JP6262632B2 - Adhesive composition, and joining member and molded article using the same - Google Patents

Description

  The present invention relates to an adhesive composition, and a joining member and a molded product using the same.

  In recent years, members using resin materials have been applied to various uses. For example, as a weather strip attached to a sash of an automobile door, a member using vulcanized rubber as a base material is suitably used.

  Patent Document 1 discloses a weather strip material in which a molded body made of vulcanized rubber is joined by welding a specific thermoplastic elastomer.

Japanese Patent Laid-Open No. 2003-253055

  As described in Patent Document 1, with the recent application of resin materials to a wide range of applications, as a joining member for joining members molded from resin materials, joining members having excellent characteristics such as adhesiveness are available. It has been demanded.

  However, conventionally, it has been difficult to form a bonding member having good adhesion to a molded body using various resin materials such as vulcanized rubber and thermoplastic resin. Further, for example, a joining member used for a weather strip is desired to have good sliding performance as a part of a product. However, as a joining member such as sliding performance and weather strip performance and adhesiveness. It has been difficult to achieve both of the above performances.

  One of the objects of the present invention is to provide a joining member having good adhesion to a molded body made of various resin materials such as vulcanized rubber and thermoplastic resin and having good sliding performance. It is in. Another object of the present invention is to provide an adhesive composition capable of forming the excellent bonding member as described above. Furthermore, one of the objects of the present invention is to provide a molded article provided with the above excellent joining member.

  One aspect of the present invention relates to an adhesive composition containing an ethylene / α-olefin block copolymer, a propylene-based polymer, a crosslinked polymer, and a silicone compound. The adhesive composition has a matrix containing the ethylene / α-olefin block copolymer and a domain containing the cross-linked polymer dispersed in the matrix. The ethylene / α-olefin block copolymer has a hard block containing 95% by mass or more of ethylene monomer units and a soft block containing more than 5% by mass of α-olefin monomer units. The melt flow rate (ASTM D-1238, temperature 190 ° C., load 2.16 kg) of the α-olefin block copolymer is 3 g / 10 min or more. The cross-linked polymer is a cross-linked product obtained by cross-linking one or two or more polymers including an ethylene / polar monomer copolymer. Further, based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer, and the crosslinked polymer, the content of the ethylene / α-olefin block copolymer is 60 to 95% by mass, The content of the propylene polymer is 1.5 to 15% by mass, and the content of the crosslinked polymer is 3.5 to 32% by mass. Moreover, content of the said silicone compound is 1-10 mass parts with respect to 100 mass parts of total amounts of the said ethylene-alpha-olefin block copolymer, the said propylene-type polymer, and the said crosslinked polymer.

  In one embodiment, the crosslinked polymer is at least one selected from the group consisting of the ethylene / polar monomer copolymer, an ethylene / α-olefin block copolymer, and an ethylene / α-olefin / non-conjugated diene copolymer. The polymer may contain a crosslinked product.

  In one embodiment, the adhesive composition may further contain paraffinic oil.

  In one embodiment, the silicone compound may include a gum or solid first silicone compound and an oily second silicone compound.

  Another aspect of the present invention relates to a joining member that joins two or more members. The joining member is formed from the adhesive composition.

  Still another aspect of the present invention relates to a molded article including two or more members and the joining member that is interposed between the members and joins the members.

  In one aspect, in the molded product, at least one of the members may include a rubber material and / or a thermoplastic resin material on a contact surface with the joining member.

  ADVANTAGE OF THE INVENTION According to this invention, the joining member which has a favorable sliding performance while having favorable adhesiveness with respect to the molded object which consists of various resin materials, such as a vulcanized rubber and a thermoplastic resin, is provided. Moreover, according to this invention, the adhesive composition which can form the said joining member is provided. Moreover, according to this invention, the molded article provided with the said joining member is provided.

  A preferred embodiment of the present invention will be described below.

  An adhesive composition according to this embodiment is a composition containing an ethylene / α-olefin block copolymer, a propylene-based polymer, a crosslinked polymer, and a silicone compound, and includes a matrix containing the ethylene / α-olefin copolymer. And a domain (crosslinked body domain) containing a crosslinked polymer dispersed in a matrix.

  In the present embodiment, the ethylene / α-olefin block copolymer has a hard block containing 95% by mass or more of ethylene monomer units and a soft block containing more than 5% by mass of α-olefin monomer units. The melt flow rate (ASTM D-1238, temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin block copolymer is 3 g / 10 min or more.

  In the present embodiment, the crosslinked polymer is a crosslinked product obtained by crosslinking one or more polymers including an ethylene / polar monomer copolymer.

  The content of the ethylene / α-olefin block copolymer in the adhesive composition is 60 to 95% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer and the crosslinked polymer.

  The content of the propylene polymer in the adhesive composition is 1.5 to 15% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer.

  The content of the crosslinked polymer in the adhesive composition is 3.5 to 32% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer and the crosslinked polymer.

  Content of the silicone compound in the said adhesive composition is 1-10 mass parts with respect to 100 mass parts of total amounts of an ethylene-alpha-olefin block copolymer, a propylene-type polymer, and a crosslinked polymer.

  Since the adhesive composition according to the present embodiment has the above-described configuration, it is possible to easily form a bonding member having good adhesion to a molded body made of various resin materials such as vulcanized rubber and thermoplastic resin. it can. Moreover, the said adhesive composition also has favorable sliding performance with favorable adhesiveness. For this reason, the said adhesive composition can be used suitably for the use as which the adhesiveness and sliding performance are requested | required, such as a corner part and fitting part of a weather strip.

  Conventionally, a corner portion (or fitting portion) of a weather strip has been formed from a thermoplastic resin. In this case, in order to ensure the slidability at the corner, it is necessary to form a slidable coating film by applying and curing a coating material such as silicone or urethane. However, such a coating film is vulnerable to physical friction and scratching, and there is a problem that the sliding performance of the part is remarkably lowered once it is peeled off.

  On the other hand, since the joining member formed of the adhesive composition has good sliding performance, the joining member itself is resistant to physical friction and scratching. Dynamic performance is maintained. For this reason, the joining member formed with the said adhesive composition is excellent in durability and a friction life.

