体ラテックス（ａ）
本発明に係るクロロプレン重合体ラテックスは、クロロプレン重合体を含む。本発明におけるクロロプレン重合体は、２－クロロ－１，３－ブタジエン（以下クロロプレン単量体と記す）に由来する単量体単位を含む重合体を意味し、クロロプレン単量体の単独重合体、及び、クロロプレン単量体とクロロプレン単量体と共重合可能な他の単量体に由来する単量体単位を含む共重合体を含む。他の単量体としては、１－クロロ－１，３－ブタジエン、２，３－ジクロロ－１，３－ブタジエン、ブタジエン、イソプレン、スチレン、アクリロニトリル、硫黄、アクリル酸及びそのエステル類、メタクリル酸及びそのエステル類などを挙げることができる。 1. Chloroprene polymer latex (a)
The chloroprene polymer latex according to the present invention includes a chloroprene polymer. The chloroprene polymer in the present invention means a polymer containing a monomer unit derived from 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene monomer), and includes a homopolymer of chloroprene monomer, It also includes a copolymer containing a monomer unit derived from a chloroprene monomer and another monomer copolymerizable with the chloroprene monomer. Other monomers include 1-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, sulfur, acrylic acid and its esters, methacrylic acid and Examples include esters thereof.
本発明に係るクロロプレン重合体ラテックスは、クロロプレン重合体を含む。本発明におけるクロロプレン重合体は、２－クロロ－１，３－ブタジエン（以下クロロプレン単量体と記す）に由来する単量体単位を含む重合体を意味し、クロロプレン単量体の単独重合体、及び、クロロプレン単量体とクロロプレン単量体と共重合可能な他の単量体に由来する単量体単位を含む共重合体を含む。他の単量体としては、１－クロロ－１，３－ブタジエン、２，３－ジクロロ－１，３－ブタジエン、ブタジエン、イソプレン、スチレン、アクリロニトリル、硫黄、アクリル酸及びそのエステル類、メタクリル酸及びそのエステル類などを挙げることができる。 1. Chloroprene polymer latex (a)
The chloroprene polymer latex according to the present invention includes a chloroprene polymer. The chloroprene polymer in the present invention means a polymer containing a monomer unit derived from 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene monomer), and includes a homopolymer of chloroprene monomer, It also includes a copolymer containing a monomer unit derived from a chloroprene monomer and another monomer copolymerizable with the chloroprene monomer. Other monomers include 1-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, sulfur, acrylic acid and its esters, methacrylic acid and Examples include esters thereof.
本発明の一実施形態に係るクロロプレン重合体ラテックスは、クロロプレン重合体ラテックスに含まれるクロロプレン重合体を１００質量％としたとき、クロロプレン単量体単位を６０～１００質量％含むことが好ましい。クロロプレン単量体単位の含有率は、例えば、６０、６５、７０、７５、８０、８５、９０、９５、９９、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The chloroprene polymer latex according to one embodiment of the present invention preferably contains 60 to 100% by mass of chloroprene monomer units when the chloroprene polymer contained in the chloroprene polymer latex is 100% by mass. The content of the chloroprene monomer unit is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 99, 100% by mass, and within the range between any two of the numerical values exemplified here. It may be.
本発明の一実施形態に係るクロロプレン重合体ラテックスは、エチレン性不飽和カルボン酸に由来する単量体単位を含むこともでき、クロロプレン重合体ラテックスに含まれるクロロプレン重合体を１００質量％としたとき、エチレン性不飽和カルボン酸に由来する単量体単位の含有率が、０質量部以上、２．０質量部未満であることができる。エチレン性不飽和カルボン酸に由来する単量体単位の含有率は、例えば、０質量部、０．１質量部、０．２質量部未満、０．２質量部、０．３質量部、０．４質量部未満、０．４質量部、０．５質量部、０．８質量部、１．０質量部、１．５質量部、２．０質量部未満であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明の一実施形態に係るクロロプレン重合体ラテックスは、エチレン性不飽和カルボン酸に由来する単量体単位を含むクロロプレン重合体を含まなくてもよい。
The chloroprene polymer latex according to one embodiment of the present invention may also contain a monomer unit derived from ethylenically unsaturated carboxylic acid, and when the chloroprene polymer contained in the chloroprene polymer latex is 100% by mass. The content of monomer units derived from ethylenically unsaturated carboxylic acid can be 0 parts by mass or more and less than 2.0 parts by mass. The content of monomer units derived from ethylenically unsaturated carboxylic acid is, for example, 0 parts by mass, 0.1 parts by mass, less than 0.2 parts by mass, 0.2 parts by mass, 0.3 parts by mass, 0 parts by mass, less than .4 parts by mass, 0.4 parts by mass, 0.5 parts by mass, 0.8 parts by mass, 1.0 parts by mass, 1.5 parts by mass, less than 2.0 parts by mass, and the numerical values exemplified here. It may be within the range between any two. The chloroprene polymer latex according to one embodiment of the present invention may not contain a chloroprene polymer containing monomer units derived from ethylenically unsaturated carboxylic acid.
本発明の一実施形態に係るクロロプレン重合体ラテックスは、１種のクロロプレン重合体を含むことができ、２種以上のクロロプレン重合体を含むこともできる。本発明の一実施形態に係るクロロプレン重合体ラテックスが、２種以上のクロロプレン重合体を含む場合、クロロプレン重合体ラテックスに含まれる２種以上のクロロプレン重合体に含まれる各単量体単位の合計含有率が上記数値範囲内であることが好ましい。
The chloroprene polymer latex according to one embodiment of the present invention may include one type of chloroprene polymer, or may include two or more types of chloroprene polymers. When the chloroprene polymer latex according to an embodiment of the present invention contains two or more types of chloroprene polymers, the total content of each monomer unit contained in the two or more types of chloroprene polymers contained in the chloroprene polymer latex. It is preferable that the ratio is within the above numerical range.
本発明の一実施形態に係るクロロプレン重合体ラテックスは、クロロプレン単量体の単独重合体を含むことが好ましい。本発明の一実施形態に係るクロロプレン重合体ラテックスは、ポリクロロプレンラテックス接着剤に含まれるクロロプレン重合体ラテックスの固形分１００質量％に対して、クロロプレン単量体の単独重合体を、固形分で、５０質量％超、１００質量％以下含むことが好ましく、８０質量％超、１００質量％以下含むことがより好ましく、９０質量％超、１００質量％以下含むことが好ましく、。クロロプレン単量体の単独重合体の含有率は、例えば、５５、６０、６５、７０、７５、８０、８５、９０、９５、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The chloroprene polymer latex according to one embodiment of the present invention preferably includes a homopolymer of chloroprene monomers. The chloroprene polymer latex according to one embodiment of the present invention has a solid content of a homopolymer of chloroprene monomer, based on 100% by mass of the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive. The content is preferably more than 50% by mass and 100% by mass or less, more preferably more than 80% by mass and 100% by mass or less, and preferably more than 90% by mass and 100% by mass or less. The content of the homopolymer of chloroprene monomer is, for example, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and is between any two of the values exemplified here. may be within the range of
本発明の一実施形態に係るクロロプレン重合体ラテックスは、カルボキシ変性クロロプレン系共重合体を含むこともでき、ポリクロロプレンラテックス接着剤に含まれるクロロプレン重合体ラテックスの固形分１００質量％に対して、カルボキシ変性クロロプレン系共重合体を、固形分で、０質量％以上、５０質量％未満含むことができ、０質量％以上、２０質量％未満、０質量％以上、１０質量部未満含むことができる。カルボキシ変性クロロプレン系共重合体の含有率は、例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５質量％、５０質量％未満であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明の一実施形態に係るクロロプレン重合体ラテックスは、カルボキシ変性クロロプレン系共重合体を含まなくてもよい。
The chloroprene polymer latex according to an embodiment of the present invention may also contain a carboxy-modified chloroprene copolymer, and the chloroprene polymer latex based on the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive has a carboxy The modified chloroprene copolymer can be contained in an amount of 0 mass % or more and less than 50 mass %, and can be contained in a solid content of 0 mass % or more and less than 20 mass %, or 0 mass % or more and less than 10 parts by mass. The content of the carboxy-modified chloroprene copolymer is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45% by mass, less than 50% by mass, and any of the values exemplified here or within a range between the two. The chloroprene polymer latex according to one embodiment of the present invention may not contain a carboxy-modified chloroprene copolymer.
＜トルエン不溶分＞
本発明に係るクロロプレン重合体ラテックスは、クロロプレン重合体を含み、該クロロプレン重合体はトルエン不溶分が２０質量％以下である。すなわち、本発明に係るクロロプレン重合体ラテックスは、トルエン不溶分が２０質量％以下である。
本発明において、トルエン不溶分とは、クロロプレン重合体のうち、トルエン溶媒に不溶なゲル分の含有率をいう。また、ゾルとはトルエン溶媒に可溶な成分をいう。本発明における優れた初期接着力の発現は、クロロプレン重合体が分子運動性に優れたゾルを多量に含むことによる。このため、接着界面におけるクロロプレン重合体分子鎖の融合が速やかに起こり、接着強度が瞬時に発現し、優れた初期接着力を発現することが可能となる。 <Toluene insoluble matter>
The chloroprene polymer latex according to the present invention includes a chloroprene polymer, and the chloroprene polymer has a toluene insoluble content of 20% by mass or less. That is, the chloroprene polymer latex according to the present invention has a toluene insoluble content of 20% by mass or less.
In the present invention, the toluene-insoluble content refers to the content of gel components insoluble in toluene solvent in the chloroprene polymer. In addition, sol refers to a component soluble in toluene solvent. The excellent initial adhesive strength in the present invention is achieved because the chloroprene polymer contains a large amount of sol having excellent molecular mobility. Therefore, fusion of the chloroprene polymer molecular chains at the adhesive interface occurs quickly, adhesive strength is instantaneously developed, and excellent initial adhesive strength can be developed.
本発明に係るクロロプレン重合体ラテックスは、クロロプレン重合体を含み、該クロロプレン重合体はトルエン不溶分が２０質量％以下である。すなわち、本発明に係るクロロプレン重合体ラテックスは、トルエン不溶分が２０質量％以下である。
本発明において、トルエン不溶分とは、クロロプレン重合体のうち、トルエン溶媒に不溶なゲル分の含有率をいう。また、ゾルとはトルエン溶媒に可溶な成分をいう。本発明における優れた初期接着力の発現は、クロロプレン重合体が分子運動性に優れたゾルを多量に含むことによる。このため、接着界面におけるクロロプレン重合体分子鎖の融合が速やかに起こり、接着強度が瞬時に発現し、優れた初期接着力を発現することが可能となる。 <Toluene insoluble matter>
The chloroprene polymer latex according to the present invention includes a chloroprene polymer, and the chloroprene polymer has a toluene insoluble content of 20% by mass or less. That is, the chloroprene polymer latex according to the present invention has a toluene insoluble content of 20% by mass or less.
In the present invention, the toluene-insoluble content refers to the content of gel components insoluble in toluene solvent in the chloroprene polymer. In addition, sol refers to a component soluble in toluene solvent. The excellent initial adhesive strength in the present invention is achieved because the chloroprene polymer contains a large amount of sol having excellent molecular mobility. Therefore, fusion of the chloroprene polymer molecular chains at the adhesive interface occurs quickly, adhesive strength is instantaneously developed, and excellent initial adhesive strength can be developed.
トルエン不溶分は、より好ましくは、１０質量％以下であり、例えば、０質量％、１質量％、２質量％、３質量％、４質量％、５質量％、６質量％、７質量％、８質量％未満、８質量％、１０質量％、１２質量％、１４質量％、１６質量％、１８質量％、２０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
クロロプレン重合体のトルエン不溶分が２０質量％を越えると、この初期接着力が低下するため好ましくない。 The toluene insoluble content is more preferably 10% by mass or less, for example, 0% by mass, 1% by mass, 2% by mass, 3% by mass, 4% by mass, 5% by mass, 6% by mass, 7% by mass, Less than 8% by mass, 8% by mass, 10% by mass, 12% by mass, 14% by mass, 16% by mass, 18% by mass, 20% by mass, and within the range between any two of the numerical values exemplified here. There may be.
