WO2014069459A1 - 樹脂ゴム複合体 - Google Patents
樹脂ゴム複合体 Download PDFInfo
- Publication number
- WO2014069459A1 WO2014069459A1 PCT/JP2013/079277 JP2013079277W WO2014069459A1 WO 2014069459 A1 WO2014069459 A1 WO 2014069459A1 JP 2013079277 W JP2013079277 W JP 2013079277W WO 2014069459 A1 WO2014069459 A1 WO 2014069459A1
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- WIPO (PCT)
- Prior art keywords
- acrylic rubber
- resin
- rubber
- plasma treatment
- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
- B29C2059/145—Atmospheric plasma
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
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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
- C09J2477/00—Presence of polyamide
- C09J2477/006—Presence of polyamide in the substrate
Definitions
- the present invention relates to a resin rubber composite. More specifically, the present invention relates to a resin rubber composite in which a polyamide-based resin molded product and acrylic rubber are directly bonded without using an adhesive.
- Patent Document 1 discloses a polyamide resin and an alkoxysilane compound subjected to plasma treatment, corona discharge treatment or ultraviolet irradiation treatment.
- R 1 , R 2 Arbitrary functional groups
- R 3 , R 4 A resin rubber laminate in which a rubber composition to which a hydrocarbon group has been added is laminated without using an adhesive is described.
- acrylic rubber there is no example of acrylic rubber as rubber to which an alkoxysilane compound is added.
- Patent Document 2 describes a method of integrally molding the other part.
- vulcanized rubber compounds such as acrylic rubber compounds
- molding materials are molded members such as injection molded members, extrudates, compression members, or single layer sheets, multilayer sheets, fibers.
- molded members such as injection molded members, extrudates, compression members, or single layer sheets, multilayer sheets, fibers.
- semi-finished product such as a structure, and this is an unvulcanized rubber compound.
- Patent Document 3 discloses a fuel hose including a resin layer and an outer rubber layer laminated on the outer periphery thereof, and after forming a resin layer such as a polyamide-based resin by extrusion molding, the outer rubber layer is extruded. Prior to molding, it is described that the outer peripheral surface of the resin layer is subjected to microwave plasma treatment under reduced pressure. However, acrylic rubber is only exemplified as rubber for extruding the outer rubber layer.
- An object of the present invention is to provide a resin rubber composite in which a polyamide-based resin molded article and acrylic rubber are effectively directly bonded without using an adhesive.
- An object of the present invention is to directly vulcanize and bond a higher fatty acid salt-sulfur vulcanized acrylic rubber composition for forming an acrylic rubber layer on a low-pressure plasma-treated polyamide resin molded article without using an adhesive. This is achieved by a resin rubber composite.
- the resin rubber composite according to the present invention has the following features.
- Plasma treatment of a polyamide-based resin molded article is performed by a low-pressure plasma treatment method, and when this is performed by an atmospheric pressure plasma treatment method, desired resin-rubber adhesion cannot be ensured.
- the polyphenylene sulfide exemplified in Patent Document 3 is used in place of the polyamide-based resin, no adhesion between the resin and the acrylic rubber can be obtained.
- a higher fatty acid salt-sulfur vulcanized acrylic rubber is used, and a triazine vulcanized system which is an acrylic rubber having other crosslinkable groups.
- the alkoxysilane compound which was an essential component in Patent Document 1, is an optional component in the present invention, and its adhesiveness is not affected by the presence or absence thereof.
- polyamide-based resin to be subjected to the low-pressure plasma treatment examples include the following as typical polyamide (PA) types and monomers.
- PA polyamide
- Type CH 2 / NHCO base monomer 46 Tetramethylenediamine-adipate 6 5 ⁇ -caprolactam, ⁇ -aminocaproic acid 66 5 Hexamethylenediamine-adipate 610 7 Hexamethylenediamine-sebacate 612 8 Hexamethylenediamine-dodecanedioate 11 10 ⁇ -Aminoundecanoic acid 12 11 ⁇ -laurolactam, ⁇ -aminododecanoic acid
- PA polyamide
- PA613, 3T, PA810, PA812, PA1010, PA1012, PA1212, PAPACM12, etc. are also used.
- These polyamide-based resins can be used alone or in combination, and can also be used by blending with other resins such as polypropylene as long as the purpose is not impaired.