  Conventionally, an attempt has been made to add a silicone compound in order to give the joining member itself slidability. However, in the conventional joining member, there are cases in which multi-layer separation occurs during injection molding, resulting in problems such as deterioration of the appearance and causing destruction during use. Further, in the conventional bonding member, the silicone compound oozes out to the surface, so that dust, soil, etc. are likely to adhere, which may cause damage to the sliding glass, coating film, and the like. Further, the addition of the silicone compound may deteriorate the adhesiveness and reduce the product durability.

  On the other hand, in the joining member formed from the above-mentioned adhesive composition, the presence of the cross-linked domain dispersed in the matrix described above causes multi-layer separation due to uneven distribution of the silicone compound, exudation of the silicone compound to the member surface, etc. It is suppressed. For this reason, in the said joining member, the outstanding effects, such as a favorable external appearance, high durability, and prevention of the damage | wound to glass etc., can be acquired, maintaining the outstanding adhesiveness.

(A) Ethylene / α-olefin block copolymer The ethylene / α-olefin block copolymer is a hard block (also referred to as a hard segment) containing 95% by mass or more of an ethylene monomer unit, and 5% of an α-olefin monomer unit. % Including soft blocks (also referred to as soft segments).

  The said adhesive composition can form the joining member excellent in adhesiveness with various resin materials by containing such an ethylene * alpha-olefin block copolymer. In particular, in this embodiment, by containing an ethylene / α-olefin block copolymer, it has excellent adhesion to a molded body containing a vulcanized rubber (for example, vulcanized EPDM (ethylene / propylene / diene rubber)). A joining member can be formed.

  The content of ethylene monomer units in the hard block is 95% by mass or more, preferably 98% by mass or more, based on the total mass of the hard block.

  In the soft block, the content of the α-olefin monomer unit may be more than 5% by mass, for example, may be more than 5% by mass and 70% by mass or less.

  The content of the hard block in the ethylene / α-olefin block copolymer may be, for example, 40% by mass or more based on the total mass of the ethylene / α-olefin block copolymer, preferably 45 to 65 mass. %. Further, the content of the soft block in the ethylene / α-olefin block copolymer may be, for example, 10 to 60% by mass, preferably 35 based on the total mass of the ethylene / α-olefin block copolymer. It is -55 mass%.

  The ethylene / α-olefin block copolymer may have at least one hard block and at least one hard block, and may have two or more each. As the ethylene / α-olefin block copolymer, a multiblock copolymer having two or more hard blocks and two soft blocks can be preferably used.

  The ethylene / α-olefin block copolymer can be obtained by copolymerization of ethylene and α-olefin. An ethylene monomer unit is a structural unit formed from ethylene, and an α-olefin monomer unit is a structural unit formed from an α-olefin.

  As an alpha olefin, a C3-C20 alpha olefin is mentioned, for example. The carbon number of the α-olefin is preferably 3-15, more preferably 3-10.

  Examples of the α-olefin include 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, etc. Among them, 1-octene can be particularly preferably used. . Moreover, an alpha olefin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The number average molecular weight (Mn) of the ethylene / α-olefin block copolymer may be, for example, 500 to 500,000, preferably 10,000 to 300,000.

  The ratio (Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the ethylene / α-olefin block copolymer may be, for example, 1.0 to 4.0, preferably 1. 7-3.5.

  The ethylene / α-olefin block copolymer preferably has at least one melting point in the range of 110 to 130 ° C. The melting point was determined by measuring a DSC curve between 0 ° C. and 200 ° C. under a temperature rising rate of 10 ° C./min using a DSC (Differential Scanning Calorimeter) in accordance with JIS K7122. Determine based on.

The ethylene / α-olefin block copolymer preferably has a density at 23 ° C. of 0.85 to 0.90 g / cm ³ , and more preferably 0.86 to 0.89 g / cm ³ . The density is measured according to ASTM D792.

  The ethylene / α-olefin block copolymer preferably has a melt flow rate of 3 g / 10 min or more measured under conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with ASTM D-1238. When the melt flow rate is less than 3 g / 10 minutes, jetting may occur, multilayer peeling, silver streak, etc. may occur during injection molding, and the appearance and strength of the joining member may deteriorate. That is, in this embodiment, the melt flow rate of the ethylene / α-olefin block copolymer is 3 g / 10 min or more, thereby suppressing the occurrence of jetting, multilayer peeling, silver streak, etc. during injection molding. And the joining member excellent in an external appearance and intensity | strength can be formed.

  The melt flow rate (ASTM D-1238, temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin block copolymer may be 10 g / 10 min or more, or 20 g / 10 min or more. . Moreover, the said melt flow rate may be 50 g / 10min or less, for example.

  The durometer A hardness (also referred to as Shore A hardness) of the ethylene / α-olefin block copolymer is preferably in the range of 50 to 85. In addition, in this specification, durometer A hardness shows the value measured based on ASTMD2240.

  The maximum tensile elongation of the ethylene / α-olefin block copolymer is preferably 500% or more, and more preferably 800% or more. In the present specification, the maximum tensile elongation is a value measured in accordance with ASTM D638. When the maximum tensile elongation of the ethylene / α-olefin block copolymer is 500% or more, it is possible to obtain a joining member that is further excellent in adhesiveness to a molded body made of a resin material.

  In addition, a molded article including a molded body containing vulcanized EPDM and a joining member bonded to the molded body can be manufactured by insert injection integral molding of vulcanized EPDM and an adhesive composition. At this time, if the maximum tensile elongation of the ethylene / α-olefin block copolymer is less than 500%, a crack considered to be caused by the difference in shrinkage rate occurs on the joining member side in the vicinity of the adhesive interface, and the member strength and Adhesive strength may be reduced. In this respect, when the maximum tensile elongation of the ethylene / α-olefin block copolymer is 500% or more, even when the molded product is produced by the integral molding as described above, the occurrence of the crack is suppressed, and a high member Strength and high adhesive strength can be obtained.

  When the adhesive composition is used for forming a weatherstrip joining member, the compression set of the ethylene / α-olefin block copolymer is preferably 80% or less, more preferably 70% or less, and 60 % Or less is more preferable. The weather strip is a part that dynamically or statically deforms to seal the window glass and the vehicle body, and it is desirable that the joint member has a small compression set. By setting the compression set of the ethylene / α-olefin block copolymer within the above range, a compression set suitable as a weatherstrip joining member can be easily realized. The compression set of the joining member can be adjusted by components other than the ethylene / α-olefin block copolymer, but the compression set is sufficiently low as an ethylene / α-olefin block copolymer having a large content. By using what has, the compression set suitable as a joining member for weather strips is easily realizable. In addition, in this specification, compression set shows the value measured on condition of 70 degreeC and 23 hours based on ASTMD395.