If the toluene-insoluble content of the chloroprene polymer exceeds 20% by mass, this initial adhesive strength will decrease, which is not preferable.
クロロプレン重合体のトルエン不溶分が２０質量％を越えると、この初期接着力が低下するため好ましくない。 The toluene insoluble content is more preferably 10% by mass or less, for example, 0% by mass, 1% by mass, 2% by mass, 3% by mass, 4% by mass, 5% by mass, 6% by mass, 7% by mass, Less than 8% by mass, 8% by mass, 10% by mass, 12% by mass, 14% by mass, 16% by mass, 18% by mass, 20% by mass, and within the range between any two of the numerical values exemplified here. There may be.
If the toluene-insoluble content of the chloroprene polymer exceeds 20% by mass, this initial adhesive strength will decrease, which is not preferable.
トルエン不溶分は、クロロプレン重合体ラテックスを凍結乾燥させることにより得られた乾燥物の質量をＡｇとし、凍結乾燥後のラテックスを、トルエンで溶解した混合物から分離したゲル分をＢｇとしたとき、以下の式で求めることができ、具体的には、実施例に記載の方法で求めることができる。
トルエン不溶分＝Ｂ／Ａ×１００（％） The toluene-insoluble content is as follows, where Ag is the mass of the dry product obtained by freeze-drying the chloroprene polymer latex, and Bg is the gel content separated from the mixture in which the latex after freeze-drying is dissolved in toluene. It can be determined using the following formula, and specifically, it can be determined using the method described in Examples.
Toluene insoluble content = B/A x 100 (%)
トルエン不溶分＝Ｂ／Ａ×１００（％） The toluene-insoluble content is as follows, where Ag is the mass of the dry product obtained by freeze-drying the chloroprene polymer latex, and Bg is the gel content separated from the mixture in which the latex after freeze-drying is dissolved in toluene. It can be determined using the following formula, and specifically, it can be determined using the method described in Examples.
Toluene insoluble content = B/A x 100 (%)
トルエン不溶分は、クロロプレン重合体ラテックス製造時の、重合条件、例えば、重合開始剤及び連鎖移動剤の種類及び量、並びに重合温度、重合時間、重合率等の製造条件を調整することにより、制御することができる。
The toluene insoluble content can be controlled by adjusting the polymerization conditions, such as the type and amount of the polymerization initiator and chain transfer agent, as well as the polymerization temperature, polymerization time, and polymerization rate, during the production of chloroprene polymer latex. can do.
なお、クロロプレン重合体ラテックスが、２種以上のクロロプレン重合体を含む場合、トルエン不溶分は、２種以上のクロロプレン重合体中に含まれるトルエン不溶分（２種以上のクロロプレン系重合体を混合した混合物のトルエン不溶分）が上記数値範囲内であることが好ましい。
In addition, when the chloroprene polymer latex contains two or more kinds of chloroprene polymers, the toluene-insoluble matter is the toluene-insoluble matter contained in the two or more kinds of chloroprene polymers (the toluene-insoluble matter contained in the two or more kinds of chloroprene polymers). It is preferable that the toluene-insoluble content of the mixture is within the above numerical range.
＜クロロプレン重合体ラテックス（ａ）の製造方法＞
本発明に係るクロロプレン重合体ラテックスの製造方法は特に限定されないが、以下の方法で製造できる。
本発明の一実施形態に係るクロロプレン重合体ラテックスの製造方法は、乳化重合工程を含むことができ、乳化重合工程では、クロロプレン単量体、又は、クロロプレン単量体及びこれと共重合可能な他の単量体を、乳化剤や分散剤や重合開始剤や連鎖移動剤等を適宜に用いて乳化重合させ、目的とする重合率に達した際に重合停止剤を添加してクロロプレン系重合体ラテックスを得ることができる。
また、このようにして得られたクロロプレン系重合体ラテックスから、スチームフラッシュ法や濃縮法等によって、未反応の単量体を除去することができる。 <Production method of chloroprene polymer latex (a)>
Although the method for producing the chloroprene polymer latex according to the present invention is not particularly limited, it can be produced by the following method.
The method for producing a chloroprene polymer latex according to an embodiment of the present invention may include an emulsion polymerization step, and in the emulsion polymerization step, a chloroprene monomer, or a chloroprene monomer and other materials copolymerizable therewith are used. These monomers are subjected to emulsion polymerization using appropriate emulsifiers, dispersants, polymerization initiators, chain transfer agents, etc., and when the desired polymerization rate is reached, a polymerization terminator is added to form a chloroprene-based polymer latex. can be obtained.
Furthermore, unreacted monomers can be removed from the chloroprene polymer latex thus obtained by a steam flash method, a concentration method, or the like.
本発明に係るクロロプレン重合体ラテックスの製造方法は特に限定されないが、以下の方法で製造できる。
本発明の一実施形態に係るクロロプレン重合体ラテックスの製造方法は、乳化重合工程を含むことができ、乳化重合工程では、クロロプレン単量体、又は、クロロプレン単量体及びこれと共重合可能な他の単量体を、乳化剤や分散剤や重合開始剤や連鎖移動剤等を適宜に用いて乳化重合させ、目的とする重合率に達した際に重合停止剤を添加してクロロプレン系重合体ラテックスを得ることができる。
また、このようにして得られたクロロプレン系重合体ラテックスから、スチームフラッシュ法や濃縮法等によって、未反応の単量体を除去することができる。 <Production method of chloroprene polymer latex (a)>
Although the method for producing the chloroprene polymer latex according to the present invention is not particularly limited, it can be produced by the following method.
The method for producing a chloroprene polymer latex according to an embodiment of the present invention may include an emulsion polymerization step, and in the emulsion polymerization step, a chloroprene monomer, or a chloroprene monomer and other materials copolymerizable therewith are used. These monomers are subjected to emulsion polymerization using appropriate emulsifiers, dispersants, polymerization initiators, chain transfer agents, etc., and when the desired polymerization rate is reached, a polymerization terminator is added to form a chloroprene-based polymer latex. can be obtained.
Furthermore, unreacted monomers can be removed from the chloroprene polymer latex thus obtained by a steam flash method, a concentration method, or the like.
（乳化剤）
乳化剤は特に限定されず、クロロプレン重合体の重合に使用されている公知のアニオン系、ノニオン系、カチオン系の乳化剤を使用することができる。 (emulsifier)
The emulsifier is not particularly limited, and known anionic, nonionic, and cationic emulsifiers used in the polymerization of chloroprene polymers can be used.
乳化剤は特に限定されず、クロロプレン重合体の重合に使用されている公知のアニオン系、ノニオン系、カチオン系の乳化剤を使用することができる。 (emulsifier)
The emulsifier is not particularly limited, and known anionic, nonionic, and cationic emulsifiers used in the polymerization of chloroprene polymers can be used.
乳化剤は、ロジン酸、又は、そのアルカリ金属塩から選ばれる１種又は２種以上を含むことが好ましい。ロジン酸としては、ウッドロジン酸、ガムロジン酸、トール油ロジン酸、又はこれらを不均化した不均化ロジン酸の何れも使用可能である。乳化剤として、ロジン酸又は、そのアルカリ金属塩を用いると、クロロプレン重合体ラテックスに機械的な刺激が加わった場合に容易にその乳化安定性が低下する。このため、クロロプレン重合体ラテックスを接着剤として用いた場合に優れた初期接着強度を発現させることができる。
The emulsifier preferably contains one or more selected from rosin acid or an alkali metal salt thereof. As the rosin acid, any of wood rosin acid, gum rosin acid, tall oil rosin acid, or disproportionated rosin acid obtained by disproportionation of these can be used. When rosin acid or an alkali metal salt thereof is used as an emulsifier, the emulsion stability of the chloroprene polymer latex easily decreases when mechanical stimulation is applied. Therefore, when the chloroprene polymer latex is used as an adhesive, excellent initial adhesive strength can be exhibited.
乳化剤としてロジン酸を使用する場合は、重合制御面、及び初期接着性能、特に湿潤状態における接着性能の観点からそのアルカリ金属塩を添加することがより好ましい。アルカリ金属塩を構成する化合物としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウムなどがある。この中でもコストや水溶性等の観点から水酸化ナトリウム、水酸化カリウムが好ましい。ロジン酸の添加量は、用いる全単量体１００質量部に対して、０．５～１０質量部が好ましく、２～６質量部がより好ましい。
When using rosin acid as an emulsifier, it is more preferable to add its alkali metal salt from the viewpoint of polymerization control and initial adhesive performance, particularly adhesive performance in a wet state. Examples of compounds constituting the alkali metal salt include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate. Among these, sodium hydroxide and potassium hydroxide are preferred from the viewpoint of cost, water solubility, and the like. The amount of rosin acid added is preferably 0.5 to 10 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the total monomers used.
乳化重合工程では、ロジン酸以外のアニオン系の乳化剤や分散剤も用いることができ、ロジン酸以外のアニオン系の乳化剤や分散剤としては、炭素数が８～２０個のアルキルスルホネート、アルキルアリールサルフェート、ナフタリンスルホン酸ナトリウムとホルムアルデヒドの縮合物、アルキルジフェニルエーテルジスルホン酸ナトリウムがある。
In the emulsion polymerization step, anionic emulsifiers and dispersants other than rosin acid can also be used, and examples of anionic emulsifiers and dispersants other than rosin acid include alkyl sulfonates and alkylaryl sulfates having 8 to 20 carbon atoms. , a condensate of sodium naphthalene sulfonate and formaldehyde, and sodium alkyl diphenyl ether disulfonate.
乳化剤は、ノニオン系の乳化剤や分散剤を併用してもよい。ノニオン系の乳化剤を併用することで、クロロプレン重合体ラテックスの低温安定性や接着剤としたときの接着性を改良することができる。
As the emulsifier, a nonionic emulsifier or dispersant may be used in combination. The combined use of a nonionic emulsifier can improve the low-temperature stability of the chloroprene polymer latex and its adhesive properties when used as an adhesive.
（連鎖移動剤）
クロロプレン単量体の乳化重合時には、クロロプレン重合体の分子量や分子量分布、トルエン不溶分を調整するために連鎖移動剤を添加することができる。連鎖移動剤は、重合初期に添加してもよく、重合途中で添加してもよい。連鎖移動剤としては、ｎ－ドデシルメルカプタンやｔ－ドデシルメルカプタン等の長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィドやジエチルキサントゲンジスルフィド等のジアルキルキサントゲンジスルフィド類がある。分子量やゲル含有量をコントロールしやすいという観点から、長鎖アルキルメルカプタン類を用いた方が好ましい。これらの連鎖移動剤は１種類を用いることもでき、２種以上を併用してもよい。連鎖移動剤の添加量は、全単量体１００質量部に対して、０．００１～１質量部とすることができる。 (Chain transfer agent)
During emulsion polymerization of chloroprene monomers, a chain transfer agent can be added to adjust the molecular weight, molecular weight distribution, and toluene-insoluble content of the chloroprene polymer. The chain transfer agent may be added at the beginning of the polymerization or during the polymerization. Chain transfer agents include long chain alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, and dialkyl xanthogen disulfides such as diisopropyl xanthogen disulfide and diethyl xanthogen disulfide. From the viewpoint of easy control of molecular weight and gel content, it is preferable to use long-chain alkyl mercaptans. One type of these chain transfer agents may be used, or two or more types may be used in combination. The amount of the chain transfer agent added can be 0.001 to 1 part by weight based on 100 parts by weight of the total monomers.