- these polyamide-based molded articles are formed by vulcanizing and bonding acrylic rubber to form a laminate, which can be combined, for example, a plate, a rod, a hollow having a flat surface, a curved surface, an uneven surface, and the like.
- a laminate which can be combined, for example, a plate, a rod, a hollow having a flat surface, a curved surface, an uneven surface, and the like.
- it is also used as an element such as a hose, an anti-vibration rubber, an air spring, a fuel guide system, a cooling fluid guide system, or an oil guide system.
- a low pressure plasma treatment method is applied to the outer surface of these polyamide resin molded articles.
- the low-pressure plasma treatment is performed in an inert gas atmosphere such as He gas, Ne gas, Ar gas, Kr gas, Xe gas, and N 2 gas in a glass vacuum vessel equipped with two parallel plate electrodes.
- He gas, Ar gas, or N 2 gas is used alone or in combination, using a high frequency power source with a frequency of 40 kHz, 13.56 MHz, or a microwave power source with a frequency of 433 MHz to 2.45 GHz, a pressure of about 10 to 1000 Pa, It is performed under conditions of about 10 to 30000 W output and about 0.1 to 60 minutes.
- a chlorine group-containing acrylic rubber which is an acrylic rubber having a chlorine group as a vulcanizable group is used.
- At least one of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms and a chlorine group-containing unsaturated compound may be used.
- a polymerized one is used.
- alkyl acrylate examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and methacrylates corresponding thereto.
- the longer the chain length of the alkyl group the more advantageous in terms of cold resistance, but disadvantageous in oil resistance, and the shorter the chain length, the opposite tendency is seen, from the balance of oil resistance and cold resistance.
- alkoxyalkyl acrylate for example, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, n-butoxyethyl acrylate, ethoxypropyl acrylate, etc. are used, preferably 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate is used. It is done.
- Alkoxyalkyl acrylates and alkyl acrylates can be used alone, but preferably the former is used in a proportion of 60 to 0% by weight and the latter is used in a proportion of 40 to 100% by weight when the alkoxyalkyl acrylate is copolymerized. Has a good balance between oil resistance and cold resistance, but when it is copolymerized at a higher ratio, normal properties and heat resistance tend to decrease.
- chlorine group-containing acrylic rubber chlorine group-containing unsaturated compounds such as chloroethyl vinyl ether, chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate, allyl chloroacetate, etc. Copolymerized at a copolymerization ratio of about 0.3 to 5% by weight, preferably about 0.3 to 5% by weight, is used.
- these chlorine group-containing unsaturated compounds those obtained by copolymerizing vinyl chloroacetate or the like form an active chlorine group-containing acrylic rubber.
- other copolymerizable ethylenically unsaturated monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, (meth) acrylonitrile, acrylic acid amide, vinyl acetate, Cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, ethylene, propylene, piperylene, butadiene, isoprene, pentadiene, and the like can be copolymerized in a proportion of about 50% by weight or less.
- a polyfunctional (meth) acrylate or oligomer having a glycol residue in the side chain such as ethylene glycol, propylene glycol, 1,4- Di (meth) acrylates of alkylene glycols such as butanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, dialkylene glycols such as tetraethylene glycol, tripropylene glycol and polypropylene glycol ( (Meth) acrylate, bisphenol A / ethylene oxide adduct diacrylate, dimethylol tricyclodecane diacrylate, glycerin methacrylate acrylate, 3-acryloyloxyglycerin monomethacrylate, and the like can be further copolymerized and used.
- alkylene glycols such as butanediol, 1,6-hexanediol, 1,9-nonanediol and
- These chlorine group-containing acrylic elastomers are vulcanized with a higher fatty acid salt-sulfur vulcanizing agent.
- higher fatty acid metal salts include alkali metal salts or alkaline earth metal salts of fatty acids having 8 to 18 carbon atoms in the alkyl group or alkenyl group, such as sodium stearate, potassium stearate, potassium myristate, sodium palmitate, stearate.
- Calcium phosphate, magnesium stearate, sodium oleate, potassium oleate, barium oleate, etc., alone or in combination, are about 0.5 to 10 parts by weight, preferably about 1.5 to 8 parts per 100 parts by weight of active chlorine group-containing acrylic rubber Used in parts by weight.
