JP5428519B2 - Laminated body of thermoplastic resin composition and rubber composition - Google Patents

Description

  The present invention relates to a laminate having a laminate structure of a thermoplastic resin composition and a diene rubber composition, which is produced using a solventless adhesive technique.

  Laminates composed of two or more layers of materials having different characteristics are used in various industrial aspects in the form of conveyor belts, hoses, tubes, films, sheets, and the like (for example, Patent Documents 1 and 2). ).

  For example, a gas hose used for piping such as LP gas has an inner tube made of a thermoplastic resin composition such as a polyamide resin, a polyester resin, an ethylene vinyl alcohol copolymer or a modified polyolefin resin, which has excellent gas barrier properties. Are made of a diene rubber composition such as acrylonitrile butadiene rubber which is flexible and excellent in oil resistance, wear resistance and aging resistance, and is bonded to each other with an adhesive, followed by vulcanization.

  Conventionally, an organic adhesive using an organic solvent such as toluene or xylene is used for bonding between a layer made of the thermoplastic resin composition of the inner tube of the laminated hose and a layer made of the diene rubber composition of the outer tube. Solvent based bonding techniques have been used.

Japanese Patent Laid-Open No. 10-52887 JP 2008-168498 A

  In recent years, de-VOC (volatile organic compounds) is being promoted in the manufacturing process from the viewpoint of reducing environmental burdens in the industrial world. Therefore, it is required to shift to a solvent-free adhesion technique that does not use an organic solvent even in a manufacturing process of a laminated body such as a belt, a hose, a tube, and a sheet having a laminated structure composed of two or more materials.

  In general, the diene rubber composition and the thermoplastic resin are inferior in compatibility. In addition, when the thermoplastic resin is in an unmelted state under the vulcanization conditions of the diene rubber composition, the molecular mobility of the thermoplastic resin is low. Since it is relatively inferior, the adhesion is not very good. When the adhesiveness is not good, the bonded thermoplastic resin composition and diene rubber composition may be peeled off during use. In such a case, the laminated hose may be crushed or blocked by a negative pressure or the like, and the laminated sheet may be a starting point of destruction.

  Therefore, there is a need for an adhesion technique that can obtain good adhesion between a solvent-free layer composed of a thermoplastic resin composition and a layer composed of a diene rubber composition.

  As a result of intensive studies, the inventor has a polarity capable of forming a covalent bond with the main chain or side chain of the thermoplastic resin in the adhesion between the layer made of the thermoplastic resin composition and the layer made of the diene rubber composition. A laminate is formed using a liquid polymer composition containing 30% by mass or more of a modified liquid polybutadiene having a group and a 1,2-bond unit content in a butadiene unit of 10 mol% or more (provided that The diene rubber composition and / or the liquid polymer composition contains a vulcanizing agent.) Further, it has been found that good adhesion can be obtained by further vulcanization treatment.

The inventor believes that the reason why good adhesiveness is obtained by the solventless adhesive technique of the present invention is due to the following mechanism, but the adhesive mechanism of the present invention is not necessarily limited to this. It is not a thing.
(1) The functional group of the thermoplastic resin and the polar group of the modified liquid butadiene form a covalent bond.
(2) The carbon-carbon double bond of the diene rubber and the carbon-carbon double bond of the side chain of the modified liquid butadiene are crosslinked by a vulcanizing agent.