クロロプレン単量体の乳化重合時には、クロロプレン重合体の分子量や分子量分布、トルエン不溶分を調整するために連鎖移動剤を添加することができる。連鎖移動剤は、重合初期に添加してもよく、重合途中で添加してもよい。連鎖移動剤としては、ｎ－ドデシルメルカプタンやｔ－ドデシルメルカプタン等の長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィドやジエチルキサントゲンジスルフィド等のジアルキルキサントゲンジスルフィド類がある。分子量やゲル含有量をコントロールしやすいという観点から、長鎖アルキルメルカプタン類を用いた方が好ましい。これらの連鎖移動剤は１種類を用いることもでき、２種以上を併用してもよい。連鎖移動剤の添加量は、全単量体１００質量部に対して、０．００１～１質量部とすることができる。 (Chain transfer agent)
During emulsion polymerization of chloroprene monomers, a chain transfer agent can be added to adjust the molecular weight, molecular weight distribution, and toluene-insoluble content of the chloroprene polymer. The chain transfer agent may be added at the beginning of the polymerization or during the polymerization. Chain transfer agents include long chain alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, and dialkyl xanthogen disulfides such as diisopropyl xanthogen disulfide and diethyl xanthogen disulfide. From the viewpoint of easy control of molecular weight and gel content, it is preferable to use long-chain alkyl mercaptans. One type of these chain transfer agents may be used, or two or more types may be used in combination. The amount of the chain transfer agent added can be 0.001 to 1 part by weight based on 100 parts by weight of the total monomers.
（重合開始剤）
乳化重合の開始剤としては、通常のラジカル重合開始剤を使用することができ、具体的には、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウム等の有機あるいは無機の過酸化物、アゾビスイソブチロニトリル等のアゾ化合物が使用される。アントラキノンスルホン酸塩や亜硫酸カリウム、亜硫酸ナトリウムなどの助触媒を適宜併用してもよい。 (Polymerization initiator)
As the initiator for emulsion polymerization, ordinary radical polymerization initiators can be used, and specifically, organic or inorganic peroxides such as benzoyl peroxide, potassium persulfate, ammonium persulfate, azobisisobutylene, etc. Azo compounds such as lonitrile are used. A co-catalyst such as anthraquinone sulfonate, potassium sulfite, or sodium sulfite may be used in combination as appropriate.
乳化重合の開始剤としては、通常のラジカル重合開始剤を使用することができ、具体的には、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウム等の有機あるいは無機の過酸化物、アゾビスイソブチロニトリル等のアゾ化合物が使用される。アントラキノンスルホン酸塩や亜硫酸カリウム、亜硫酸ナトリウムなどの助触媒を適宜併用してもよい。 (Polymerization initiator)
As the initiator for emulsion polymerization, ordinary radical polymerization initiators can be used, and specifically, organic or inorganic peroxides such as benzoyl peroxide, potassium persulfate, ammonium persulfate, azobisisobutylene, etc. Azo compounds such as lonitrile are used. A co-catalyst such as anthraquinone sulfonate, potassium sulfite, or sodium sulfite may be used in combination as appropriate.
（水酸化カリウム及び水酸化ナトリウム）
乳化重合工程では、水酸化ナトリウム及び／又は水酸化カリウムを用いることができる。水酸化ナトリウム及び水酸化カリウムの添加量は、単量体１００質量部に対して、０．０１～２．０質量部とすることができる。 (potassium hydroxide and sodium hydroxide)
In the emulsion polymerization step, sodium hydroxide and/or potassium hydroxide can be used. The amount of sodium hydroxide and potassium hydroxide added can be 0.01 to 2.0 parts by weight per 100 parts by weight of the monomer.
乳化重合工程では、水酸化ナトリウム及び／又は水酸化カリウムを用いることができる。水酸化ナトリウム及び水酸化カリウムの添加量は、単量体１００質量部に対して、０．０１～２．０質量部とすることができる。 (potassium hydroxide and sodium hydroxide)
In the emulsion polymerization step, sodium hydroxide and/or potassium hydroxide can be used. The amount of sodium hydroxide and potassium hydroxide added can be 0.01 to 2.0 parts by weight per 100 parts by weight of the monomer.
（重合転化率）
クロロプレン単量体の重合転化率は、５０質量％以上、９０質量％未満であることが好ましく、６０～８５質量％がより好ましい。クロロプレン単量体の重合転化率が５０％未満である場合は、クロロプレン重合体ラテックスの固形分が低下し、接着剤塗布後の乾燥工程に負荷が掛かったり、接着層の均一化が困難であったりするだけでなく、残留クロロプレン単量体による臭気や粘着力、接着力を悪化させたりするなどの問題を起こすことがある。重合転化率が９０質量％以上の場合は、クロロプレン重合体中に分岐が増たり、分子量が大きくなるために分子量分布が広がり、本発明において重要な性能であるコンタクト性、耐水性を悪化させる問題を起こすことがある。重合転化率（質量％）は［（重合体質量／単量体質量の総和）×１００］により求められる。 (Polymerization conversion rate)
The polymerization conversion rate of the chloroprene monomer is preferably 50% by mass or more and less than 90% by mass, more preferably 60 to 85% by mass. If the polymerization conversion rate of the chloroprene monomer is less than 50%, the solid content of the chloroprene polymer latex will decrease, which will put a burden on the drying process after applying the adhesive and make it difficult to make the adhesive layer uniform. In addition, residual chloroprene monomers may cause problems such as odor and deterioration of adhesive strength. When the polymerization conversion rate is 90% by mass or more, branching increases in the chloroprene polymer and the molecular weight increases, resulting in a broadened molecular weight distribution, which deteriorates contact properties and water resistance, which are important performances in the present invention. may occur. The polymerization conversion rate (mass %) is determined by [(polymer mass/total monomer mass)×100].
クロロプレン単量体の重合転化率は、５０質量％以上、９０質量％未満であることが好ましく、６０～８５質量％がより好ましい。クロロプレン単量体の重合転化率が５０％未満である場合は、クロロプレン重合体ラテックスの固形分が低下し、接着剤塗布後の乾燥工程に負荷が掛かったり、接着層の均一化が困難であったりするだけでなく、残留クロロプレン単量体による臭気や粘着力、接着力を悪化させたりするなどの問題を起こすことがある。重合転化率が９０質量％以上の場合は、クロロプレン重合体中に分岐が増たり、分子量が大きくなるために分子量分布が広がり、本発明において重要な性能であるコンタクト性、耐水性を悪化させる問題を起こすことがある。重合転化率（質量％）は［（重合体質量／単量体質量の総和）×１００］により求められる。 (Polymerization conversion rate)
The polymerization conversion rate of the chloroprene monomer is preferably 50% by mass or more and less than 90% by mass, more preferably 60 to 85% by mass. If the polymerization conversion rate of the chloroprene monomer is less than 50%, the solid content of the chloroprene polymer latex will decrease, which will put a burden on the drying process after applying the adhesive and make it difficult to make the adhesive layer uniform. In addition, residual chloroprene monomers may cause problems such as odor and deterioration of adhesive strength. When the polymerization conversion rate is 90% by mass or more, branching increases in the chloroprene polymer and the molecular weight increases, resulting in a broadened molecular weight distribution, which deteriorates contact properties and water resistance, which are important performances in the present invention. may occur. The polymerization conversion rate (mass %) is determined by [(polymer mass/total monomer mass)×100].
（重合温度）
クロロプレン重合体は、０～４５℃の範囲で重合することができるが、特に５～１５℃の低温で重合することが好ましい。クロロプレン単独重合体は、トランス－１，４－結合が８５％以上を占めることが知られており、その分子構造は比較的規則性に富むものである。クロロプレン単独重合体は、この分子構造の規則性の高さゆえに典型的な結晶性のポリマーとしての性質を持つ。重合温度を５～１５℃の低温に設定することで、ポリクロロプレン分子内のトランス－１，４－結合の比率がさらに高まるため、結晶化速度がより高いクロロプレン単独重合体を得ることができ、これを接着剤とした際に充分な接着力が達成される。 (Polymerization temperature)
The chloroprene polymer can be polymerized at a temperature in the range of 0 to 45°C, but it is particularly preferable to polymerize at a low temperature of 5 to 15°C. It is known that trans-1,4-bonds account for 85% or more of a chloroprene homopolymer, and its molecular structure is relatively highly regular. Chloroprene homopolymer has typical crystalline polymer properties due to its highly regular molecular structure. By setting the polymerization temperature to a low temperature of 5 to 15°C, the ratio of trans-1,4-bonds in the polychloroprene molecule is further increased, making it possible to obtain a chloroprene homopolymer with a higher crystallization rate. Sufficient adhesive strength is achieved when this is used as an adhesive.
クロロプレン重合体は、０～４５℃の範囲で重合することができるが、特に５～１５℃の低温で重合することが好ましい。クロロプレン単独重合体は、トランス－１，４－結合が８５％以上を占めることが知られており、その分子構造は比較的規則性に富むものである。クロロプレン単独重合体は、この分子構造の規則性の高さゆえに典型的な結晶性のポリマーとしての性質を持つ。重合温度を５～１５℃の低温に設定することで、ポリクロロプレン分子内のトランス－１，４－結合の比率がさらに高まるため、結晶化速度がより高いクロロプレン単独重合体を得ることができ、これを接着剤とした際に充分な接着力が達成される。 (Polymerization temperature)
The chloroprene polymer can be polymerized at a temperature in the range of 0 to 45°C, but it is particularly preferable to polymerize at a low temperature of 5 to 15°C. It is known that trans-1,4-bonds account for 85% or more of a chloroprene homopolymer, and its molecular structure is relatively highly regular. Chloroprene homopolymer has typical crystalline polymer properties due to its highly regular molecular structure. By setting the polymerization temperature to a low temperature of 5 to 15°C, the ratio of trans-1,4-bonds in the polychloroprene molecule is further increased, making it possible to obtain a chloroprene homopolymer with a higher crystallization rate. Sufficient adhesive strength is achieved when this is used as an adhesive.
（重合停止剤）
クロロプレン重合体の製造では、所望の分子量及び分布の重合体を得る目的で、所定の重合率に到達した時点で、重合停止剤を添加し、反応を停止させる。重合停止剤としては、フェノチアジン、ｐ－ｔ－ブチルカテコール、ハイドロキノン、ハイドロキノンモノメチルエーテル、ジエチルヒドロキシルアミンがある。 (Polymerization terminator)
In the production of a chloroprene polymer, a polymerization terminator is added to stop the reaction when a predetermined polymerization rate is reached, in order to obtain a polymer with a desired molecular weight and distribution. Examples of the polymerization terminator include phenothiazine, pt-butylcatechol, hydroquinone, hydroquinone monomethyl ether, and diethylhydroxylamine.
クロロプレン重合体の製造では、所望の分子量及び分布の重合体を得る目的で、所定の重合率に到達した時点で、重合停止剤を添加し、反応を停止させる。重合停止剤としては、フェノチアジン、ｐ－ｔ－ブチルカテコール、ハイドロキノン、ハイドロキノンモノメチルエーテル、ジエチルヒドロキシルアミンがある。 (Polymerization terminator)
In the production of a chloroprene polymer, a polymerization terminator is added to stop the reaction when a predetermined polymerization rate is reached, in order to obtain a polymer with a desired molecular weight and distribution. Examples of the polymerization terminator include phenothiazine, pt-butylcatechol, hydroquinone, hydroquinone monomethyl ether, and diethylhydroxylamine.
（固形分濃度）
クロロプレン重合体ラテックスの固形分濃度は、特に制限するものではないが、通常４０～６５質量％である。 (solid content concentration)
The solid content concentration of the chloroprene polymer latex is not particularly limited, but is usually 40 to 65% by mass.
クロロプレン重合体ラテックスの固形分濃度は、特に制限するものではないが、通常４０～６５質量％である。 (solid content concentration)
The solid content concentration of the chloroprene polymer latex is not particularly limited, but is usually 40 to 65% by mass.