- Sulfur or a sulfur donor such as polymer sulfur as a sulfur vulcanizing agent is used at a ratio of about 0.1 to 5 parts by weight, preferably about 0.3 to 3 parts by weight, per 100 parts by weight of the chlorine group-containing acrylic rubber.
- chlorine group-containing acrylic rubbers are appropriately added with fillers such as carbon black, silica, graphite, clay, talc, plasticizers, lubricants, processing aids, etc.
- fillers such as carbon black, silica, graphite, clay, talc, plasticizers, lubricants, processing aids, etc.
- an alkoxysilane as described in Patent Document 1 is added in an amount of about 5 parts by weight or less, preferably about 0.05 to 1 part by weight based on 100 parts by weight of the chlorine group-containing acrylic rubber. Can also be used.
- alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -Glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) -aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) -amino Examples include propylmethyldimethoxysilane, ⁇ -anilinopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, N-
- the preparation of the composition with or without the addition of the alkoxysilane compound is carried out by kneading using a closed kneader, roll or the like, and the prepared composition is used as it is or as a polyamide resin system as a solution, dispersion or the like. After being applied to the surface of the molded article, it is vulcanized and bonded according to the normal vulcanization conditions of acrylic rubber.
- Example 1 Low-pressure plasma treatment of polyamide (PA66; Toray products Amilan CM3001-G30) flat plate injection molded product (25 ⁇ 60 ⁇ 2mm) in a glass vacuum vessel with Al parallel plates under the following conditions Went. Atmosphere: He gas Pressure: Approximately 60Pa Frequency: 40kHz Output: 200W Time: 10 minutes
- the adhesive strength and the rubber remaining area ratio were measured by a 90 ° peel test in accordance with JIS K6256 (2006) corresponding to ISO 813 as an adhesive evaluation.
- Example 2 In Example 1, Formulation Example I containing no silane compound was used as the higher fatty acid salt-sulfur vulcanized acrylic rubber composition.
- Example 2 Comparative Example 1 In Example 2, a polyamide flat plate not subjected to low-pressure plasma treatment was used.
- Example 2 instead of the low-pressure plasma treatment, a polyamide flat plate subjected to atmospheric pressure plasma treatment performed under the following conditions was used.
- Process gas He Distance between test piece and plasma nozzle: 15mm Processing speed: 100mm / second
- Example 2 instead of a polyamide flat plate subjected to low-pressure plasma treatment, a polyphenylene sulfide (Tosoh SPSIL PPS GS-30) flat plate similarly treated with low-pressure plasma was used.
- a polyphenylene sulfide Tosoh SPSIL PPS GS-30
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polyamides (AREA)
Abstract
Description
R1,R2:任意の官能性基
R3,R4:炭化水素基