That is, the present invention is as follows.
[1] A laminate comprising a thermoplastic resin composition (a), a liquid polymer composition (b) and a diene rubber composition (c) combined in this order, wherein the liquid polymer composition (b) 30 masses of a modified liquid polybutadiene having a polar group capable of forming a covalent bond with atoms of the main chain or side chain of the thermoplastic resin and having a 1,2-bond unit content of 25 mol% or more in the butadiene unit %, And the liquid polymer composition (b) and / or the diene rubber composition (c) contains a vulcanizing agent.
[2] The laminate according to [1], wherein the polar group is at least one selected from the group consisting of a maleic anhydride group, an epoxy group, and a (meth) acrylate group.
[3] The thermoplastic resin (a) is at least one selected from the group consisting of a polyamide resin, a polyester resin, an ethylene vinyl alcohol copolymer resin, and a modified polyolefin resin, [1] or [2 ] The laminated body as described in above.
[4] The laminate according to any one of [1] to [3], wherein the diene rubber composition (c) is an acrylonitrile butadiene rubber composition.
[5] The thermoplastic resin composition (a) is a polyamide-based resin, and the polar group is at least one selected from the group consisting of a maleic anhydride group, an epoxy group, and a (meth) acrylate group. The laminate according to [4], wherein the group content is in the range of 5 to 25% by mass of the modified liquid polybutadiene and the 1,2-bond unit content is in the range of 50 to 95 mol%.
[6] A laminate obtained by vulcanizing the laminate according to any one of [1] to [5] at a temperature lower than the melting point of the thermoplastic resin composition (a).
[7] The thermoplastic resin composition (a), the liquid polymer composition (b) and the diene rubber composition (c) are combined in this order and applied at a temperature lower than the melting point of the thermoplastic resin composition (a). The method for producing a laminate according to any one of [1] to [6], wherein

  According to the present invention, it is possible to strongly bond a thermoplastic resin composition and a diene rubber composition without using a conventionally used solvent-based adhesive.

FIG. 1: shows the perspective view of a sheet-like laminated body as an example among the laminated bodies of this invention. FIG. 2 shows a perspective view of a sheet-like laminate as an example of the laminate of the present invention. FIG. 3 shows a perspective view of a tubular laminate as an example of the laminate of the present invention.

The present invention is described in detail below.
[Constituent elements of laminate]
<< Thermoplastic resin composition (a) >>
The thermoplastic resin can be appropriately selected according to the desired function / performance and processability, the type of polar group of the modified polybutadiene, and the like.
When the gas barrier property is required, the thermoplastic resin is preferably a polyamide resin, a polyester resin, an ethylene vinyl alcohol copolymer resin, a modified polyolefin resin, or a copolymer or a mixture thereof.

Examples of the polyamide resin (PA) include aliphatic polyamide resins, amorphous polyamide resins, aromatic polyamide resins, and mixtures thereof.
The aliphatic polyamide resin may have any structure that does not have an aromatic ring in the main chain and side chain. Specifically, polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, and nylon 12 are used. Copolyamides such as nylon 6-66 copolymer and nylon 6-610 copolymer can be exemplified, and polyamide elastomers such as nylon 6,6-polyethylene glycol block copolymer can also be exemplified.
The aromatic polyamide resin may have a structure having an aromatic ring in the main chain and / or side chain, and specifically, meta or paraxylylenediamine and a dicarboxylic acid having about 4 to 12 carbon atoms. An example is a polyxylylene polymer that is polycondensed from an acid. Such polymers have properties such as gas barrier properties, low water absorption, and low hygroscopicity.
The amorphous polyamide resin is not particularly limited as long as it has no crystallinity or poor crystallinity, but generally it is a semi-aromatic resin having an aromatic ring in the main chain and / or side chain. Specifically, a polymer of a dicarboxylic acid such as terephthalic acid and isophthalic acid and a diamine such as hexamethylenediamine, a terpolymer, and the like can be exemplified. Such an amorphous polyamide resin is excellent in gas barrier properties in a high humidity environment.
The polyamide-based resin of the present invention is preferably an aliphatic polyamide resin, particularly preferably nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, or a copolymer thereof. This is because it has good gas barrier properties, moldability, and flexibility.
As the commercially available polyamide-based resin, for example, Amilan (registered trademark, manufactured by Toray Industries, Inc .: nylon 6, nylon 66, nylon 610, copolymer nylon), Rilsan (registered trademark, manufactured by Arkema, nylon 11, nylon 12) is preferable. Can be used.