  The content of the ethylene / α-olefin block copolymer in the adhesive composition is 60 to 95% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer and the crosslinked polymer. When the content is less than 60% by mass, the injection moldability of the adhesive composition and the adhesion of the resulting joining member to the resin material (particularly vulcanized rubber) may be deteriorated. Moreover, when content exceeds 95 mass%, while the adhesiveness with respect to the resin material of the joining member obtained will deteriorate, there exists a tendency for sliding performance to become difficult to be obtained.

  The content of the ethylene / α-olefin block copolymer in the adhesive composition is preferably 65 to 95% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer. More preferably, it is 70-90 mass%.

(B) Crosslinked polymer The crosslinked polymer is a crosslinked product obtained by crosslinking one or two or more kinds of polymers including an ethylene / polar monomer copolymer (hereinafter, sometimes referred to as “uncrosslinked polymer”).

  The crosslinked polymer is dispersed in a matrix (sea phase) containing an ethylene / α-olefin block copolymer to form a domain (island phase). The adhesive composition contains a cross-linked polymer, so that deterioration of moldability and adhesiveness due to the addition of the silicone compound is suppressed. That is, since the adhesive composition has a crosslinked polymer, the effect of sliding performance by the silicone compound can be remarkably obtained while maintaining excellent moldability and adhesion to the resin material.

  In addition, the adhesive composition contains a cross-linked polymer, so that it is favorable for a resin material (for example, a vulcanized rubber such as vulcanized EPDM) in which good adhesiveness is difficult to obtain with a conventional joining member. A joining member to be joined with adhesiveness can be obtained. The reason for this is not necessarily clear, but (i) the domain formed by the cross-linked polymer prevents the localization of the silicone compound and suppresses the decrease in local adhesion, (ii) the injected adhesive composition has Relieving internal stress generated at the adhesive interface with the resin material during cooling and solidification, (iii) Chemical adhesive force derived from polar monomer units (resin material and adhesive force, filler dispersed in the resin material (carbon It is conceivable that an adhesive force with black, silica or the like is developed.

  Further, in the adhesive composition, since a domain containing a crosslinked polymer is formed, fine irregularities are formed on the surface of the bonding member formed from the adhesive composition. Due to the unevenness, the bonding member is considered to have excellent adhesion when fused to the resin material, to suppress surface tackiness, and to have excellent sliding performance.

  Examples of ethylene / polar monomer copolymers include ethylene / methyl acrylate copolymer (EMA), ethylene / ethyl acrylate copolymer (EEA), ethylene / butyl acrylate copolymer (EBA), and ethylene / methyl methacrylate. Examples thereof include a copolymer (EMMA) and an ethylene / vinyl acetate copolymer.

  The ethylene / polar monomer copolymer is based on the total amount of ethylene units and polar monomer units, and the content of polar monomer units is preferably 15 to 90% by mass, more preferably 20 to 90% by mass, More preferably, it is 30-90 mass% or more. When the content of the polar monomer unit is 15% by mass or more, the adhesion to a resin material (particularly a vulcanized rubber such as vulcanized EPDM), the appearance of injection molding and the sliding performance tend to be further improved.

  Here, as described later, the crosslinked polymer can be obtained by dynamic crosslinking. When the content of the polar monomer unit is 15% by mass or more, the appearance of the dynamically crosslinked product containing the crosslinked polymer is strongly matte. It will be a thing. Further, when the content of the polar monomer unit is increased to 20% by mass and 30% by mass, the matte feeling becomes stronger, and the matte feeling continues to increase to about 60% by mass. If it is 60-90 mass%, there is not much difference in a matte feeling, and if it exceeds 90 mass%, a matte feeling will fall. From these facts, by setting the content of polar monomer units in the above specific range, the degree of cross-linking and / or incompatibility of the cross-linked polymer becomes remarkable, and a sea island structure with high contrast (separation between matrix and domain) It is considered that the adhesiveness, injection moldability, the effect of suppressing the uneven distribution of the silicone compound, and the like are improved by the structure.

  The crosslinked polymer is obtained by crosslinking an uncrosslinked polymer containing an ethylene / polar monomer copolymer. The uncrosslinked polymer may contain a polymer other than the ethylene / polar monomer copolymer. For example, the uncrosslinked polymer may contain one or more selected from the group consisting of an ethylene / α-olefin block copolymer and an ethylene / α-olefin / non-conjugated diene copolymer.

  Examples of the ethylene / α-olefin block copolymer as the uncrosslinked polymer include those similar to the ethylene / α-olefin block copolymer described in (a) above.

  Examples of the ethylene / α-olefin / non-conjugated diene copolymer as the uncrosslinked polymer include ethylene / propylene / 5-vinyl-2-norbornene copolymer and ethylene / propylene / 5-ethylidene-2-norbornene. Can be mentioned.

  The crosslinked polymer may be obtained by crosslinking an uncrosslinked polymer including, for example, an ethylene / polar monomer copolymer and an ethylene / α-olefin block copolymer. According to such a crosslinked polymer, it is possible to obtain a joining member that is further excellent in adhesiveness with a resin material (particularly vulcanized rubber).

  In this embodiment, the blending amount of the ethylene / α-olefin block copolymer is preferably 10 to 50% by mass with respect to the total amount of the ethylene / polar monomer copolymer and the ethylene / α-olefin block copolymer. More preferably, it is 10-40 mass%. By setting the blending amount of the ethylene / α-olefin block copolymer within the above range, it is possible to further improve the adhesiveness with a resin material (particularly vulcanized rubber) while maintaining excellent moldability.

  The crosslinked polymer may be obtained by crosslinking an uncrosslinked polymer containing an ethylene / polar monomer copolymer and an ethylene / α-olefin / nonconjugated diene copolymer. By using such a crosslinked polymer, there is a tendency that a domain having a suitable average diameter described later is easily formed. In addition, the uncrosslinked polymer easily undergoes a crosslinking reaction, and the productivity of the crosslinked polymer is improved. Furthermore, according to such a crosslinked polymer, the compression set of the joining member can be further suppressed.

  In this embodiment, the blending amount of the ethylene / α-olefin / non-conjugated diene copolymer is preferably 0 with respect to the total amount of the ethylene / polar monomer copolymer and the ethylene / α-olefin / non-conjugated diene copolymer. It is 5-10 mass%, More preferably, it is 1-8 mass%.