２．塩素化ポリオレフィン樹脂エマルジョン（ｂ）
塩素化ポリオレフィン樹脂エマルジョンとは、ポリオレフィン樹脂を塩素化させた樹脂エマルジョンである。塩素化ポリオレフィン樹脂エマルジョンは、ポリクロロプレンラテックス接着剤のポリオレフィン樹脂に対する接着性を付与するための成分である。 2. Chlorinated polyolefin resin emulsion (b)
The chlorinated polyolefin resin emulsion is a resin emulsion obtained by chlorinating a polyolefin resin. The chlorinated polyolefin resin emulsion is a component for imparting adhesive properties of the polychloroprene latex adhesive to the polyolefin resin.
塩素化ポリオレフィン樹脂エマルジョンとは、ポリオレフィン樹脂を塩素化させた樹脂エマルジョンである。塩素化ポリオレフィン樹脂エマルジョンは、ポリクロロプレンラテックス接着剤のポリオレフィン樹脂に対する接着性を付与するための成分である。 2. Chlorinated polyolefin resin emulsion (b)
The chlorinated polyolefin resin emulsion is a resin emulsion obtained by chlorinating a polyolefin resin. The chlorinated polyolefin resin emulsion is a component for imparting adhesive properties of the polychloroprene latex adhesive to the polyolefin resin.
塩素化ポリオレフィン樹脂エマルジョンの添加量は特に限定するものではないが、ポリオレフィン樹脂との接着性の観点からクロロプレン重合体ラテックスの固形分換算で１００質量部に対して、塩素化ポリオレフィン樹脂エマルジョンを固形分換算で１～２０質量部用いることが好ましく、固形分換算で３～１５質量部用いることがより好ましい。塩素化ポリオレフィン樹脂エマルジョンの添加量は、固形分換算で、例えば、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The amount of the chlorinated polyolefin resin emulsion added is not particularly limited, but from the viewpoint of adhesion to the polyolefin resin, the solid content of the chlorinated polyolefin resin emulsion should be set to 100 parts by mass in terms of solid content of the chloroprene polymer latex. It is preferable to use 1 to 20 parts by mass in terms of solid content, and more preferably 3 to 15 parts by mass in terms of solid content. The amount of the chlorinated polyolefin resin emulsion added is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 in terms of solid content. , 18, 19, and 20 parts by mass, and may be within a range between any two of the numerical values exemplified here.
塩素化ポリオレフィン樹脂におけるポリオレフィンは、特に限定されないが、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合樹脂、エチレン－ブテン共重合樹脂、プロピレン－ブテン共重合樹脂、エチレン－プロピレン－ブテン共重合樹脂、エチレン－プロピレン－ジエン共重合樹脂などが挙げられ、プロピレン－ブテン共重合樹脂、エチレン－プロピレン－ブテン共重合樹脂が好ましい。
The polyolefin in the chlorinated polyolefin resin is not particularly limited, but includes polyethylene, polypropylene, ethylene-propylene copolymer resin, ethylene-butene copolymer resin, propylene-butene copolymer resin, ethylene-propylene-butene copolymer resin, and ethylene-propylene. -diene copolymer resins, etc., with propylene-butene copolymer resins and ethylene-propylene-butene copolymer resins being preferred.
塩素化ポリオレフィン樹脂エマルジョンの塩素含有率は特に限定するものではないが、１０～４０質量％であるのが好ましい。塩素含有率を１０％質量以上とすることで、クロロプレン重合体ラテックスとの相溶性を向上させることができる。また、塩素含有率を４０質量％以下とすることで、ポリオレフィン樹脂等の被着体との接着性の低下を防止することができる。塩素含有率は、例えば、１０、１５、２０、２５、３０、３５、３９、４０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The chlorine content of the chlorinated polyolefin resin emulsion is not particularly limited, but is preferably 10 to 40% by mass. By setting the chlorine content to 10% by mass or more, the compatibility with the chloroprene polymer latex can be improved. Further, by setting the chlorine content to 40% by mass or less, it is possible to prevent a decrease in adhesiveness with an adherend such as a polyolefin resin. The chlorine content is, for example, 10, 15, 20, 25, 30, 35, 39, 40% by mass, and may be within a range between any two of the numerical values exemplified here.
塩素化ポリオレフィン樹脂は、塩素化、かつ、酸変性されたものであることが好ましく、無水マレイン酸変性されたものであることがより好ましい。
The chlorinated polyolefin resin is preferably chlorinated and acid-modified, more preferably maleic anhydride-modified.
塩素化ポリオレフィン樹脂エマルジョンには、本発明の効果を損なわない範囲で界面活性剤を添加してもよく、例えば、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤が挙げられる。本発明では、得られるポリクロロプレンラテックス接着剤の貯蔵安定性を向上する観点から、ノニオン性界面活性剤を用いてもよい。
Surfactants may be added to the chlorinated polyolefin resin emulsion within a range that does not impair the effects of the present invention, such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Examples include agents. In the present invention, a nonionic surfactant may be used from the viewpoint of improving the storage stability of the resulting polychloroprene latex adhesive.
塩素化ポリオレフィン樹脂エマルジョンとして用いることが可能な市販品としては、東洋紡株式会社製ＥＷ－５３０３、ＥＨ－８０１などがある。
Commercially available products that can be used as chlorinated polyolefin resin emulsions include EW-5303 and EH-801 manufactured by Toyobo Co., Ltd.
３．粘着付与樹脂エマルジョン（ｃ）
粘着付与樹脂エマルジョンは、クロロプレン重合体ラテックス接着剤の初期接着強度を向上させるために添加するものである。特に、被着体としてポリオレフィン樹脂を用いた場合の接着性を向上させることができる。 3. Tackifying resin emulsion (c)
The tackifying resin emulsion is added to improve the initial adhesive strength of the chloroprene polymer latex adhesive. In particular, the adhesiveness can be improved when a polyolefin resin is used as the adherend.
粘着付与樹脂エマルジョンは、クロロプレン重合体ラテックス接着剤の初期接着強度を向上させるために添加するものである。特に、被着体としてポリオレフィン樹脂を用いた場合の接着性を向上させることができる。 3. Tackifying resin emulsion (c)
The tackifying resin emulsion is added to improve the initial adhesive strength of the chloroprene polymer latex adhesive. In particular, the adhesiveness can be improved when a polyolefin resin is used as the adherend.
粘着付与樹脂エマルジョンの添加量は特に限定するものではないが、被着体との接着性の観点から、クロロプレン重合体ラテックスの固形分換算で１００質量部に対して、固形分換算で１～１００質量部用いることが好ましく、固形分換算で２０～７０質量部用いることがより好ましい。粘着付与樹脂エマルジョンの添加量は、例えば、０、１０、２０、３０、４０、５０、６０、７０、８０、９０、１００質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The amount of the tackifier resin emulsion added is not particularly limited, but from the viewpoint of adhesion to the adherend, it is 1 to 100 parts by weight in terms of solid content per 100 parts by mass in terms of solid content of the chloroprene polymer latex. It is preferable to use parts by mass, and more preferably 20 to 70 parts by mass in terms of solid content. The amount of the tackifying resin emulsion added is, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 parts by mass, and is in the range between any two of the numerical values exemplified here. It may be within.
粘着付与樹脂の種類については特に限定するものではないが、ガムロジン、トールロジン、ウッドロジン、不均斉化ロジン、重合ロジン、これらロジンのグリセリンエステルやペンタエリスリトールエステル、これらの水素添加物などのロジン系樹脂、テルペンフェノール樹脂の水素添加物などのテルペンフェノール系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、ジシクロペンタジエン系石油樹脂ピュアーモノマー系石油樹脂、これらの水素添加物などの石油系樹脂、スチレン系樹脂、クマロンインデン系樹脂、アルキルフェノール系樹脂、キシレン樹脂、ダンマル、コーパル、シェラックなどが挙げられ、テルペンフェノール系樹脂及びアルキルフェノール系樹脂等のフェノール樹脂を含むことが好ましく、テルペンフェノール系樹脂を含むことがより好ましい。粘着付与樹脂は、塩素化ポリオレフィン樹脂を除くものとできる。
The type of tackifier resin is not particularly limited, but includes rosin-based resins such as gum rosin, tall rosin, wood rosin, symmetrical rosin, polymerized rosin, glycerin esters and pentaerythritol esters of these rosins, and hydrogenated products thereof; Terpene phenol resins such as hydrogenated products of terpene phenol resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, dicyclopentadiene petroleum resins Pure monomer petroleum resins , these hydrogenated products include petroleum resins, styrene resins, coumaron indene resins, alkylphenol resins, xylene resins, dammar, copal, shellac, etc., and phenols such as terpene phenol resins and alkylphenol resins. It is preferable that a resin is included, and it is more preferable that a terpene phenol resin is included. The tackifying resin can be anything other than a chlorinated polyolefin resin.
粘着付与樹脂エマルジョンの市販品としては、テルペンフェノール樹脂エマルジョンである荒川化学工業株式会社製タマノルＥ－１００、タマノルＥ－２００ＮＴ等がある。
Commercially available tackifying resin emulsions include Tamanol E-100 and Tamanol E-200NT manufactured by Arakawa Chemical Industries, Ltd., which are terpene phenol resin emulsions.
４．ｐＨ調整剤（ｄ）
ｐＨ調整剤は、クロロプレン重合体ラテックスの初期接着力や貯蔵安定性を向上させるために配合するものである。ｐＨ調整剤としては、弱酸や緩衝液が使用可能であり、クエン酸、グリコール酸などのヒドロキシ酸や、ホウ酸、アミノ酸が挙げられ、アミノ酸から選ばれる少なくとも一種の化合物を含むことが望ましい。アミノ酸としては、具体的には、グリシン、アラニン、トレオニン、プロリンがある。コストや接着性能、ハンドリングの容易さ等からアミノ酸の一種であるグリシンの使用がさらに好ましい。 4. pH adjuster (d)
The pH adjuster is added to improve the initial adhesive strength and storage stability of the chloroprene polymer latex. As the pH adjuster, weak acids and buffers can be used, and examples thereof include hydroxy acids such as citric acid and glycolic acid, boric acid, and amino acids, and it is desirable to include at least one compound selected from amino acids. Specifically, amino acids include glycine, alanine, threonine, and proline. It is more preferable to use glycine, which is a type of amino acid, in terms of cost, adhesive performance, ease of handling, etc.
ｐＨ調整剤は、クロロプレン重合体ラテックスの初期接着力や貯蔵安定性を向上させるために配合するものである。ｐＨ調整剤としては、弱酸や緩衝液が使用可能であり、クエン酸、グリコール酸などのヒドロキシ酸や、ホウ酸、アミノ酸が挙げられ、アミノ酸から選ばれる少なくとも一種の化合物を含むことが望ましい。アミノ酸としては、具体的には、グリシン、アラニン、トレオニン、プロリンがある。コストや接着性能、ハンドリングの容易さ等からアミノ酸の一種であるグリシンの使用がさらに好ましい。 4. pH adjuster (d)
The pH adjuster is added to improve the initial adhesive strength and storage stability of the chloroprene polymer latex. As the pH adjuster, weak acids and buffers can be used, and examples thereof include hydroxy acids such as citric acid and glycolic acid, boric acid, and amino acids, and it is desirable to include at least one compound selected from amino acids. Specifically, amino acids include glycine, alanine, threonine, and proline. It is more preferable to use glycine, which is a type of amino acid, in terms of cost, adhesive performance, ease of handling, etc.
ｐＨ調整剤の添加量は、特に限定するものではないが、クロロプレンゴムラテックス接着剤組成物のｐＨを７～１０の範囲に調整できる量を使用することが好ましい。より好ましくは、ｐＨの範囲を８～１０に調整することが望ましい。
The amount of the pH adjuster added is not particularly limited, but it is preferable to use an amount that can adjust the pH of the chloroprene rubber latex adhesive composition to a range of 7 to 10. More preferably, the pH range is adjusted to 8-10.