As the polyester resin, a polyester resin comprising a dicarboxylic acid component and a diol component can be used.
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and the like, and mixtures thereof. Specifically, as the aliphatic dicarboxylic acid, adipic acid having 2 to 20 carbon atoms, sebacic acid, dodecane carboxylic acid and the like are used, and as the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like are alicyclic. Examples of the dicarboxylic acid include cyclohexanedicarboxylic acid.
Examples of the diol component include aliphatic glycols, alicyclic glycols, and the like, and mixtures thereof. Specifically, as the aliphatic glycol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and the like are used as the alicyclic diol. , 4-cyclohexanediol and the like are exemplified.
Further, polyester-based elastomers such as polybutylene terephthalate-polytetramethylene oxide glycol block copolymer and polybutylene terephthalate-polycaprolactone block copolymer are also included in the polyester-based resin. The polyester resin may be modified with maleic anhydride, epoxy, or the like.
As commercially available polyester resins, for example, Hytrel (registered trademark, manufactured by Toray DuPont) and Bond First VC-40 (manufactured by Sumitomo Chemical Co., Ltd.) can be preferably used.

The ethylene-vinyl alcohol copolymer resin (EVOH) is not particularly limited as long as it is a copolymer of ethylene and polyvinyl alcohol, taking into consideration various characteristics such as gas barrier properties, moldability, flexibility, and thermal stability. However, if the gas barrier property and moldability are regarded as important, the ethylene copolymerization ratio is preferably 20 to 50 mol%, more preferably 30 to 40 mol%.
As a commercially available ethylene-vinyl alcohol copolymer resin, for example, EVAL (registered trademark, manufactured by Kuraray Co., Ltd., ethylene copolymerization rate of 24 to 48 mol%) can be preferably used. Among EVAL, those having an ethylene copolymerization ratio of 32 to 38 mol% (F, C, H grade) can be particularly preferably used.

Examples of the modified polyolefin resin include, for example, homopolymers of olefins, mutual copolymers, other copolymerizable materials, for example, copolymers with other vinyl monomers, and mixtures thereof. Examples thereof include those obtained by modifying an olefin resin with maleic anhydride or an epoxy group.
Specific examples of such polyolefin resins include various types of low density to high density polyethylene (LLDPE (cotton-like low density polyethylene, VLDPE (including very low density polyethylene)), polypropylene, polybutene, and their mutual co-polymerization. Polymer, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid copolymer (EAA), ethylene-methyl acrylate copolymer (EMA), ethylene- Examples include methyl methacrylate copolymer (EMMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-glycidyl methacrylate copolymer (E-GMA), etc. These polyolefin resins may be used alone or in combination of two kinds. The above can be mixed and used.
The method of modifying these polyolefin resins with maleic anhydride or epoxy is not particularly limited, and can be performed by a conventionally known method such as a graft polymerization method. Moreover, what is marketed as modified polyolefin resin can also be purchased and used.
As a commercially available modified polyolefin resin, for example, Admer (registered trademark, manufactured by Mitsui Chemicals) and Bond First (registered trademark, manufactured by Sumitomo Chemical) can be preferably used.

Examples of additives that may be included in the thermoplastic resin composition as desired include fillers, reinforcing agents, plasticizers, anti-aging agents, softeners, tackifiers, lubricants, dispersants, processing aids, and flame retardants. And foaming agents. These various additives can be appropriately selected according to the type of resin.
If desired, soft components such as rubber and thermoplastic elastomer can be added to give flexibility.

<< Liquid polymer composition (b) >>
The liquid polymer composition is a composition containing various modified products of a liquid polymer having a carbon-carbon double bond in the side chain.
Such a liquid polymer is a sulfur vulcanizing compound, that is, a compound using sulfur as a vulcanizing agent and combining with a vulcanization accelerator having a nitrogen atom, or a sulfur atom and a nitrogen atom that can be a sulfur donor without using sulfur. There is no particular limitation as long as it can be vulcanized by blending using a vulcanization accelerator having the following, is liquid at normal temperature and has a carbon-carbon double bond in the main chain and side chain. Examples thereof include liquid polyisoprene containing 1,2-bond units in isoprene units, and liquid polybutadiene containing 1,2-bond units in butadiene units.
The modification of the liquid polymer is a polar group capable of forming a covalent bond with the main chain or side chain atoms of the thermoplastic resin, for example, an acid anhydride group such as a maleic anhydride group, an epoxy group, a terminal isocyanate group, a hydroxyl group, It can be carried out by adding a carboxyl group, amino or the like by graft addition or the like.
The polar group of the modified liquid polymer depends on the polar group of the thermoplastic resin, and a suitable one is appropriately selected in consideration of various conditions such as reactivity of the polar group and steric hindrance.
The content of 1,2-bond units is 25 mol% or more, preferably in the range of 50 to 95 mol%, more preferably in the range of 75 to 90 mol%. From the viewpoint of adhesion due to crosslinking with the diene rubber composition (c), a higher content is preferable, and from the viewpoint of physical properties such as flexibility of the liquid polymer composition after crosslinking and curing, it is not so high. preferable.