  The crosslinked polymer is obtained by crosslinking an uncrosslinked polymer including an ethylene / polar monomer copolymer, an ethylene / α-olefin block copolymer, and an ethylene / α-olefin / non-conjugated diene copolymer. It may be. According to such a crosslinked polymer, a domain having a suitable average diameter is easily formed. Moreover, according to such a crosslinked polymer, adhesiveness with a resin material (particularly vulcanized rubber) can be further improved, and the compression set of the joining member can be further reduced.

  In this embodiment, the blending amount of the ethylene / α-olefin block copolymer is an ethylene / polar monomer copolymer, an ethylene / α-olefin block copolymer, and an ethylene / α-olefin / non-conjugated diene copolymer. Preferably it is 9.5-49.5 mass% with respect to the total amount, More preferably, it is 9-49 mass%.

  In this embodiment, the blending amount of the ethylene / α-olefin / non-conjugated diene copolymer is selected from the group consisting of ethylene / polar monomer copolymer, ethylene / α-olefin block copolymer, and ethylene / α-olefin / non-conjugated. Preferably it is 0.5-10 mass% with respect to the total amount of a diene copolymer, More preferably, it is 0.5-8 mass%.

  The content of the crosslinked polymer in the adhesive composition is 3.5 to 32% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer and the crosslinked polymer. When the content of the cross-linked polymer is less than 3.5% by mass, the adhesion to the resin material (particularly vulcanized rubber) is deteriorated, the sliding performance is deteriorated, and the adhesive member surface is tacky and dust is generated. In some cases, problems such as being likely to adhere to the surface may occur. Moreover, when content of a crosslinked polymer exceeds 32 mass%, the problem that adhesiveness with a resin material (especially vulcanized rubber) falls and injection moldability may deteriorate may arise.

  The content of the crosslinked polymer in the adhesive composition is preferably 7 to 32% by mass, more preferably 10 to 32, based on the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer and the crosslinked polymer. % By mass. When the content of the crosslinked polymer is within the above range, it is possible to further improve moldability and adhesiveness while maintaining good sliding performance with the silicone compound.

  The domain formed by the crosslinked polymer (crosslinked body domain) preferably has an average diameter of 1 to 50 μm, more preferably 2 to 40 μm, and even more preferably 5 to 25 μm. When the average diameter of the crosslinked domain is 1 μm or more, uneven distribution of the silicone compound in the adhesive composition is more significantly suppressed. For this reason, when the average diameter of the crosslinked body domain is 1 μm or more, problems such as multi-layer peeling during injection molding, generation of silicone bleed after molding, and deterioration of long-term slidability in the joining member become more prominent. Can be suppressed. On the other hand, when the average diameter of the crosslinked body exceeds 50 μm, jetting, foaming, silver streak and the like are likely to occur during injection molding, and moldability may be deteriorated.

  The average diameter of the cross-linked domain is measured by the following method. First, a slice is cut out from a measurement sample (adhesive composition or molded product thereof) containing a cross-linked domain using a frozen microtome and dyed using osmium tetrachloride or ruthenium tetrachloride. Next, the dyed product is observed at a magnification of × 1200 using a TEM (transmission electron microscope). The contour of the cross-linked domain dispersed in the test piece is outlined, the longest diameter d1 is measured, and then the shortest diameter d2 passing through the center of the longest diameter is measured, and the domain diameter d = (d1 + d2) / 2. . Select 10 domains with the longest diameter of 0.2 μm or more. The average of the ten domain diameters d is the average diameter of the cross-linked domains.

  In this embodiment, the crosslinked polymer may be formed by, for example, dynamic crosslinking. According to the dynamic crosslinking, a crosslinked polymer that forms a suitable crosslinked body domain can be easily obtained. Dynamic cross-linking is a method in which cross-linking is performed simultaneously with kneading to give shear, and for example, kneading can be performed by kneading a resin composition containing an uncross-linked polymer, a propylene-based polymer and a cross-linking agent.

  Examples of the crosslinking agent used for dynamic crosslinking include organic peroxides, sulfur vulcanizing crosslinking agents, resin crosslinking crosslinking agents, hydrosilyl crosslinking agents, and the like, among which organic peroxides are preferred. . Further, an organic peroxide and an organohydrogenpolysiloxane that is a hydrosilyl-based crosslinking agent can be used in combination.

  As the organic peroxide, peroxyketal, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxydicarbonate and the like are preferable.

  Specific examples of the organic peroxide include 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Di (t-butylperoxy) cyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Oxy) hexane, di (2-t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5- Di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-hexylperoxybenzoate, t Examples include butyl peroxy-3-methylbenzoate, diisopropyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, and the like. .

Examples of the organohydrogenpolysiloxane include those containing 2 or more, preferably 3 or more hydrogen atoms (SiH groups) bonded to silicon atoms, and less than about 100 SiH groups. The number (or degree of polymerization) of silicon atoms in one molecule is about 3 to 200, and polysiloxanes having a linear, cyclic, branched, and three-dimensional network (resin-like) molecular structure can be used. Specifically, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane , Both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked Dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methyl Hydrogen diphenylsiloxane-dimethylsiloxane copolymer _{(CH 3)} 2 _HSiO consisting _1/2 units and _{SiO 4/2} units, and copolymers _{thereof, (CH} 3) 2 _{HSiO 1/2} units and _{SiO 4/2} Examples thereof include a copolymer composed of units and (C ₆ H ₅ ) ₁ SiO _1/2 units. When the organic peroxide and the organohydrogenpolysiloxane are used in combination, the particle size of the crosslinked domain tends to be uniform and a bonded member having more excellent characteristics can be obtained than when the organic peroxide is used alone.

(C) Propylene-type polymer As a propylene-type polymer, the polymer which has a propylene monomer unit 60 mass% or more is mentioned. The said adhesive composition can form the joining member excellent in adhesiveness with various resin materials by containing a propylene polymer. In particular, in the present embodiment, by containing a propylene polymer, it has excellent adhesion to a molded body containing a thermoplastic resin (for example, olefin thermoplastic elastomer, styrene thermoplastic elastomer, polypropylene, etc.). A joining member can be formed.

  The propylene-based polymer is preferably a polymer selected from the group consisting of propylene and a propylene / α-olefin copolymer.