を添加したゴム組成物とを、接着剤を介することなく積層し、貼り合わせた樹脂ゴム積層体が記載されている。しかしながら、アルコキシシラン化合物が添加されるゴムとしてのアクリルゴムの例示はみられない。
(1) ポリアミド系樹脂成形品のプラズマ処理は、低圧プラズマ処理法によって行われ、これを大気圧プラズマ処理法によって行った場合には、所望の樹脂-ゴム間接着性を確保することができない。
(2) ポリアミド系樹脂の代りに、特許文献3に例示されているポリフェニレンスルフィドを用いた場合には、樹脂-アクリルゴム間の接着性を全く得ることができない。
(3) ポリアミド系樹脂成形品の表面に加硫接着されるアクリルゴムとしては、高級脂肪酸塩-イオウ加硫系アクリルゴムが用いられ、他の架橋性基を有するアクリルゴムであるトリアジン加硫系アクリルゴム、ジチオカルバミン酸(塩)加硫系アクリルゴム、有機アンモニウム加硫系アクリルゴム等を用いた場合には、後記接着性試験において、ある程度の接着強度はみられるものの、ゴム残率はいずれも0%である。
(4) 特許文献1では必須成分とされていたアルコキシシラン化合物は、本発明では任意成分であり、それの存在または不存在によって接着性が影響されることはない。
種類 CH 2 /NHCO基数 原料モノマー
46 4 テトラメチレンジアミン-アジピン酸塩
6 5 ε-カプロラクタム、ε-アミノカプロン酸
66 5 ヘキサメチレンジアミン-アジピン酸塩
610 7 ヘキサメチレンジアミン-セバシン酸塩
612 8 ヘキサメチレンジアミン-ドデカン二酸塩
11 10 ω-アミノウンデカン酸
12 11 ω-ラウロラクタム、ω-アミノドデカン酸
ポリアミド(PA66;東レ製品アミランCM3001-G30)製平板状射出成形品(25×60×2mm)を、Al製平行平板を備えたガラス製の真空容器内で、次の条件下での低圧プラズマ処理を行った。
雰囲気:Heガス
圧力:約60Pa
周波数:40kHz
出力:200W
時間:10分間
(配合例I)
実施例1において、高級脂肪酸塩-イオウ加硫系アクリルゴム組成物として、シラン化合物を含有しない配合例Iが用いられた。
実施例1~2において、低圧プラズマ処理されるポリアミドとして、PA46(DSM社製スタニールTW241F6)が用いられた。
実施例2において、低圧プラズマ処理が行われないポリアミド平板が用いられた。
実施例2において、低圧プラズマ処理の代りに、次の条件下で行われた大気圧プラズマ処理されたポリアミド平板が用いられた。
プロセスガス:He
試験片とプラズマノズルの間隔:15mm
処理速度:100mm/秒
実施例2において、低圧プラズマ処理されたポリアミド平板の代りに、同様に低圧プラズマ処理されたポリフェニレンスルフィド(東ソー製サスティールPPS GS-30)平板が用いられた。
Claims (2)
- 低圧プラズマ処理されたポリアミド系樹脂成形品にアクリルゴム層を形成する高級脂肪酸塩-イオウ加硫系アクリルゴム組成物を、接着剤を介さずに直接加硫接着させた樹脂ゴム複合体。
- 高級脂肪酸塩-イオウ加硫系アクリルゴムが加硫性基として塩素基を有するアクリルゴムである請求項1記載の樹脂ゴム複合体。
Priority Applications (4)
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JP2014514638A JP5855242B2 (ja) | 2012-11-01 | 2013-10-29 | 樹脂ゴム複合体の製造法 |
EP13851061.5A EP2915664A4 (en) | 2012-11-01 | 2013-10-29 | RESIN-RUBBER COMPOSITE |
US14/439,979 US20150291743A1 (en) | 2012-11-01 | 2013-10-29 | Resin-rubber composite |
CN201380055226.5A CN104822527A (zh) | 2012-11-01 | 2013-10-29 | 树脂橡胶复合物 |
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JP2012-241846 | 2012-11-01 | ||
JP2012241846 | 2012-11-01 |
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WO2014069459A1 true WO2014069459A1 (ja) | 2014-05-08 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/JP2013/079277 WO2014069459A1 (ja) | 2012-11-01 | 2013-10-29 | 樹脂ゴム複合体 |
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US (1) | US20150291743A1 (ja) |
EP (1) | EP2915664A4 (ja) |
JP (1) | JP5855242B2 (ja) |
CN (1) | CN104822527A (ja) |
WO (1) | WO2014069459A1 (ja) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57115431A (en) * | 1980-12-30 | 1982-07-17 | Mitsubishi Petrochem Co Ltd | Surface treatment of thermoplastic synthetic resin molded product |
JPS57170910A (en) * | 1981-04-14 | 1982-10-21 | Nippon Mektron Ltd | Ethylene-acrylate elastomer and method for vulcanizing the same |
JPS59221336A (ja) * | 1983-05-31 | 1984-12-12 | Idemitsu Petrochem Co Ltd | 熱可塑性樹脂の処理方法 |
JPH0872203A (ja) | 1994-08-31 | 1996-03-19 | Bridgestone Corp | 樹脂とゴムとの積層体 |
JPH11302491A (ja) * | 1998-04-23 | 1999-11-02 | Nok Corp | シール成形用アクリルゴム組成物 |
JP2002179874A (ja) * | 2000-12-15 | 2002-06-26 | Nippon Mektron Ltd | 塩素含有アクリルエラストマー組成物 |