Furthermore, the liquid polymer composition used in the present invention may contain a modified liquid polymer having a carbon-carbon double bond in the side chain alone or in a mixture of two or more, and other modified or unmodified The liquid polymer may be contained.
As other non-modified liquid polymers, specifically, liquid polyisoprene containing 1,2-bond units in isoprene units, liquid polybutadiene containing 1,2-bond units in butadiene units, and the like, Liquid polybutene, liquid polyisobutene, liquid polyisoprene, liquid polybutadiene, liquid poly α-olefin, liquid ethylene α-olefin copolymer, liquid ethylene propylene copolymer, liquid ethylene-propylene-diene copolymer, liquid ethylene butylene copolymer Examples of the modified liquid polymer include hydroxy group-terminated modified polybutadiene and its hydrogenated product, hydroxy group-terminated modified polyisoprene and its hydrogenated product. Hydroxy group-modified polymers such as Epoxy group-modified polymers such as epoxy-modified polybutadiene; (meth) acrylate group-modified polymers such as acrylate-modified polybutadiene; hydrolyzable silicon group-containing polyolefins such as silane-grafted polyolefin and silane-terminated polyolefin; maleic anhydride-modified polyisoprene and maleic anhydride Acid anhydride group-modified polymers such as modified polybutadiene, maleic anhydride modified polybutene, maleic anhydride modified ethylene propylene copolymer, maleic anhydride modified ethylene alpha olefin copolymer; carboxy modified polybutadiene, carboxy modified polyisoprene, carboxy group terminal Carboxy group modified polymers such as acrylonitrile butadiene copolymer (CTBN); Amino group modified polymers such as amino group terminal acrylonitrile butadiene copolymer (ATBN) Rimmer are exemplified.

The liquid polymer composition (b) used in the present invention is characterized in that no solvent is used. Here, the solvent is a low-medium-boiling point solvent such as toluene or ketone that is generally used for an adhesive and has a boiling point of 150 ° C. or lower. Since the liquid polymer composition of the present invention does not contain a solvent, the workability is good and the environmental load can be reduced.
In addition, the liquid polymer composition (b) used in the present invention may have a content of the above-mentioned modified liquid polymer of 100% by mass, but in addition to the modified liquid polymer, the range does not impair the object of the present invention. Thus, additives can be blended as required. Examples of additives include carbon black, clay and other fillers, paraffinic oil (process oil, etc.) softeners, vulcanizing agents (crosslinking agents), vulcanization accelerators, vulcanization aids, plasticizers, Examples include processing aids, anti-aging agents, pigments, antistatic agents, antioxidants, flame retardants, adhesion aids, tackifiers, silane coupling agents, polymers, and the like. When a plasticizer is blended, the plasticizer preferably has a boiling point of 150 ° C. or higher.

As the modified liquid polymer, a polymer obtained by grafting a maleic anhydride group or an epoxy group to liquid polybutadiene containing 1,2-bond units in a range of 25 to 95 mol% is preferable. This is because the compatibility with the thermoplastic resin composition (a) and the diene rubber composition (c) is excellent, and the adhesiveness becomes strong due to the high reactivity of the maleic anhydride group or the epoxy group. When the polar group content is a maleic anhydride group, it is preferably contained in the range of 2 to 25% by mass in the modified liquid butadiene, and when it is an epoxy group, the modified liquid butadiene is contained. The oxirane oxygen concentration is preferably contained in the range of 5 to 10% by mass. Further, when it is an acrylate group, it is preferably contained in the range of 2 to 20% by mass in the modified liquid butadiene, or when it is a methacrylate group, 3 to 3 in the modified liquid butadiene. It is preferably contained in the range of 40% by mass.
Examples of commercially available modified liquid polymers include maleic anhydride-modified NISSO-PB BN-1015 (manufactured by Nippon Soda Co., Ltd.), Rykon, Lycobond (trademark registration, manufactured by Sartomer), epoxy-modified NISSO-PB JP-200. (Nippon Soda Co., Ltd.), acrylate-modified NISSO-PB TEA-1000, TE-2000 (Nippon Soda Co., Ltd.), Leica Krill (trademark registration, manufactured by Sartomer) can be preferably used.