  Examples of the α-olefin in the propylene / α-olefin copolymer include the same α-olefin as the α-olefin in the ethylene / α-olefin block copolymer described above.

  As the propylene-based polymer, those having high crystallinity and those having low crystallinity can be widely used. The melting point of the propylene polymer is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 130 ° C. or higher. By using a propylene polymer having a melting point of 70 ° C. or higher, the compression set of the joining member formed from the resin composition can be further improved. The upper limit of the melting point of the propylene-based polymer may be 175 ° C or 165 ° C. The melting point was determined by measuring a DSC curve between 0 ° C. and 200 ° C. under a temperature rising rate of 10 ° C./min using a DSC (Differential Scanning Calorimeter) in accordance with JIS K7122. Determine based on.

  The propylene-based polymer preferably has a melt flow rate of 0.1 to 300 g / 10 minutes measured under conditions of a temperature of 190 ° C. and a load of 21.18 N in accordance with ASTM D-1238. More preferably, it is 5-100 g / 10min. Within this range, when dynamic crosslinking of the crosslinked domains is performed using a propylene-based polymer, the average diameter of the crosslinked domains can be easily controlled within a suitable range.

  As the propylene-based polymer, homopolypropylene, block polypropylene, random polypropylene, random block polypropylene, amorphous polypropylene having lower crystallinity than random polypropylene, and the like can be appropriately selected and used.

  Examples of the polypropylene-based polymer include “Prime PP” manufactured by Prime Polymer Co., Ltd., “Novatech” and “Wintech” manufactured by Nippon Polypro Co., Ltd., Sun Allomer Ltd. Examples include homopolypropylene, block polypropylene, and random polypropylene sold under trade names such as “Qualia”.

  Further, examples of the amorphous polypropylene include “Prime TPO” manufactured by Prime Polymer Co., which is a polypropylene-ethylene copolymer, “VERSIFY” manufactured by Dow Chemical Co., “Vistamaxx” manufactured by ExxonMobil Chemical Co., and the like. Examples of the propylene-1-butene copolymer include “TAFTHREN” manufactured by Sumitomo Chemical Co., Ltd., “TAFMER PN” manufactured by Mitsui Chemicals, Inc. and “TAFMER XM”. Examples of the propylene-ethylene-1-butene copolymer include “TAFMER XM” manufactured by Mitsui Chemicals.

  As the propylene-based polymer, for example, amorphous polypropylene can be preferably used from the viewpoint of imparting flexibility suitable as a weather strip.

  The content of the propylene polymer in the adhesive composition is 1.5 to 15% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer. When the content is less than 1.5% by mass, the adhesion to a resin material (particularly a thermoplastic resin) tends to deteriorate. On the other hand, if the content exceeds 15% by mass, multilayer peeling, silicone compound seepage and the like are likely to occur during injection molding, and the appearance of the joining member and the adhesion to the resin material tend to deteriorate.

  The content of the propylene polymer in the adhesive composition is preferably 2 to 15% by mass, more preferably 4 based on the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer. -14 mass%.

  In the present embodiment, for example, a propylene-based polymer is used in the dynamic crosslinking of the crosslinked polymer, and a precursor composition in which a crosslinked domain is formed in a matrix of the propylene-based polymer can be formed. And in this embodiment, a crosslinked polymer and a propylene-type polymer can be mix | blended with an adhesive composition by mixing this precursor composition with another component. At this time, a propylene-based polymer can be appropriately added so as to satisfy the above-mentioned preferable content.

(D) Silicone Compound The silicone compound is a component that imparts slidability. In the adhesive composition according to this embodiment, a combination of the above-described components makes it possible to achieve both good slidability due to the silicone compound and excellent adhesiveness to the resin material.

  Examples of the silicone compound include a gum-like or solid first silicone compound and an oil-like second silicone compound. The silicone compound may contain one of these or both.

  Examples of the first silicone compound include silicone gum, silicone resin, and silicone powder.

The silicone gum preferably has a weight average molecular weight of 1 × 10 ⁵ or more. The weight average molecular weight of the silicone gum may be 1 × 10 ⁶ or less, for example. Examples of the silicone gum include dimethyl silicone, methyl phenyl silicone, acrylic silicone, and the like.

Examples of the silicone resin include MQ resin. The MQ resin is, for example, a resin having R ₃ SiO _1/2 units (M units) and SiO _4/2 units (Q units) (R is an unsubstituted or substituted carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group).

  Examples of the hydrocarbon group represented by R include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, and an allyl group. Substituted with a cyano group such as a chloromethyl group, a chloropropyl group or a trifluoropropyl group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms. A cyanoethyl group, an glycidoxypropyl group substituted with an epoxy group, an epoxycyclohexylethyl group, a methacryloxypropyl group substituted with a (meth) acryl group, an acryloxypropyl group, an aminopropyl group substituted with an amino group, A mercaptopropyl group substituted with a mercapto group, such as an aminoethylaminopropyl group, etc. It is below.

In MQ resin, it is preferable that the content rate of M unit and Q unit is 30-50 mol%, respectively. The MQ resin may further have R ₂ SiO _2/2 units (D units) and RSiO _3/2 units (T units), and the content ratio of these units is 20 mol% or less. It is preferable. In addition, the content rate of each unit is a content rate on the basis of the total number of the structural units containing one Si atom.

The weight average molecular weight of MQ resin becomes like this. Preferably it is 1 * 10 < ⁴ > -1 * 10 < ⁶ >, More preferably, it is 5 * 10 < ⁴ > -5 * 10 < ⁵ >.

The silicone powder is, for example, particles composed of a crosslinked body of silicone resin, and preferably near-spherical particles. The crosslinked body of the silicone resin preferably has a structure crosslinked in a three-dimensional network represented by (RSiO _3/2 ) n. Silicone powder can also be called polyorganosilsesquioxane cured product powder.

  Examples of the silicone powder include “KMP-590”, “KMP-701”, “X-52-854”, and “X-52-162” manufactured by Shin-Etsu Chemical Co., Ltd. as commercially available products.

  The silicone powder may be, for example, resin-crosslinked spheres of acrylic silicone. Examples of such silicone powder include “Charine R200” manufactured by Nissin Chemical Industry Co., Ltd.