JP2006205732A (ja) | 2005-01-28 | 2006-08-10 | Degussa Ag | 複合部材の製造方法及びかかる複合部材 |
JP2008230244A (ja) | 2007-02-22 | 2008-10-02 | Tokai Rubber Ind Ltd | 燃料ホースの製法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3481041D1 (de) * | 1983-05-31 | 1990-02-22 | Idemitsu Petrochemical Co | Verfahren zum behandeln thermoplastischen kunststoffes. |
JPH07116325B2 (ja) * | 1987-02-16 | 1995-12-13 | 日本合成ゴム株式会社 | ゴム組成物、架橋可能なゴム組成物、オイルシールおよびゴムホース |
US5271977A (en) * | 1989-02-10 | 1993-12-21 | Bridgestone Corporation | Low permeable rubber hose |
JPH06184388A (ja) * | 1992-12-16 | 1994-07-05 | Nok Corp | アクリルゴム組成物 |
US5707701A (en) * | 1994-08-31 | 1998-01-13 | Bridgestone Corporation | Resin/rubber laminate |
JP3391174B2 (ja) * | 1995-11-16 | 2003-03-31 | エヌオーケー株式会社 | アクリルゴム組成物 |
DE19715296C2 (de) * | 1997-04-11 | 1999-05-27 | Continental Ag | Verfahren zur Herstellung eines Rohlings für Fahrzeugreifen |
JP3528562B2 (ja) * | 1997-12-19 | 2004-05-17 | Nok株式会社 | ハロゲン含有アクリルゴム組成物 |
JP3838902B2 (ja) * | 2001-11-07 | 2006-10-25 | 電気化学工業株式会社 | ゴム組成物 |
JP2004042486A (ja) * | 2002-07-12 | 2004-02-12 | Daicel Degussa Ltd | 複合体及びその製造方法 |
DE102005031606A1 (de) * | 2005-07-06 | 2007-01-11 | Robert Bosch Gmbh | Verfahren zur Herstellung eines beschichteten Bauteils |
JP5617638B2 (ja) * | 2008-10-29 | 2014-11-05 | 日本ゼオン株式会社 | 燃料ホース用の架橋性ニトリル共重合体ゴム組成物の製造方法および燃料ホース用のゴム架橋物 |
JP2010159377A (ja) * | 2009-01-09 | 2010-07-22 | Nok Corp | アクリルゴム組成物 |
JP4828665B2 (ja) * | 2009-10-09 | 2011-11-30 | 三井・デュポンポリケミカル株式会社 | 成形体用アイオノマー組成物並びに成形体及びその製造方法 |
-
2013
- 2013-10-29 WO PCT/JP2013/079277 patent/WO2014069459A1/ja active Application Filing
- 2013-10-29 CN CN201380055226.5A patent/CN104822527A/zh active Pending
- 2013-10-29 JP JP2014514638A patent/JP5855242B2/ja active Active
- 2013-10-29 US US14/439,979 patent/US20150291743A1/en not_active Abandoned
- 2013-10-29 EP EP13851061.5A patent/EP2915664A4/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57115431A (en) * | 1980-12-30 | 1982-07-17 | Mitsubishi Petrochem Co Ltd | Surface treatment of thermoplastic synthetic resin molded product |
JPS57170910A (en) * | 1981-04-14 | 1982-10-21 | Nippon Mektron Ltd | Ethylene-acrylate elastomer and method for vulcanizing the same |
JPS59221336A (ja) * | 1983-05-31 | 1984-12-12 | Idemitsu Petrochem Co Ltd | 熱可塑性樹脂の処理方法 |
JPH0872203A (ja) | 1994-08-31 | 1996-03-19 | Bridgestone Corp | 樹脂とゴムとの積層体 |
JPH11302491A (ja) * | 1998-04-23 | 1999-11-02 | Nok Corp | シール成形用アクリルゴム組成物 |
JP2002179874A (ja) * | 2000-12-15 | 2002-06-26 | Nippon Mektron Ltd | 塩素含有アクリルエラストマー組成物 |
JP2006205732A (ja) | 2005-01-28 | 2006-08-10 | Degussa Ag | 複合部材の製造方法及びかかる複合部材 |
JP2008230244A (ja) | 2007-02-22 | 2008-10-02 | Tokai Rubber Ind Ltd | 燃料ホースの製法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014069459A1 (ja) | 2016-09-08 |
JP5855242B2 (ja) | 2016-02-09 |
EP2915664A4 (en) | 2016-07-13 |
US20150291743A1 (en) | 2015-10-15 |
EP2915664A1 (en) | 2015-09-09 |
CN104822527A (zh) | 2015-08-05 |
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