ｐＨ調整剤としてグリシンを使用する場合には、クロロプレン重合体ラテックス１００質量部に対して、好ましくは０．１～３０質量部、好ましくは０．１～２０質量部、より好ましくは２～１６質量部、更に好ましくは３～１３質量部を使用すると、十分な接着力を有利なコストで発現させることができる。ｐＨ調整剤の添加量は、例えば、０.１、１、２、３、５、１０、１５、２０、２５、３０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
When using glycine as a pH adjuster, it is preferably 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 2 to 16 parts by weight, based on 100 parts by weight of the chloroprene polymer latex. %, more preferably from 3 to 13 parts by weight, sufficient adhesive strength can be developed at an advantageous cost. The amount of the pH adjuster added is, for example, 0.1, 1, 2, 3, 5, 10, 15, 20, 25, 30 parts by mass, and within the range between any two of the numerical values exemplified here. It may be.
５．可塑剤（ｅ）
ポリクロロプレンラテックス接着剤は、可塑剤を含んでいてもよい。可塑剤の添加量は、クロロプレン重合体ラテックスの固形分１００質量部に対し、固形分で、０．１～２０質量部とでき、好ましくは１～１０質量部、より好ましくは２～８質量部である。可塑剤の添加量は、例えば、０．１、１、２、４、６、８、１０、１２、１４、１６、１８、２０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。可塑剤を添加することにより、得られるポリクロロプレンラテックス接着剤の初期強度が向上するとともに、乾燥後の接着剤皮膜の風合いを柔らかくすることができる。特に、ポリウレタンフォーム用の接着剤として使用する際には可塑剤を添加することがよい。可塑剤は、クロロプレン重合体との相溶性が良好なものが良く、特に限定するものではないが、例えば、ジブチルセバケート、ジブチルフタレート、ジオクチルアジペート、ジオクチルアゼレート、ジオクチルセバケート、ジオクチルフタレート、トリクレジルホスフェート、クレジルジフェニルホスフェート等がある。 5. Plasticizer (e)
Polychloroprene latex adhesives may also contain plasticizers. The amount of the plasticizer added can be 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the solid content of the chloroprene polymer latex. It is. The amount of plasticizer added is, for example, 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 parts by mass, and is between any two of the numerical values exemplified here. may be within the range of By adding a plasticizer, the initial strength of the resulting polychloroprene latex adhesive can be improved, and the texture of the adhesive film after drying can be softened. In particular, when used as an adhesive for polyurethane foam, it is preferable to add a plasticizer. The plasticizer is preferably one that has good compatibility with the chloroprene polymer, and is not particularly limited, but examples include dibutyl sebacate, dibutyl phthalate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, dioctyl phthalate, and Examples include cresyl phosphate and cresyl diphenyl phosphate.
ポリクロロプレンラテックス接着剤は、可塑剤を含んでいてもよい。可塑剤の添加量は、クロロプレン重合体ラテックスの固形分１００質量部に対し、固形分で、０．１～２０質量部とでき、好ましくは１～１０質量部、より好ましくは２～８質量部である。可塑剤の添加量は、例えば、０．１、１、２、４、６、８、１０、１２、１４、１６、１８、２０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。可塑剤を添加することにより、得られるポリクロロプレンラテックス接着剤の初期強度が向上するとともに、乾燥後の接着剤皮膜の風合いを柔らかくすることができる。特に、ポリウレタンフォーム用の接着剤として使用する際には可塑剤を添加することがよい。可塑剤は、クロロプレン重合体との相溶性が良好なものが良く、特に限定するものではないが、例えば、ジブチルセバケート、ジブチルフタレート、ジオクチルアジペート、ジオクチルアゼレート、ジオクチルセバケート、ジオクチルフタレート、トリクレジルホスフェート、クレジルジフェニルホスフェート等がある。 5. Plasticizer (e)
Polychloroprene latex adhesives may also contain plasticizers. The amount of the plasticizer added can be 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the solid content of the chloroprene polymer latex. It is. The amount of plasticizer added is, for example, 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 parts by mass, and is between any two of the numerical values exemplified here. may be within the range of By adding a plasticizer, the initial strength of the resulting polychloroprene latex adhesive can be improved, and the texture of the adhesive film after drying can be softened. In particular, when used as an adhesive for polyurethane foam, it is preferable to add a plasticizer. The plasticizer is preferably one that has good compatibility with the chloroprene polymer, and is not particularly limited, but examples include dibutyl sebacate, dibutyl phthalate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, dioctyl phthalate, and Examples include cresyl phosphate and cresyl diphenyl phosphate.
６．その他の成分
＜酸化防止剤＞
ポリクロロプレンラテックス接着剤は、一般に酸素による劣化を受けやすい。本発明では、発明の効果を損なわない範囲で、酸化防止剤などの安定剤を適宜使用することができる。 6. Other ingredients <antioxidants>
Polychloroprene latex adhesives are generally susceptible to oxygen degradation. In the present invention, stabilizers such as antioxidants can be used as appropriate within a range that does not impair the effects of the invention.
＜酸化防止剤＞
ポリクロロプレンラテックス接着剤は、一般に酸素による劣化を受けやすい。本発明では、発明の効果を損なわない範囲で、酸化防止剤などの安定剤を適宜使用することができる。 6. Other ingredients <antioxidants>
Polychloroprene latex adhesives are generally susceptible to oxygen degradation. In the present invention, stabilizers such as antioxidants can be used as appropriate within a range that does not impair the effects of the invention.
ポリクロロプレンラテックス接着剤に配合する酸化防止剤の添加量は、クロロプレン重合体ラテックスの固形分１００質量部に対して酸化防止剤を固形分換算で０．１～３質量部とすることが好ましい。この範囲に設定することによって、得られる接着剤の柔軟性の経時安定性を改良することができる。酸化防止剤が水に不溶であったり、クロロプレン重合体ラテックスの乳化状態を不安定化させたりする場合には、予め水系分散体に調製してから添加するとよい。本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、酸化防止剤を含まなくてもよい。
The amount of antioxidant added to the polychloroprene latex adhesive is preferably 0.1 to 3 parts by mass in terms of solid content per 100 parts by mass of solid content of the chloroprene polymer latex. By setting it within this range, the stability over time of the flexibility of the resulting adhesive can be improved. When the antioxidant is insoluble in water or destabilizes the emulsified state of the chloroprene polymer latex, it is preferable to prepare an aqueous dispersion in advance and then add it. The polychloroprene latex adhesive according to one embodiment of the invention may be antioxidant-free.
ポリクロロプレンラテックス接着剤には、本発明の効果を阻害しない範囲で、上記以外の添加剤として、充填材、顔料、着色剤、湿潤剤、消泡剤、増粘剤などを適宜使用することができる。
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、ポリビニルアルコールを含むことができる。ポリビニルアルコールの含有量は、ポリクロロプレンラテックス接着剤に含まれるクロロプレン重合体ラテックスの固形分１００質量％に対して、２質量％以下とすることができ、２質量％未満とすることができる。ポリビニルアルコールの含有量は、例えば、０、０．５、１.０、１．５、１．９、２．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、ポリビニルアルコールの含有量を一定の数値以下とすることにより、又はポリビニルアルコールを含まないものとすることにより、得られるポリクロロプレンラテックス接着剤の初期接着力を向上させることもできる。 In the polychloroprene latex adhesive, fillers, pigments, colorants, wetting agents, antifoaming agents, thickeners, etc. may be appropriately used as additives other than those mentioned above, to the extent that they do not impede the effects of the present invention. can.
A polychloroprene latex adhesive according to one embodiment of the invention may include polyvinyl alcohol. The content of polyvinyl alcohol can be 2% by mass or less, and can be less than 2% by mass, based on 100% by mass of the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive. The content of polyvinyl alcohol is, for example, 0, 0.5, 1.0, 1.5, 1.9, 2.0 parts by mass, and within the range between any two of the numerical values exemplified here. There may be. The polychloroprene latex adhesive according to one embodiment of the present invention is obtained by controlling the content of polyvinyl alcohol to a certain value or less, or by not containing polyvinyl alcohol. It is also possible to improve initial adhesion.
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、ポリビニルアルコールを含むことができる。ポリビニルアルコールの含有量は、ポリクロロプレンラテックス接着剤に含まれるクロロプレン重合体ラテックスの固形分１００質量％に対して、２質量％以下とすることができ、２質量％未満とすることができる。ポリビニルアルコールの含有量は、例えば、０、０．５、１.０、１．５、１．９、２．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、ポリビニルアルコールの含有量を一定の数値以下とすることにより、又はポリビニルアルコールを含まないものとすることにより、得られるポリクロロプレンラテックス接着剤の初期接着力を向上させることもできる。 In the polychloroprene latex adhesive, fillers, pigments, colorants, wetting agents, antifoaming agents, thickeners, etc. may be appropriately used as additives other than those mentioned above, to the extent that they do not impede the effects of the present invention. can.
A polychloroprene latex adhesive according to one embodiment of the invention may include polyvinyl alcohol. The content of polyvinyl alcohol can be 2% by mass or less, and can be less than 2% by mass, based on 100% by mass of the solid content of the chloroprene polymer latex contained in the polychloroprene latex adhesive. The content of polyvinyl alcohol is, for example, 0, 0.5, 1.0, 1.5, 1.9, 2.0 parts by mass, and within the range between any two of the numerical values exemplified here. There may be. The polychloroprene latex adhesive according to one embodiment of the present invention is obtained by controlling the content of polyvinyl alcohol to a certain value or less, or by not containing polyvinyl alcohol. It is also possible to improve initial adhesion.
また、本発明の一実施形態に係るポリクロロプレンラテックス接着剤には、クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）以外の、その他の樹脂エマルジョン（ラテックス）を、補助的に配合しても差し支えない。その他の樹脂エマルジョン（ラテックス）としては、具体的には、（変性）酢酸ビニル、酢酸ビニル・アクリル混合、アクリル・スチレン混合、ウレタンなどの樹脂エマルジョンが挙げられる。その他の樹脂エマルジョン（ラテックス）の配合量は、ポリクロロプレンラテックス接着剤の固形分１００質量％に対して、３０質量％（固形分換算）以下とすることができ、例えば、０、５、１０、１５、２０、２５、３０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）以外のその他の樹脂エマルジョン（ラテックス）を含まなくてもよい。
In addition, the polychloroprene latex adhesive according to an embodiment of the present invention may include other resin emulsions ( latex) may be added as an adjunct. Specific examples of other resin emulsions (latex) include resin emulsions such as (modified) vinyl acetate, vinyl acetate/acrylic mixture, acrylic/styrene mixture, and urethane. The amount of the other resin emulsion (latex) can be 30% by mass or less (in terms of solid content) based on 100% by mass of the solid content of the polychloroprene latex adhesive, for example, 0, 5, 10, The content may be 15, 20, 25, or 30% by mass, and may be within a range between any two of the numerical values exemplified here. The polychloroprene latex adhesive according to one embodiment of the present invention contains a resin emulsion (latex) other than the chloroprene polymer latex (a), the chlorinated polyolefin resin emulsion (b), and the tackifier resin emulsion (c). You don't have to.