Examples of the second silicone compound include dimethyl silicone oil, methyl phenyl silicone oil, and modified oils having a weight average molecular weight of 1 × 10 ⁵ or less and a kinematic viscosity of 1 × 10 ⁵ mm ² / sec or less. Here, as a modified product, hydrogen polysiloxane in which a part of methyl group or phenyl group is substituted with hydrogen, alkyl-modified silicone oil substituted with alkyl group, fluorine-modified with fluorine atom or fluorinated alkyl group Examples thereof include silicone oil, polyether-modified silicone oil, and amino-modified silicone oil.

  An organohydrogenpolysiloxane used as a crosslinking aid in the above-described dynamic crosslinking can also be included in the second silicone compound.

(E) Other components The adhesive composition according to this embodiment may further contain components (additives) other than those described above.

  The adhesive composition may further contain, for example, paraffinic oil. Since the hardness of the joining member formed by adding paraffinic oil is lowered, the hardness of the joining member can be appropriately adjusted by adding paraffinic oil.

  The adhesive composition is, for example, a crosslinked product of ethylene / propylene / diene rubber (EPDM); a crosslinked product of ethylene / α-olefin random copolymer; a styrene / butadiene / styrene block copolymer, a styrene / isoprene / styrene block. It may further contain a copolymer or a cross-linked product of these water additives. Moreover, the adhesive composition may further have a domain formed from the crosslinked body.

  Further, an olefinic thermoplastic elastomer may be further added to the adhesive composition. By adding an olefinic thermoplastic elastomer, compression set may be able to be kept lower.

  As the olefinic thermoplastic elastomer, for example, a dynamically crosslinked olefinic thermoplastic elastomer can be suitably used.

  The olefinic thermoplastic elastomer may contain ethylene / propylene / diene rubber (and its cross-linked product) and polypropylene as main components. The olefinic thermoplastic elastomer may contain paraffinic oil. That is, in the present embodiment, an adhesive composition containing paraffinic oil, a crosslinked EPDM, PP, and the like may be obtained by adding an olefinic thermoplastic elastomer.

  Examples of olefin-based thermoplastic elastomers include “Thermorun” manufactured by Mitsubishi Chemical, “Exelink” manufactured by JSR, “Esporex TPE” manufactured by Sumitomo Chemical, “Milastomer” manufactured by Mitsui Chemicals, “Surlink” manufactured by Techno Apec, and Exxon Chemical “Santoprene” manufactured by Riken Technos, “Activimer G” manufactured by Riken Technos, and the like.

  The content of the additive is not particularly limited, and may be, for example, 10 to 30 parts by mass with respect to 100 parts by mass of the total amount of the ethylene / α-olefin block copolymer, the propylene-based polymer, and the crosslinked polymer. It is good also as 15-25 mass parts.

  The adhesive composition according to the present embodiment is used to form a joining member that joins members. The joining member can be formed by, for example, injection molding.

  Moreover, according to the adhesive composition which concerns on this embodiment, a molded article provided with two or more members and the joining member which interposes between these members and joins between members can be manufactured.

  The member joined by the joining member is preferably a member formed from a resin material from the viewpoint that the above-described effects are remarkably exhibited. Moreover, the said member can use suitably the thing containing a rubber material and / or a thermoplastic resin in a contact surface with a joining member. The rubber material may be, for example, vulcanized rubber or vulcanized EPDM. The thermoplastic resin may be polypropylene, olefinic thermoplastic elastomer, styrene thermoplastic elastomer, or the like.

  The joining member can be suitably used as a corner member or a fitting member of an automobile weather strip. Examples of weather strips include sunroof seals, trunk lids (Luggage), roof sides, door outers (doors), waist seals, door inner seals (open trims, welt body sides), glass run channels, etc. Any of these can be suitably applied.

  Moreover, the use of the joining member is not limited to the weather strip, and can be suitably used for applications requiring good adhesiveness and slidability. The joining member can be suitably applied to, for example, toys and sundries. That is, the molded product may be, for example, a weather strip, and may be a toy, miscellaneous goods, or the like.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

[Example group A]
(Preparation of dynamically crosslinked products MR-1, MR-2 and FC-1)
The raw materials were mixed with a Hensyl mixer with the composition shown in Table 1. The mixture is put into a twin screw extruder PCM30 L / D32 (manufactured by Ikegai Co., Ltd.) whose temperature is kept at 150 to 170 ° C., and dynamic crosslinking is performed under the conditions of a screw rotation speed of 250 rpm and an extrusion rate of 5 kg / hr. It was. The dynamic cross-linked product was discharged from the extruder head without a die (release extrusion). The discharged product was cooled in a water bath to approximately 40 to 80 ° C., air-dried, and then pulverized to a size allowing a φ5 mm punch hole to pass through by a pulverizer. This was used as dynamic cross-linked products MR-1, MR-2, and FC-1. In the following table, the composition of the raw materials is shown by mass ratio.

Details of the raw materials listed in Table 1 are as follows.
(I) Ethylene / Polar monomer copolymer “LEVAPREN 400”
Ethylene-vinyl acetate copolymer, manufactured by LANXESS (LANXESS Deutschland GmbH), vinyl acetate content: 40% by mass, Mooney viscosity (ML (1 + 4), 100 ° C.): 20.
(Ii) Ethylene / α-olefin block copolymer / “INFUSE 9817”
Ethylene / octene block copolymer, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 190 ° C., ASTM D1238): 15 g / 10 min, DSC melting point: 120 ° C., Shore A hardness (ASTM D2240): 71 Maximum tensile elongation (ASTM D638): 1500%, density (23 ° C., ASTM D792): 0.877 g / cm ³ , compression set (70 ° C., 23 hours, ASTM D395): 58%.
(Iii) Propylene polymer “PN-2060”
TAFMER PN-2060, manufactured by Mitsui Chemicals, propylene / butene block copolymer, MFR (load 2.16 kg, 230 ° C., ASTM D1238): 6 g / 10 min, DSC melting point: 161 ° C., Shore A hardness (ASTM D2240): 84.
(Iv) Other ・ "SIBSTER 062M"
Styrene / isobutylene block copolymer manufactured by Kaneka Corporation, Shore A hardness (ASTM D2240): 20.
・ "A-DCP"
Reaction aid, NK ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd., diacryldicyclopentadiene.
・ "KF-99"
Reaction aid, silicone compound, methyl hydrogen silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
・ "Perhexa 25B40"
Organic peroxide, silica dilution of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, purity of organic peroxide 40% by mass, manufactured by NOF Corporation.