<< Diene rubber composition (c) >>
The diene rubber is a sulfur vulcanizing compound, that is, a compound that uses sulfur as a vulcanizing agent (crosslinking agent) and combines with a vulcanization accelerator having a nitrogen atom, or a sulfur atom that can be a sulfur donor without using sulfur. There is no particular limitation as long as it can be vulcanized by blending using a vulcanization accelerator having nitrogen atoms. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (high cis butadiene rubber, low cis butadiene rubber) (BR), carboxylated butadiene rubber (XBR), styrene butadiene rubber (SBR), carboxylated styrene- Butadiene copolymer rubber (XSBR), chloroprene rubber (CR), carboxylated chloroprene rubber (XCR), acrylonitrile butadiene rubber (NBR), carboxylated acrylonitrile-butadiene copolymer rubber (XNBR), acrylonitrile-butadiene-isoprene copolymer Combined rubber (NBIR), acrylonitrile-isoprene copolymer rubber (NIR), acrylate butadiene rubber (ABR), butyl rubber (IIR), norbornene rubber (NOR), chlorobutyl rubber (CIIR) Bromobutyl rubber (BIIR), epoxidized natural rubber (ENR), styrene-isoprene-butadiene copolymer rubber (SIBR), hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR), α-methylstyrene-butadiene copolymer rubber (MSBR), copolymer rubber (PBR) with vinylpyridine-butadiene, and vinylpyridine-styrene-butadiene copolymer rubber (PSBR). These can be used alone or in combination of two or more.

Acrylonitrile butadiene rubber (NBR) may be particularly preferred because of its excellent mechanical strength and high chemical resistance and heat resistance.
The acrylonitrile butadiene rubber preferably has a Mooney viscosity (ML (1 + 4) 100 ° C.) of 35 to 85, and the bound acrylonitrile content center value is preferably 18 to 45% by mass, more preferably 20 to 40% by mass. . This is because durability and moldability are excellent.

The liquid polymer composition (b) and / or the diene rubber composition (c) of the present invention can be independently blended with additives as needed within a range not impairing the object of the present invention.
Examples of additives include carbon black, clay and other fillers, paraffinic oil (process oil, etc.) softeners, vulcanizing agents (crosslinking agents), vulcanization accelerators, vulcanization aids, plasticizers, Examples thereof include processing aids, anti-aging agents, pigments, antistatic agents, antioxidants, flame retardants, adhesion aids, and polymers.
However, the vulcanizing agent (crosslinking agent) is contained in either or both of the liquid polymer composition (b) and the diene rubber composition (c).
Examples of the filler include carbon black, silica, clay, talc, calcium carbonate, mica, and diatomaceous earth.

  Examples of the vulcanizing agent (crosslinking agent) include vulcanizing agents such as sulfur-based, organic peroxide-based, metal oxide-based, phenol resin, and quinonedioxime. Examples of the sulfur vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide and the like. For example, 0.1 to 5.0 parts by weight of the diene rubber or liquid polymer is preferably used. Examples of organic peroxide-based vulcanizing agents include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-di (t-butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like are exemplified, and for example, about 1 to 15 parts by weight may be used with respect to 100 parts by weight of diene rubber or liquid polymer. Furthermore, examples of the phenol resin vulcanizing agent include bromides of alkyl phenol resins, mixed vulcanization systems containing halogen donors such as tin chloride and chloroprene, and alkyl phenol resins.