７．ポリクロロプレンラテックス接着剤の特性
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、以下の手順で測定される初期接着強度１及び２が以下を満たすことが好ましい。
＜初期接着強度の測定方法＞
密度３０ｋｇ／ｍ３のウレタンフォーム（厚さ２０ｍｍ×長さ５０ｍｍ×幅５０ｍｍ）とポリプロピレンシート（厚さ１ｍｍ×長さ５０ｍｍ×幅２５ｍｍ）を被着体に用い、２３℃雰囲気下で接着剤を７０ｇ／ｍ２となるようにそれぞれの被着体にスプレー塗布する。塗布後２３℃雰囲気中で1０分間（初期接着強度１）又は２０分間（初期接着強度２）放置後、接着剤が未乾燥の状態でウレタンフォームとポリプロピレンの接着面同士を重ね合わせ、厚さ２１ｍｍの被着体（積層体）を２ｍｍに圧縮して１０秒間保持し、その後直ちに引張り試験機（Ａ＆Ｄ製テンシロン；引張り速度２００ｍｍ／ｍｉｎ）で接着面と垂直方向に引張り試験を行い、接着強度を測定する。 7. Characteristics of Polychloroprene Latex Adhesive It is preferable that the polychloroprene latex adhesive according to one embodiment of the present invention has initial adhesive strengths 1 and 2 measured by the following procedure that satisfy the following.
<Method for measuring initial adhesive strength>
Urethane foam (thickness 20 mm x length 50 mm x width 50 mm) with a density of 30 kg/ m3 and polypropylene sheet (thickness 1 mm x length 50 mm x width 25 mm) were used as adherends, and adhesive was applied in an atmosphere of 23 °C. Spray coat onto each adherend so that the amount is 70 g/m 2 . After application, leave in an atmosphere at 23°C for 10 minutes (initial adhesive strength 1) or 20 minutes (initial adhesive strength 2), then overlap the adhesive surfaces of the urethane foam and polypropylene with the adhesive still undried to a thickness of 21 mm. The adherend (laminate) was compressed to 2 mm and held for 10 seconds, and then immediately subjected to a tensile test in the direction perpendicular to the adhesive surface using a tensile tester (A&D Tensilon; tensile speed 200 mm/min) to determine the adhesive strength. Measure.
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、以下の手順で測定される初期接着強度１及び２が以下を満たすことが好ましい。
＜初期接着強度の測定方法＞
密度３０ｋｇ／ｍ３のウレタンフォーム（厚さ２０ｍｍ×長さ５０ｍｍ×幅５０ｍｍ）とポリプロピレンシート（厚さ１ｍｍ×長さ５０ｍｍ×幅２５ｍｍ）を被着体に用い、２３℃雰囲気下で接着剤を７０ｇ／ｍ２となるようにそれぞれの被着体にスプレー塗布する。塗布後２３℃雰囲気中で1０分間（初期接着強度１）又は２０分間（初期接着強度２）放置後、接着剤が未乾燥の状態でウレタンフォームとポリプロピレンの接着面同士を重ね合わせ、厚さ２１ｍｍの被着体（積層体）を２ｍｍに圧縮して１０秒間保持し、その後直ちに引張り試験機（Ａ＆Ｄ製テンシロン；引張り速度２００ｍｍ／ｍｉｎ）で接着面と垂直方向に引張り試験を行い、接着強度を測定する。 7. Characteristics of Polychloroprene Latex Adhesive It is preferable that the polychloroprene latex adhesive according to one embodiment of the present invention has initial adhesive strengths 1 and 2 measured by the following procedure that satisfy the following.
<Method for measuring initial adhesive strength>
Urethane foam (thickness 20 mm x length 50 mm x width 50 mm) with a density of 30 kg/ m3 and polypropylene sheet (thickness 1 mm x length 50 mm x width 25 mm) were used as adherends, and adhesive was applied in an atmosphere of 23 °C. Spray coat onto each adherend so that the amount is 70 g/m 2 . After application, leave in an atmosphere at 23°C for 10 minutes (initial adhesive strength 1) or 20 minutes (initial adhesive strength 2), then overlap the adhesive surfaces of the urethane foam and polypropylene with the adhesive still undried to a thickness of 21 mm. The adherend (laminate) was compressed to 2 mm and held for 10 seconds, and then immediately subjected to a tensile test in the direction perpendicular to the adhesive surface using a tensile tester (A&D Tensilon; tensile speed 200 mm/min) to determine the adhesive strength. Measure.
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、上記の手順で測定される初期接着強度１が、１．０Ｎ／ｃｍ２以上であることが好ましく、２．０Ｎ／ｃｍ２以上であることがより好ましい。初期接着強度１は、例えば、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０、５．５、６．０、６．５、７．０Ｎ／ｃｍ２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The polychloroprene latex adhesive according to an embodiment of the present invention preferably has an initial adhesive strength 1 of 1.0 N/cm 2 or more, preferably 2.0 N/cm 2 or more, as measured by the above procedure. It is more preferable. The initial adhesive strength 1 is, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6. 0, 6.5, 7.0 N/cm 2 , and may be within the range between any two of the numerical values exemplified here.
本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、上記の手順で測定される初期接着強度２が、３．５Ｎ／ｃｍ２以上であることが好ましく、４．０Ｎ／ｃｍ２以上であることがより好ましい。初期接着強度１は、例えば、３．５、４．０、４．５、５．０、５．５、６．０、６．５、７．０Ｎ／ｃｍ２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The polychloroprene latex adhesive according to an embodiment of the present invention preferably has an initial adhesive strength 2 of 3.5 N/cm 2 or more, preferably 4.0 N/cm 2 or more, as measured by the above procedure. It is more preferable. The initial adhesive strength 1 is, for example, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0 N/cm 2 , and the numerical values exemplified here It may be within the range between any two.
以上説明した本発明のポリクロロプレンラテックス接着剤は、様々な種類の被着体に用いることができるが、特に、ポリオレフィン樹脂を被着体とする場合に好適に使用することができる。本発明に係るポリクロロプレンラテックス接着剤は、接着剤使用時に、接着層の乾燥時間を短くし、かつ、乾燥温度を常温とし、湿潤状態であっても、ポリオレフィン樹脂と優れた初期接着力を有するため、被着体の少なくとも一方をポリオレフィン樹脂とする、ポリオレフィン樹脂接着用ポリクロロプレンラテックス接着剤とできる。本発明の一実施形態に係るポリクロロプレンラテックス接着剤は、例えば、自動車内装材として使用されるポリオレフィン樹脂とポリウレタンフォームや、ポリオレフィン樹脂とファブリックなどの接着用として有用である。
The polychloroprene latex adhesive of the present invention described above can be used for various types of adherends, but it can be particularly suitably used when the adherend is a polyolefin resin. The polychloroprene latex adhesive according to the present invention shortens the drying time of the adhesive layer when used as an adhesive, keeps the drying temperature at room temperature, and has excellent initial adhesive strength with polyolefin resin even in a wet state. Therefore, a polychloroprene latex adhesive for adhering to a polyolefin resin can be used, in which at least one of the adherends is made of a polyolefin resin. The polychloroprene latex adhesive according to one embodiment of the present invention is useful for adhering, for example, polyolefin resin and polyurethane foam used as automobile interior materials, polyolefin resin and fabric, and the like.
以下に実施例をあげて本発明を更に詳細に説明する。また、これらはいずれも例示的なものであって、本発明の内容を限定するものではない。
The present invention will be explained in more detail with reference to Examples below. Further, all of these are illustrative and do not limit the content of the present invention.
＜調整例１＞
「クロロプレン重合体ラテックスａ－１の製造」
内容積１０リットルの反応器を用い、窒素気流下で、水９０質量部、不均化ロジン酸４．５質量部、水酸化カリウム０．５質量部、ホルムアルデヒドナフタレンスルホン酸縮合物のナトリウム塩０．３質量部を仕込み、溶解後、撹拌しながらクロロプレン単量体１００質量部とｎ－ドデシルメルカプタン０．１質量部を加えた。過硫酸カリウムを開始剤として用い、窒素雰囲気下、１０℃で重合し、重合率が７０％に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応クロロプレン単量体を除去し、更に減圧下で水分を蒸発させ濃縮を行い、固形分濃度が５５質量％となるように調整し、トルエン不溶分が１．９質量％のクロロプレン重合体ラテックスａ－１を得た。 <Adjustment example 1>
"Manufacture of chloroprene polymer latex a-1"
Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C. under a nitrogen atmosphere using potassium persulfate as an initiator, and when the polymerization rate reached 70%, an emulsion of phenothiazine was added to stop the polymerization. Unreacted chloroprene monomer was removed under reduced pressure, water was further evaporated under reduced pressure, and the solid content was adjusted to 55% by mass. Polymer latex a-1 was obtained.
「クロロプレン重合体ラテックスａ－１の製造」
内容積１０リットルの反応器を用い、窒素気流下で、水９０質量部、不均化ロジン酸４．５質量部、水酸化カリウム０．５質量部、ホルムアルデヒドナフタレンスルホン酸縮合物のナトリウム塩０．３質量部を仕込み、溶解後、撹拌しながらクロロプレン単量体１００質量部とｎ－ドデシルメルカプタン０．１質量部を加えた。過硫酸カリウムを開始剤として用い、窒素雰囲気下、１０℃で重合し、重合率が７０％に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応クロロプレン単量体を除去し、更に減圧下で水分を蒸発させ濃縮を行い、固形分濃度が５５質量％となるように調整し、トルエン不溶分が１．９質量％のクロロプレン重合体ラテックスａ－１を得た。 <Adjustment example 1>
"Manufacture of chloroprene polymer latex a-1"
Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C. under a nitrogen atmosphere using potassium persulfate as an initiator, and when the polymerization rate reached 70%, an emulsion of phenothiazine was added to stop the polymerization. Unreacted chloroprene monomer was removed under reduced pressure, water was further evaporated under reduced pressure, and the solid content was adjusted to 55% by mass. Polymer latex a-1 was obtained.
＜調整例２＞
「クロロプレン重合体ラテックスａ－２の製造」
内容積１０リットルの反応器を用い、窒素気流下で、水９０質量部、不均化ロジン酸４．５質量部、水酸化カリウム０．５質量部、ホルムアルデヒドナフタレンスルホン酸縮合物のナトリウム塩０．３質量部を仕込み、溶解後、撹拌しながらクロロプレン単量体１００質量部とｎ－ドデシルメルカプタン０．１質量部を加えた。過硫酸カリウムを開始剤として用い、窒素雰囲気下、１０℃で重合し、重合率が９０％に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応クロロプレン単量体を除去し、更に減圧下で水分を蒸発させ濃縮を行い、固形分濃度が５５質量％となるように調整し、トルエン不溶分が２５質量％のクロロプレン重合体ラテックスａ－２を得た。 <Adjustment example 2>
"Manufacture of chloroprene polymer latex a-2"
Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C. under a nitrogen atmosphere using potassium persulfate as an initiator, and when the polymerization rate reached 90%, an emulsion of phenothiazine was added to stop the polymerization. Unreacted chloroprene monomer was removed under reduced pressure, and water was further evaporated and concentrated under reduced pressure to adjust the solid content concentration to 55% by mass, resulting in a chloroprene polymer with a toluene insoluble content of 25% by mass. Latex a-2 was obtained.
「クロロプレン重合体ラテックスａ－２の製造」
内容積１０リットルの反応器を用い、窒素気流下で、水９０質量部、不均化ロジン酸４．５質量部、水酸化カリウム０．５質量部、ホルムアルデヒドナフタレンスルホン酸縮合物のナトリウム塩０．３質量部を仕込み、溶解後、撹拌しながらクロロプレン単量体１００質量部とｎ－ドデシルメルカプタン０．１質量部を加えた。過硫酸カリウムを開始剤として用い、窒素雰囲気下、１０℃で重合し、重合率が９０％に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応クロロプレン単量体を除去し、更に減圧下で水分を蒸発させ濃縮を行い、固形分濃度が５５質量％となるように調整し、トルエン不溶分が２５質量％のクロロプレン重合体ラテックスａ－２を得た。 <Adjustment example 2>
"Manufacture of chloroprene polymer latex a-2"
Using a reactor with an internal volume of 10 liters, under a nitrogen stream, 90 parts by mass of water, 4.5 parts by mass of disproportionated rosin acid, 0.5 parts by mass of potassium hydroxide, and 0 parts of sodium salt of formaldehyde naphthalene sulfonic acid condensate. After dissolving, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecylmercaptan were added while stirring. Polymerization was carried out at 10° C. under a nitrogen atmosphere using potassium persulfate as an initiator, and when the polymerization rate reached 90%, an emulsion of phenothiazine was added to stop the polymerization. Unreacted chloroprene monomer was removed under reduced pressure, and water was further evaporated and concentrated under reduced pressure to adjust the solid content concentration to 55% by mass, resulting in a chloroprene polymer with a toluene insoluble content of 25% by mass. Latex a-2 was obtained.