(Examples A-1 and A-2, Comparative Examples A-1 to A-5)
The raw materials having the compositions described in Table 2 and Table 3 were mixed with a Hensyl mixer. The mixture is put into a twin screw extruder PCM30 L / D32 (manufactured by Ikegai Co., Ltd.) whose cylinder is kept at 150 to 160 ° C., and a screw die is attached to the extruder head with a hole die kept at 170 ° C. Mixing and dispersing were performed under the conditions of 250 rpm and an extrusion rate of 5 kg / hr, the strand was extruded, the strand was cooled in a water tank, and cut with a cutter to produce a pellet having a length of about 3 mm. The produced pellets were used as the resin compositions of Examples A-1 to A-2 and Comparative Examples A-1 to A-5.

Details of the raw materials described in Table 2 and Table 3 are as follows.
(V) Silicone compound “X-22-2101”
Silicone masterbatch, pellets in which silicone gum is dispersed in polypropylene, silicone gum content: 50% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.
・ "KF96-1000cs"
Dimethyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
・ "KF96-27,000cs"
Dimethyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., KF96H-10,000cs and KF96H-50,000cs mixed at 8: 6.
(Vi) Stabilizer “AO-60”
ADK STAB AO-60, hindered phenol antioxidant, manufactured by ADEKA Corporation.
・ "LA-63P"
ADK STAB LA-63P, hindered amine light stabilizer, manufactured by ADEKA Corporation.
・ "LA-36"
ADK STAB LA-36, benzotriazole UVA, manufactured by ADEKA Corporation.
・ "PEP36A"
ADK STAB PEP36A, phosphite antioxidant, manufactured by ADEKA Corporation.

(Adhesion evaluation)
A pre-vulcanized EPDM sheet (in Table 4 and Table 5, "vulcanized EPDM") or Miralastomer W700B (olefin-based thermoplastic elastomer, manufactured by Mitsui Chemicals, Inc., in Table 4 and Table 5, "TPO") Prepare these, insert these sheets into an injection mold, melt-inject the resin compositions prepared in the above-mentioned Examples and Comparative Examples, join the inserted sheets in the mold, cool, and evaluate adhesion A sample was used.

  More specifically, the resin compositions (pellets) produced in the above-described examples and comparative examples were put into a hopper of an 80 ton injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., molding machine name: FS80S12ASE). The pellets were preliminarily dried at 90 ° C. for 3 hours immediately before injection molding. A sheet mold was attached to the injection molding machine. The mold was cooled by circulating water at 40 ° C. The sheet mold was a mold having a depth of 3 mm, a width of 103 mm, and a length of 130 mm. A vulcanized EPDM sheet or TPO sheet was inserted into the mold, and the mold was clamped, and the pellets were melted and injected. The cylinder temperature is set to 220 ° C., 220 ° C., 210 ° C., and 180 ° C. for the nozzle, front, middle, and rear, respectively, and the pellet is melted at 60% of the maximum screw rotation speed while applying pressure, and the injection hydraulic pressure is 50 % Injection speed was 80 to 60%, holding pressure was 30 to 10%, and the injection time was 5 seconds. The injection was carried out to the vulcanized EPDM sheet or TPO sheet and the resin composition was shaped. After taking the cooling time of 30 seconds, the mold was opened, and the joining sheet (adhesion evaluation sample) was taken out.

-Adhesion evaluation 1 (tensile breaking strength, tensile breaking elongation)
The joining sheet was punched out into JIS K6251 No. 3 dumbbell so that the joining surface was the center of the dumbbell. Using a tensile tester (Strograph E-L manufactured by Toyo Seiki Co., Ltd.), the breaking strength and breaking elongation were measured based on JIS K6251 at a tensile speed of 200 mm / min.

・ Adhesion evaluation 2 (bending and peeling)
After leaving the joining sheet at room temperature for 48 to 68 hours, the joining sheet was cut into a width of 30 mm to obtain a test sheet. A line was drawn on both sides of a 15 mm portion in parallel from the joint line of the test sheet. A finger was placed between the joint and the marked line, picked with the thumb and forefinger of both hands, the test sheet was bent (folded) to 180 ° C. at the joint surface, and held for 3 seconds after folding. If it did not peel completely, it was bent to the opposite side by the same operation. This operation was repeated when it was not completely removed.

  When 180 ° bending was performed six times (counting once on one side), bending was performed within 135 °, and the total peeled area on both sides was visually identified. Evaluation evaluation of peeling area is (A) hardly peeled: peeling area / total bonding area is 0 to less than 10%, (B) less than 20%, (C) 20 to 50%, (D) 50 to 80%, (E) Almost peeling: 80 to 100%, (F) Complete peeling: 100%. In addition, when it became 100% complete peeling before performing 6 times, the frequency | count of bending at the time of complete peeling was recorded. For samples that cannot be peeled off completely after 6 times, the bending operation is performed up to 20 times, but when bent, the region becomes “(E) almost peeled: 80-100%” or “(F) 100% completely peeled” The number of times was recorded (in the table, “80% or more peeling number”). When 80% was not peeled after bending 20 times, it was set as “20 bending or more”. The test was performed at room temperature.

  The evaluation results are shown in Tables 4 and 5. In Tables 4 and 5, the content of the ethylene / α-olefin block copolymer relative to the total amount standard of the ethylene / α-olefin block copolymer, propylene-based polymer and cross-linked polymer (in the table, “( The a) content ”), the content of the crosslinked polymer (in the table,“ (b) content ”), and the content of the propylene polymer (in the table,“ (c) content ”) are also shown. The silicone compound content (“silicone compound content” in the table) with respect to 100 parts by mass of the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer is also shown.

  In Examples A-1 and A-2, excellent adhesion (breaking strength, breaking elongation, bending resistance) to the vulcanized EPDM sheet and TPO sheet was shown. When the adhesive composition according to the present invention is used for a corner or a fitting portion of a weather strip, the test result of the adhesion evaluation 2 is more important than the test result of the adhesion evaluation 1. Weatherstrip corners and mating parts may be peeled off at the joint surface due to deformation when the door is closed, deformation that occurs when the glass starts to move in or when it enters, or deformation when it is fitted and assembled into the automobile body. Adhesion evaluation 2 for bending and imparting deformation to the joint surface is an evaluation method that matches this, and those that excel in adhesion evaluation 2 can be suitably used for weather strip applications.