  Examples of the vulcanization accelerator include aldehyde / ammonia, guanidine, thiourea, thiazole, sulfenamide, thiuram, and dithiocarbamate vulcanization accelerators. Examples of aldehyde / ammonia vulcanization accelerators include hexamethylenetetramine (H); guanidine vulcanization accelerators such as diphenylguanidine; and thiourea vulcanization accelerators such as ethylene thiourea. The thiazole vulcanization accelerator includes, for example, dibenzothiazyl disulfide (DM), N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), 2-mercaptobenzothiazole and its Zn salt; Examples of the vulcanization accelerator include tetramethylthiuram disulfide (TT), dipentamethylene thiuram tetrasulfide and the like; examples of the dithiocarbamate vulcanization accelerator include Na-dimethyldithiocarbamate and Zn-dimethyldithiocarbamate. , Te-die Dithiocarbamate, Cu- dimethyldithiocarbamate, Fe- dimethyldithiocarbamate, pipecolic pin Pekori Le dithiocarbamate, and the like, respectively.

  As the vulcanization aid, general rubber aids can be used together, and examples thereof include zinc white, stearic acid, oleic acid, and Zn salts thereof.

  The content of the vulcanizing agent, vulcanization accelerator, and vulcanization aid is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of the liquid polymer component or diene rubber component. is there. If it is less than 0.1 parts by mass, vulcanization is insufficient and the three-dimensional crosslinking density is low, and if it exceeds 10 parts by mass, the three-dimensional crosslinking density is high.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; Adipic acid propylene glycol polyester, adipic acid butylene glycol polyester, and the like. As the softening agent, commonly used ones such as various paraffinic oils can be used, and specific examples include process oils. What is necessary is just to mix | blend a plasticizer and a softener with a general content in view of the use of the laminated body of this invention.

  Anti-aging agents include N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6PPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), N-isopropyl-N Examples thereof include '-phenyl-p-phenylenediamine (IPPD) and styrenated phenol (SP). Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). What is necessary is just to mix | blend anti-aging agent and antioxidant with a general content in view of the use of the laminated body of this invention.

  Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives. Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, and brominated polyether. What is necessary is just to mix | blend an antistatic agent and a flame retardant with a general content in view of the use of the laminated body of this invention.

  Adhesion aids include triazine thiol compounds such as 1,3,5-triazine-2,4,6-trithiol, 6-butylamino-1,3,5-triazine-2,4-dithiol, cobalt naphthenate , Resorcin, cresol, resorcin-formalin latex, monomethylol melamine, monomethylol urea, ethylene maleimide and the like. What is necessary is just to mix | blend an adhesion support agent with the content normally used for a hose. Examples of the polymer other than the liquid polymer or the diene rubber include resins usually used according to physical properties required for the liquid polymer composition (b) or the diene rubber composition (c) used in the present invention, heat A plastic elastomer or the like can be used.

  In the composition of the present invention, the various additives described above may be used alone or in combination of two or more. Moreover, the said additive can be suitably selected according to the kind etc. of a liquid polymer component or a diene rubber component.

[Manufacturing method of laminate]
"Construction"
The laminate of the present invention is formed by laminating an adhesive layer made of a liquid polymer composition directly on a resin layer made of a thermoplastic composition, and further laminating a rubber layer made of a diene rubber composition directly thereon. It may have any structure (for example, FIGS. 1 and 3), and has a structure in which an adhesive layer is further laminated on the surface of the resin layer opposite to the adhesive layer, and a rubber layer is further laminated thereon. It is good also as a thing (for example, FIG. 2).
Further, a complicated structure may be formed by further laminating a layer on the surface of the resin layer or rubber layer opposite to the adhesive layer.
<< Molding of thermoplastic resin composition >>
What is necessary is just to shape | mold into a desired shape by the method selected suitably by the characteristic of a thermoplastic resin etc. from a well-known method, and a method in particular is not limited. When forming into a sheet shape, it can shape | mold by press molding, for example, When forming into a tube shape, it can shape | mold by extrusion molding, for example.
<Application of liquid polymer composition>
It can be used in place of a conventional solvent-based adhesive. The coating amount is not particularly limited, but can be appropriately set depending on the viscosity of the composition. It is preferable to apply so as to have a uniform thickness.
Since it is liquid at normal temperature and the solvent does not evaporate, it is excellent in workability and environment.
<Molding of diene rubber composition>
It can be formed by a known method.
In the case of a sheet-like laminate, a press-molded sheet can be bonded together.
In the case of a tubular laminate, the thermoplastic resin composition may be extruded and formed into a tube shape, and the liquid polymer composition may be applied to the surface of the thermoplastic resin composition, followed by coating extrusion molding.
<Vulcanization>
Known methods can be used. The temperature is not particularly limited as long as the temperature is lower than the melting point of the thermoplastic resin. For example, it is heated and vulcanized at 125 to 200 ° C. (limited to the melting point of the thermoplastic resin composition or less) for about 5 to 200 minutes. Although the vulcanization method is not particularly limited, it is preferable to use a vulcanization can vulcanization method and set the vulcanization conditions to a temperature of 125 ° C. to 160 ° C., a pressure of 1 to 10 MPa, and a time of 30 to 90 minutes.