得られたクロロプレン重合体のトルエン不溶分は以下の方法に従い測定した。
〔トルエン不溶分測定〕
ラテックス試料を凍結乾燥し精秤してＡ（ｇ）とした。２３℃で２０時間、トルエンで溶解（０．６％に調製）し、遠心分離機を使用し、更に２００メッシュの金網を用いてゲル分を分離した。分離したゲル分を風乾後１１０℃雰囲気下で、１時間乾燥し、精秤してＢ（ｇ）とした。ゲル分は下式に従って算出した。
トルエン不溶分＝Ｂ／Ａ×１００（％） The toluene insoluble content of the obtained chloroprene polymer was measured according to the following method.
[Toluene insoluble content measurement]
The latex sample was freeze-dried and accurately weighed to give A(g). The mixture was dissolved in toluene (adjusted to 0.6%) at 23° C. for 20 hours, and the gel fraction was separated using a centrifuge and a 200-mesh wire mesh. The separated gel fraction was air-dried in an atmosphere of 110° C. for 1 hour, and accurately weighed to obtain B(g). The gel content was calculated according to the formula below.
Toluene insoluble content = B/A x 100 (%)
〔トルエン不溶分測定〕
ラテックス試料を凍結乾燥し精秤してＡ（ｇ）とした。２３℃で２０時間、トルエンで溶解（０．６％に調製）し、遠心分離機を使用し、更に２００メッシュの金網を用いてゲル分を分離した。分離したゲル分を風乾後１１０℃雰囲気下で、１時間乾燥し、精秤してＢ（ｇ）とした。ゲル分は下式に従って算出した。
トルエン不溶分＝Ｂ／Ａ×１００（％） The toluene insoluble content of the obtained chloroprene polymer was measured according to the following method.
[Toluene insoluble content measurement]
The latex sample was freeze-dried and accurately weighed to give A(g). The mixture was dissolved in toluene (adjusted to 0.6%) at 23° C. for 20 hours, and the gel fraction was separated using a centrifuge and a 200-mesh wire mesh. The separated gel fraction was air-dried in an atmosphere of 110° C. for 1 hour, and accurately weighed to obtain B(g). The gel content was calculated according to the formula below.
Toluene insoluble content = B/A x 100 (%)
［実施例１］
クロロプレン重合体ラテックス（ａ）として、上述で得られたクロロプレン重合体ラテックスａ－１を固形分換算で１００質量部、塩素化ポリオレフィン樹脂エマルジョン（ｂ）としてＥＷ－５３０３（東洋紡社製、無水マレイン酸変性塩素化エチレン－プロピレン－ブテン共重合樹脂エマルジョン、塩素含有率１７質量％）を固形分換算で５質量部、粘着付与樹脂エマルジョン（ｃ）としてタマノルＥ－１００（荒川化学工業製）を固形分換算で５０質量部、ｐＨ調整剤（ｄ）としてグリシンを固形分換算で１０質量部、可塑剤としてジブチルセバケートを固形分換算で９質量部添加し、実施例１のポリクロロプレンラテックス接着剤を得た。 [Example 1]
As the chloroprene polymer latex (a), 100 parts by mass of the chloroprene polymer latex a-1 obtained above was used in terms of solid content, and as the chlorinated polyolefin resin emulsion (b), EW-5303 (manufactured by Toyobo Co., Ltd., maleic anhydride) was added. Modified chlorinated ethylene-propylene-butene copolymer resin emulsion, chlorine content 17% by mass) was 5 parts by mass in terms of solid content, and Tamanol E-100 (manufactured by Arakawa Chemical Industries) was used as the tackifying resin emulsion (c) in solid content. 50 parts by mass in terms of solid content, 10 parts by mass of glycine as a pH adjuster (d) in terms of solid content, and 9 parts by mass of dibutyl sebacate as a plasticizer in terms of solid content, and the polychloroprene latex adhesive of Example 1. Obtained.
クロロプレン重合体ラテックス（ａ）として、上述で得られたクロロプレン重合体ラテックスａ－１を固形分換算で１００質量部、塩素化ポリオレフィン樹脂エマルジョン（ｂ）としてＥＷ－５３０３（東洋紡社製、無水マレイン酸変性塩素化エチレン－プロピレン－ブテン共重合樹脂エマルジョン、塩素含有率１７質量％）を固形分換算で５質量部、粘着付与樹脂エマルジョン（ｃ）としてタマノルＥ－１００（荒川化学工業製）を固形分換算で５０質量部、ｐＨ調整剤（ｄ）としてグリシンを固形分換算で１０質量部、可塑剤としてジブチルセバケートを固形分換算で９質量部添加し、実施例１のポリクロロプレンラテックス接着剤を得た。 [Example 1]
As the chloroprene polymer latex (a), 100 parts by mass of the chloroprene polymer latex a-1 obtained above was used in terms of solid content, and as the chlorinated polyolefin resin emulsion (b), EW-5303 (manufactured by Toyobo Co., Ltd., maleic anhydride) was added. Modified chlorinated ethylene-propylene-butene copolymer resin emulsion, chlorine content 17% by mass) was 5 parts by mass in terms of solid content, and Tamanol E-100 (manufactured by Arakawa Chemical Industries) was used as the tackifying resin emulsion (c) in solid content. 50 parts by mass in terms of solid content, 10 parts by mass of glycine as a pH adjuster (d) in terms of solid content, and 9 parts by mass of dibutyl sebacate as a plasticizer in terms of solid content, and the polychloroprene latex adhesive of Example 1. Obtained.
［実施例２］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更した以外は、実施例１と同様の条件にて実施例２のポリクロロプレンラテックス接着剤を得た。 [Example 2]
As shown in Table 1, a polychloroprene latex adhesive of Example 2 was obtained under the same conditions as Example 1 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更した以外は、実施例１と同様の条件にて実施例２のポリクロロプレンラテックス接着剤を得た。 [Example 2]
As shown in Table 1, a polychloroprene latex adhesive of Example 2 was obtained under the same conditions as Example 1 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
［実施例３］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）としてＥＷ－５３０３（東洋紡社製、塩素含有率１７質量％）の代わりにＥＨ－８０１（東洋紡社製、塩素含有率１６質量％）を添加した以外は、実施例１と同様の条件にて実施例３のポリクロロプレンラテックス接着剤を得た。 [Example 3]
As shown in Table 1, EH-801 (manufactured by Toyobo, chlorine content 16% by mass) was added instead of EW-5303 (manufactured by Toyobo, chlorine content 17% by mass) as the chlorinated polyolefin resin emulsion (b). A polychloroprene latex adhesive of Example 3 was obtained under the same conditions as Example 1 except for the following.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）としてＥＷ－５３０３（東洋紡社製、塩素含有率１７質量％）の代わりにＥＨ－８０１（東洋紡社製、塩素含有率１６質量％）を添加した以外は、実施例１と同様の条件にて実施例３のポリクロロプレンラテックス接着剤を得た。 [Example 3]
As shown in Table 1, EH-801 (manufactured by Toyobo, chlorine content 16% by mass) was added instead of EW-5303 (manufactured by Toyobo, chlorine content 17% by mass) as the chlorinated polyolefin resin emulsion (b). A polychloroprene latex adhesive of Example 3 was obtained under the same conditions as Example 1 except for the following.
［実施例４］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更した以外は、実施例３と同様の条件にて実施例４のポリクロロプレンラテックス接着剤を得た。 [Example 4]
As shown in Table 1, a polychloroprene latex adhesive of Example 4 was obtained under the same conditions as Example 3 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更した以外は、実施例３と同様の条件にて実施例４のポリクロロプレンラテックス接着剤を得た。 [Example 4]
As shown in Table 1, a polychloroprene latex adhesive of Example 4 was obtained under the same conditions as Example 3 except that the amount of chlorinated polyolefin resin emulsion (b) added was changed.
［実施例５及び６］
表１に示すとおり、粘着付与樹脂エマルジョン（ｃ）の添加量を変更した以外は、実施例１と同様の条件にて実施例５及び６のポリクロロプレンラテックス接着剤を得た。 [Example 5 and 6]
As shown in Table 1, polychloroprene latex adhesives of Examples 5 and 6 were obtained under the same conditions as in Example 1, except that the amount of tackifier resin emulsion (c) added was changed.
表１に示すとおり、粘着付与樹脂エマルジョン（ｃ）の添加量を変更した以外は、実施例１と同様の条件にて実施例５及び６のポリクロロプレンラテックス接着剤を得た。 [Example 5 and 6]
As shown in Table 1, polychloroprene latex adhesives of Examples 5 and 6 were obtained under the same conditions as in Example 1, except that the amount of tackifier resin emulsion (c) added was changed.
［実施例７］
表１に示すとおり、可塑剤を添加しなかったこと以外は、実施例１と同様の条件にて実施例７のポリクロロプレンラテックス接着剤を得た。 [Example 7]
As shown in Table 1, a polychloroprene latex adhesive of Example 7 was obtained under the same conditions as Example 1 except that no plasticizer was added.
表１に示すとおり、可塑剤を添加しなかったこと以外は、実施例１と同様の条件にて実施例７のポリクロロプレンラテックス接着剤を得た。 [Example 7]
As shown in Table 1, a polychloroprene latex adhesive of Example 7 was obtained under the same conditions as Example 1 except that no plasticizer was added.
［実施例８及び９］
表１に示すとおり、ｐＨ調整剤（ｄ）の添加量を変更した以外は、実施例１と同様の条件にて実施例８及び９のポリクロロプレンラテックス接着剤を得た。 [Example 8 and 9]
As shown in Table 1, polychloroprene latex adhesives of Examples 8 and 9 were obtained under the same conditions as in Example 1, except that the amount of the pH adjuster (d) added was changed.
表１に示すとおり、ｐＨ調整剤（ｄ）の添加量を変更した以外は、実施例１と同様の条件にて実施例８及び９のポリクロロプレンラテックス接着剤を得た。 [Example 8 and 9]
As shown in Table 1, polychloroprene latex adhesives of Examples 8 and 9 were obtained under the same conditions as in Example 1, except that the amount of the pH adjuster (d) added was changed.
［比較例１］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）及び粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例１のポリクロロプレンラテックス接着剤を得た。 [Comparative example 1]
As shown in Table 1, the polychloroprene latex adhesive of Comparative Example 1 was prepared under the same conditions as Example 1, except that the chlorinated polyolefin resin emulsion (b) and tackifying resin emulsion (c) were not added. Obtained.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）及び粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例１のポリクロロプレンラテックス接着剤を得た。 [Comparative example 1]
As shown in Table 1, the polychloroprene latex adhesive of Comparative Example 1 was prepared under the same conditions as Example 1, except that the chlorinated polyolefin resin emulsion (b) and tackifying resin emulsion (c) were not added. Obtained.