  Hereinafter, the present invention will be specifically described with reference to examples. However, it goes without saying that the present invention is not limited to these examples.

1. Evaluation method of adhesive strength Using a laminate sample for evaluating adhesive strength obtained as described below, a tensile tester (Autograph AGS-5kNG, Shimadzu Corporation) as a measuring instrument in an environment of 23 ° C. and 50% RH. 180 degree peeling test (JIS K 6854-1: 1999) of the laminate sample for adhesive strength evaluation was performed under the condition of a gripper moving speed of 50 mm / min. The mode of destruction was described by JIS K 6866: 1999.
Judgment of the adhesive strength was determined as “」 ”as excellent when the adhesive strength was 4.0 N / mm or more, and“ ◯ ”as 3.0 N / mm or better as good. Less than mm was determined to be impossible, and “x” was determined. “◎” and “◯” are acceptable, and “×” is unacceptable.
The measurement results are shown in Table 1 for the examples and in Table 2 for the comparative examples.

2. Preparation of each component <2-1> Thermoplastic resin composition The thermoplastic resin composition described in Table 1 (Example) and Table 2 (Comparative Example) was heated to 200 to 230 ° C using a hot press. Under the conditions, a sheet having a thickness of 0.5 mm was formed. The obtained sheet was cut into a length of 150 mm and a width of 150 mm to obtain a sheet-like sample of the thermoplastic resin composition.
In the column of adherend 1 (thermoplastic resin composition) in Tables 1 and 2, PA is polyamide (Amilan CM6041XF, manufactured by Toray Industries, Inc.), and EVA-MAH is maleic anhydride graft-modified ethylene. Vinyl acetate copolymer resin (HPR VR102, manufactured by Mitsui DuPont Polychemical Co., Ltd.), epoxy-COPE is an epoxy-modified copolyester resin (Bond First VC-40, manufactured by Sumitomo Chemical Co., Ltd.), and E-GMA is ethylene. -Glycidyl methacrylate copolymer resin (Bond First E, manufactured by Sumitomo Chemical Co., Ltd.) is meant.

<2-2> Liquid polymer composition In each Example and the comparative example, the liquid polymer composition as described below was used. The functional group, base polymer and diene type of each liquid polymer composition are as described in Table 1 (Examples) and Table 2 (Comparative Examples).
In Examples 1, 4 to 6, maleic anhydride group-modified liquid polybutadiene (NISSO-PB BN1015, manufactured by Nippon Soda Co., Ltd.) was used.
In Example 2, epoxy group-modified liquid polybutadiene (NISSO-PB JP200, manufactured by Nippon Soda Co., Ltd.) was used.
In Example 3, acrylate group-modified liquid polybutadiene (NISSO-PB TEA-1000, manufactured by Nippon Soda Co., Ltd.) was used.
In Comparative Example 1, carboxyl group-modified liquid polybutadiene (NISSO-PBC-1000, manufactured by Nippon Soda Co., Ltd.) was used.
In Comparative Examples 2, 3, and 4, amino group-terminated acrylonitrile butadiene rubber (HYCAR ATBN 1300 × 16, manufactured by Ube Industries, Ltd.) was used.