［比較例２］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更し、粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例２のポリクロロプレンラテックス接着剤を得た。 [Comparative example 2]
As shown in Table 1, Comparative Example 2 was prepared under the same conditions as Example 1, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifier resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更し、粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例２のポリクロロプレンラテックス接着剤を得た。 [Comparative example 2]
As shown in Table 1, Comparative Example 2 was prepared under the same conditions as Example 1, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifier resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
［比較例３］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更し、粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例３と同様の条件にて比較例３のポリクロロプレンラテックス接着剤を得た。 [Comparative example 3]
As shown in Table 1, Comparative Example 3 was prepared under the same conditions as Example 3, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifying resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）の添加量を変更し、粘着付与樹脂エマルジョン（ｃ）を添加しなかったこと以外は、実施例３と同様の条件にて比較例３のポリクロロプレンラテックス接着剤を得た。 [Comparative example 3]
As shown in Table 1, Comparative Example 3 was prepared under the same conditions as Example 3, except that the amount of chlorinated polyolefin resin emulsion (b) was changed and the tackifying resin emulsion (c) was not added. A polychloroprene latex adhesive was obtained.
［比較例４］
表１に示すとおり、クロロプレン重合体ラテックス（ａ）として、クロロプレン重合体ラテックスａ－１の代わりにクロロプレン重合体ラテックスａ－２を添加した以外は、実施例１と同様の条件にて比較例４のポリクロロプレンラテックス接着剤を得た。 [Comparative example 4]
As shown in Table 1, Comparative Example 4 was carried out under the same conditions as Example 1, except that chloroprene polymer latex a-2 was added as chloroprene polymer latex (a) instead of chloroprene polymer latex a-1. A polychloroprene latex adhesive was obtained.
表１に示すとおり、クロロプレン重合体ラテックス（ａ）として、クロロプレン重合体ラテックスａ－１の代わりにクロロプレン重合体ラテックスａ－２を添加した以外は、実施例１と同様の条件にて比較例４のポリクロロプレンラテックス接着剤を得た。 [Comparative example 4]
As shown in Table 1, Comparative Example 4 was carried out under the same conditions as Example 1, except that chloroprene polymer latex a-2 was added as chloroprene polymer latex (a) instead of chloroprene polymer latex a-1. A polychloroprene latex adhesive was obtained.
［比較例５］
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例５のポリクロロプレンラテックス接着剤を得た。 [Comparative example 5]
As shown in Table 1, a polychloroprene latex adhesive of Comparative Example 5 was obtained under the same conditions as in Example 1 except that the chlorinated polyolefin resin emulsion (b) was not added.
表１に示すとおり、塩素化ポリオレフィン樹脂エマルジョン（ｂ）を添加しなかったこと以外は、実施例１と同様の条件にて比較例５のポリクロロプレンラテックス接着剤を得た。 [Comparative example 5]
As shown in Table 1, a polychloroprene latex adhesive of Comparative Example 5 was obtained under the same conditions as in Example 1 except that the chlorinated polyolefin resin emulsion (b) was not added.
以上で得られた各ポリクロロプレンラテックス接着剤組成物につき、以下の通り接着強度の評価を行った。なお、表１の配合処方は固形分換算での質量部である。
The adhesive strength of each of the polychloroprene latex adhesive compositions obtained above was evaluated as follows. Note that the formulations in Table 1 are parts by mass in terms of solid content.
〔初期接着強度１、初期接着強度２〕
密度３０ｋｇ／ｍ３ のウレタンフォーム（厚さ２０ｍｍ×長さ５０ｍｍ×幅５０ｍｍ）とポリプロピレンシート（厚さ１ｍｍ×長さ５０ｍｍ×幅２５ｍｍ）を被着体に用い、２３℃雰囲気下で接着剤を７０ｇ／ｍ２となるようにそれぞれの被着体にスプレー塗布した。塗布後２３℃雰囲気中で1０分間（初期接着強度１）又は２０分間（初期接着強度２）放置後、接着剤が未乾燥の状態でウレタンフォームとポリプロピレンの接着面同士を重ね合わせ、厚さ２１ｍｍの被着体（積層体）を２ｍｍに圧縮して１０秒間保持した。その後直ちに引張り試験機（Ａ＆Ｄ製テンシロン；引張り速度２００ｍｍ／ｍｉｎ）で接着面と垂直方向に引張り試験を行い、接着強度を測定した。 [Initial adhesive strength 1, initial adhesive strength 2]
Urethane foam (thickness 20 mm x length 50 mm x width 50 mm) with a density of 30 kg/ m3 and polypropylene sheet (thickness 1 mm x length 50 mm x width 25 mm) were used as adherends, and adhesive was applied in an atmosphere of 23 °C. Each adherend was spray coated at a weight of 70 g/m 2 . After application, leave it for 10 minutes (initial adhesive strength 1) or 20 minutes (initial adhesive strength 2) in an atmosphere at 23°C, then overlap the adhesive surfaces of the urethane foam and polypropylene with the adhesive still undried to a thickness of 21 mm. The adherend (laminate) was compressed to 2 mm and held for 10 seconds. Immediately thereafter, a tensile test was conducted in a direction perpendicular to the adhesive surface using a tensile tester (Tensilon manufactured by A&D; tensile speed: 200 mm/min) to measure adhesive strength.
密度３０ｋｇ／ｍ３ のウレタンフォーム（厚さ２０ｍｍ×長さ５０ｍｍ×幅５０ｍｍ）とポリプロピレンシート（厚さ１ｍｍ×長さ５０ｍｍ×幅２５ｍｍ）を被着体に用い、２３℃雰囲気下で接着剤を７０ｇ／ｍ２となるようにそれぞれの被着体にスプレー塗布した。塗布後２３℃雰囲気中で1０分間（初期接着強度１）又は２０分間（初期接着強度２）放置後、接着剤が未乾燥の状態でウレタンフォームとポリプロピレンの接着面同士を重ね合わせ、厚さ２１ｍｍの被着体（積層体）を２ｍｍに圧縮して１０秒間保持した。その後直ちに引張り試験機（Ａ＆Ｄ製テンシロン；引張り速度２００ｍｍ／ｍｉｎ）で接着面と垂直方向に引張り試験を行い、接着強度を測定した。 [Initial adhesive strength 1, initial adhesive strength 2]
Urethane foam (thickness 20 mm x length 50 mm x width 50 mm) with a density of 30 kg/ m3 and polypropylene sheet (thickness 1 mm x length 50 mm x width 25 mm) were used as adherends, and adhesive was applied in an atmosphere of 23 °C. Each adherend was spray coated at a weight of 70 g/m 2 . After application, leave it for 10 minutes (initial adhesive strength 1) or 20 minutes (initial adhesive strength 2) in an atmosphere at 23°C, then overlap the adhesive surfaces of the urethane foam and polypropylene with the adhesive still undried to a thickness of 21 mm. The adherend (laminate) was compressed to 2 mm and held for 10 seconds. Immediately thereafter, a tensile test was conducted in a direction perpendicular to the adhesive surface using a tensile tester (Tensilon manufactured by A&D; tensile speed: 200 mm/min) to measure adhesive strength.
表１から明らかなように、本発明によるポリクロロプレンラテックス接着剤は、初期接着力、特に湿潤状態における接着力が改善され、優れた初期接着強度の求められる用途に好適な接着剤、特にポリオレフィン樹脂やポリウレタンフォームの接着に使用されるスプレータイプの接着剤として好適に用いられることが確認された。
As is clear from Table 1, the polychloroprene latex adhesive according to the present invention has improved initial adhesive strength, especially adhesive strength in a wet state, and is suitable for applications requiring excellent initial adhesive strength, especially for polyolefin resins. It has been confirmed that it can be suitably used as a spray-type adhesive for adhering polyurethane foams and polyurethane foams.
Claims (4)
- クロロプレン重合体ラテックス（ａ）、塩素化ポリオレフィン樹脂エマルジョン（ｂ）、粘着付与樹脂エマルジョン（ｃ）、及びｐＨ調整剤（ｄ）を含有するポリクロロプレンラテックス接着剤であって、
前記クロロプレン重合体ラテックス（ａ）が、トルエン不溶分が２０質量％以下であるクロロプレン重合体を含む、ポリクロロプレンラテックス接着剤。 A polychloroprene latex adhesive comprising a chloroprene polymer latex (a), a chlorinated polyolefin resin emulsion (b), a tackifier resin emulsion (c), and a pH adjuster (d),
A polychloroprene latex adhesive, wherein the chloroprene polymer latex (a) contains a chloroprene polymer having a toluene insoluble content of 20% by mass or less. - 前記ポリクロロプレンラテックス接着剤に含まれる、前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、
前記塩素化ポリオレフィン樹脂エマルジョン（ｂ）を固形分換算で１～２０質量部、
前記粘着付与樹脂エマルジョン（Ｃ）を固形分換算で１～１００質量部、
前記ｐＨ調整剤（ｄ）を固形分換算で０．１～３０質量部、
含有する、請求項１に記載のポリクロロプレンラテックス接着剤。 When the chloroprene polymer latex (a) contained in the polychloroprene latex adhesive is 100 parts by mass in terms of solid content,
1 to 20 parts by mass of the chlorinated polyolefin resin emulsion (b) in terms of solid content,
1 to 100 parts by mass of the tackifying resin emulsion (C) in terms of solid content,
0.1 to 30 parts by mass of the pH adjuster (d) in terms of solid content,
The polychloroprene latex adhesive according to claim 1, comprising: - 前記クロロプレン重合体ラテックス（ａ）を固形分換算で１００質量部としたとき、
可塑剤（ｅ）を固形分換算で０．１～１００質量部、
含有する、請求項１又は請求項２に記載のポリクロロプレンラテックス接着剤。 When the chloroprene polymer latex (a) is 100 parts by mass in terms of solid content,
0.1 to 100 parts by mass of plasticizer (e) in terms of solid content,
The polychloroprene latex adhesive according to claim 1 or 2, comprising: - 請求項１又は請求項２に記載のポリクロロプレンラテックス接着剤であって、被着体の少なくとも一方をポリオレフィン樹脂とする、ポリオレフィン樹脂接着用ポリクロロプレンラテックス接着剤。 The polychloroprene latex adhesive according to claim 1 or 2, wherein at least one of the adherends is a polyolefin resin.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001019922A (en) * | 1999-07-05 | 2001-01-23 | Denki Kagaku Kogyo Kk | Adhesive composition using chloroprene latex |
| JP2002275442A (en) * | 2001-03-15 | 2002-09-25 | Hitachi Kasei Polymer Co Ltd | Chloroprene-based latex-type adhesive composition |
| JP2004197028A (en) * | 2002-12-20 | 2004-07-15 | Aica Kogyo Co Ltd | Aqueous adhesive composition |
| WO2018008509A1 (en) * | 2016-07-05 | 2018-01-11 | デンカ株式会社 | Latex composition and one-pack type aqueous adhesive composed of said latex composition |
| WO2018043586A1 (en) * | 2016-09-02 | 2018-03-08 | デンカ株式会社 | Chloroprene rubber latex adhesive composition |
| WO2022025118A1 (en) * | 2020-07-31 | 2022-02-03 | 昭和電工株式会社 | Chloroprene rubber latex adhesive composition and method for producing same, adhesive layer, and laminate |
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- 2023-05-31 WO PCT/JP2023/020265 patent/WO2023238748A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001019922A (en) * | 1999-07-05 | 2001-01-23 | Denki Kagaku Kogyo Kk | Adhesive composition using chloroprene latex |
| JP2002275442A (en) * | 2001-03-15 | 2002-09-25 | Hitachi Kasei Polymer Co Ltd | Chloroprene-based latex-type adhesive composition |
| JP2004197028A (en) * | 2002-12-20 | 2004-07-15 | Aica Kogyo Co Ltd | Aqueous adhesive composition |
| WO2018008509A1 (en) * | 2016-07-05 | 2018-01-11 | デンカ株式会社 | Latex composition and one-pack type aqueous adhesive composed of said latex composition |
| WO2018043586A1 (en) * | 2016-09-02 | 2018-03-08 | デンカ株式会社 | Chloroprene rubber latex adhesive composition |
| WO2022025118A1 (en) * | 2020-07-31 | 2022-02-03 | 昭和電工株式会社 | Chloroprene rubber latex adhesive composition and method for producing same, adhesive layer, and laminate |
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