<2-3> Diene Rubber Composition 100 parts by mass of acrylonitrile butadiene rubber (NBR) (Nipol 1042, manufactured by Nippon Zeon Co., Ltd.), 40 parts by mass of carbon black (GPF carbon, manufactured by Nippon Nihon Carbon Co., Ltd.), stearic acid (beads) 2 parts by mass of stearic acid NY (manufactured by NOF Corporation), 2 parts by mass of anti-aging agent (NOCRACK 224, manufactured by Ouchi Shinsei Chemical Co., Ltd.), and 5 parts by mass of vulcanizing agent (oil-treated sulfur, manufactured by Karuizawa Smelter) Was kneaded at 100 ° C. using a Banbury mixer to prepare an NBR rubber composition.
The obtained NBR rubber composition was formed into a sheet having a thickness of 2 mm under a condition of 100 ° C. using a hot press. The obtained sheet was cut out in a size of 150 mm long × 150 mm wide to obtain a sheet-like sample of a diene rubber composition.

3. Adhesion between thermoplastic resin composition and diene rubber composition A liquid polymer composition (adhesive) is applied to one side of a sheet-like sample (adhered body 1) (150 mm x 150 mm x 0.5 mm) of the thermoplastic resin composition. It was applied (application amount 100 g / m ² ), and a diene rubber composition sheet-like sample (adhered body 2) (150 mm × 150 mm × 2 mm) was bonded thereto. Thereafter, a vulcanization treatment was performed at 148 ° C. for 45 minutes to obtain an adhesive strength evaluation sample. It was cut out to a width of 25 mm and used as a 180 degree peel sample.

4). Description of Test Results As is clear from Table 1, the laminate samples of Examples 1 to 6 have higher adhesive strength than the laminate samples of Comparative Examples 1 to 4, and all of the values are 3.5 N / It clearly exceeded the acceptance criteria (3.0 N / mm or more). In particular, the laminate samples of Examples 1 and 2 have an adhesive strength of 4.5 N / mm or more, which clearly exceeds the acceptance standard (4.0 N / mm or more), and is particularly excellent. It was. In Table 1, CF40 or CF50 is a mixed failure of CF (cohesive failure) and AF (interface failure), of which CF is about 40% or about 50%.
In Comparative Examples 1 to 4, all were AF (interfacial fracture), but in Comparative Examples 1 and 2, the interface between the adherend 1 (thermoplastic resin) and the adhesive was peeled off. The interface with the adherend 2 (diene rubber) was peeled off.

DESCRIPTION OF SYMBOLS 1 Laminate 2 Resin layer which consists of thermoplastic resin composition (a) 3 Adhesive layer which consists of liquid polymer composition (b) 4 Rubber layer which consists of diene-type rubber composition (c)

Claims (6)

A laminate comprising a thermoplastic resin composition (a), a liquid polymer composition (b) and a diene rubber composition (c) combined in this order, wherein the liquid polymer composition (b) 30% by mass or more of a modified liquid polybutadiene having a polar group capable of forming a covalent bond with the main chain or side chain atom of the resin and having a 1,2-bond unit content of 25 mol% or more in the butadiene unit and, the liquid polymer composition (b) and / or the diene rubber composition (c) is seen containing a vulcanizing agent,
The polar group is at least one selected from the group consisting of a maleic anhydride group, an epoxy group and a (meth) acrylate group;
The liquid polymer composition (b) does not use a solvent . The laminate according to claim 1, wherein the thermoplastic resin composition (a) is at least one selected from the group consisting of polyamide resins, polyester resins, ethylene vinyl alcohol copolymer resins, and modified polyolefin resins. body. The laminate according to claim 1 or 2 , wherein the diene rubber composition (c) is an acrylonitrile butadiene rubber composition. The thermoplastic resin composition (a) is a polyamide resin, in the range of 5 to 25 wt% of content the modified liquid polybutadiene before Kikyoku groups, and the 1,2-bond units content The laminate according to claim 3 , which is in the range of 50 to 95 mol%. A laminate obtained by vulcanizing the laminate according to any one of claims 1 to 4 at a temperature lower than the melting point of the thermoplastic resin composition (a). Combining the thermoplastic resin composition (a), the liquid polymer composition (b) and the diene rubber composition (c) in this order, and vulcanizing at a temperature lower than the melting point of the thermoplastic resin composition (a). The manufacturing method of the laminated body in any one of Claims 1-4 characterized by these.