[Example group B]
(Production of dynamic cross-linked products MR-3, MR-4 and MR-5)
In the composition shown in Table 6, the raw materials of mixture 1 were mixed with a Hensyl mixer. Separately from the mixture 1, the raw materials of the mixture 2 were mixed with a Hensyl mixer with the composition shown in Table 6.

  A heavy-weight hooder F1 was installed so that the mixture 1 could be quantitatively dropped into the barrel most upstream part insertion hole of a twin screw extruder TEM41 L / D = 62 (manufactured by Toshiba Machine Co., Ltd.). A side feeder was connected to the middle (middle stream) of the TEM 41 barrel, and a weight feeder F2 was installed in the side feeder hole so that the mixture 2 could be dropped in a certain amount. A watering cut type hot cut pelletizer was attached to the head. The temperature of the barrel upstream from the side feeder is adjusted to 160 to 140 ° C., the barrel block to which the side feeder is connected and the vicinity of the barrel are adjusted to 110 to 130 ° C., and the barrels after the side feeder are adjusted to 130 to 160 The temperature was adjusted to ℃, and the temperature of the head was adjusted to 200 ° C and the hot cut pelletizer to 170 ° C. The screw rotation was 350 rpm, the mixture 1 from F1 was fed to the twin screw extruder at 30 kg / hr, and the mixture 2 was fed from F2 to the twin screw extruder according to the composition ratio described in Table 6 (for example, MR-3 In this case, F1 = 30 kg / hr and F2 = 1.6 kg / hr were fed). The dynamic cross-linked product started by the organic peroxide (peroxide) in the mixture 2 was cut into pellets by a hot cut pelletizer, and dropped into a water bath with water to be sprayed and cooled. The pellet was dried by a dehydrator and pneumatic transportation to obtain a pellet having a diameter of about 3 mm. When the pellets were connected in a rosary shape, the pellets were pulverized by a pulverizer so as to pass through a φ3 mm punch hole.

Details of the raw materials listed in Table 6 are as follows.
(I) Ethylene / α-olefin / non-conjugated diene copolymer / “3092PM”
Mitsui EPT3092PM, manufactured by Mitsui Chemicals, Mooney viscosity (ML (1 + 4), 125 ° C., ASTM D1646): 61, ethylene content: 65% by weight, ENB (diene component) content: 4.6% by weight, non-oil-extended pellet.

(Examples B-1 to B-3, Comparative Examples B-1 to B-2)
With the composition shown in Table 7, the raw materials were mixed with a Hensyl mixer to prepare a mixture 3. From the upstream of the twin screw extruder TEM41 L / D = 62, a liquid injection valve was attached to the 1/3 barrel block and the 2/3 barrel block, and a gear pump was connected to each liquid injection valve. A heavy-weight hooder F1 was installed in the barrel uppermost stream insertion hole. A strand die was installed on the head of the twin screw extruder. The temperature of the barrel of the twin screw extruder was adjusted to 150 to 160 ° C, and the temperature of the head and the die was adjusted to 180 ° C. Feed the mixture 3 from F1 to the twin screw extruder, and from the gear pump G1 connected to the 1 / 3rd position from the upstream, “KF96-27,000 cs”, from the gear pump G2 connected to the 2 / 3rd position from the upstream While “KF96-1000cs” was poured into the twin-screw extruder, it was kneaded at a screw rotation of 150 rpm. The kneaded composition was extruded into a strand form from a die, cooled in a water tank, and cut with a fan cutter to produce a pellet of about φ3 × 3 mm. The feed amount from F1 was 35 kg / hr, and the feed amounts of G1 and G2 were fed at the composition amounts according to Table 7. In Comparative Examples B-1 and B-2, the mixture 3 was kneaded under the same kneading conditions as above without pouring liquid to produce pellets.

(Adhesion evaluation)
Evaluation similar to the adhesion evaluation 1 and the adhesion evaluation 2 of Example group A was performed. The evaluation results were as shown in Table 8 and Table 9.

(Slidability evaluation)
・ Sliding evaluation 1 (sliding resistance coefficient)
About the resin composition of an Example and a comparative example, injection molding was performed on the same conditions as the above-mentioned injection insert molding, and the sheet | seat of thickness 3mm, width 103mm, and length 130mm was produced. Note that the surface of the injection mold was finished so that the surface roughness Ra of the surface to be measured was 0.3 to 0.6 μm. The produced sheet was cut into a width of 26 mm to obtain a test sheet.

  The test sheet was fixed to the longitudinal center of the sample fixture. The free part width (velocity width) was 16 mm, and glass 50 mm □ was placed on the free part at the position shown in the reciprocating sliding tester, and a weight was placed on the glass so that a load f1 of 17 N was applied in the vertical direction. After standing for 5 minutes, the motor was operated, and the glass was operated at an average speed of 150 mm / sec (the working distance in the horizontal direction at the center of the glass was 140 mm). When the absolute value of the first maximum horizontal load is f2 and the horizontal load of the blank is f0, the static sliding resistance coefficient = (f2−f0) / f1. After that, sliding was continued, and the average (n = 4) of the absolute values of the positive and negative large horizontal loads of the seventh to tenth times was set to f3, and the dynamic sliding resistance coefficient = (f3-f0) / f1.

・ Sliding evaluation 2 (Friction coefficient by Haydon)
The static / dynamic friction coefficient was measured using HEIDON-14 (Slipping tester trade name, manufactured by Shinto Kagaku Co., Ltd.). Number of faces to be measured Injection under the same conditions as the above injection insert molding, except that the injection amount is adjusted using an injection mold that has been surface blasted so that the surface roughness Ra is 2.0 to 3.0 μm A sheet having a thickness of about 1.5 mm, a width of 60 mm, and a length of 80 mm was produced. The width was cut to 10 to 11 mm and fixed to a flat indenter sold exclusively for Haydon. The length that can be installed with glass was about 63 mm. A 500 g weight was placed on the flat indenter (vertical load), the glass was operated at a speed of 100 mm / min, and the static / dynamic friction coefficient was measured.

  The evaluation results are shown in Table 8 and Table 9. In Tables 8 and 9, the content of the ethylene / α-olefin block copolymer relative to the total amount standard of the ethylene / α-olefin block copolymer, propylene-based polymer and crosslinked polymer (in the table, “( The a) content ”), the content of the crosslinked polymer (in the table,“ (b) content ”), and the content of the propylene polymer (in the table,“ (c) content ”) are also shown. The silicone compound content (“silicone compound content” in the table) with respect to 100 parts by mass of the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer is also shown.

[Example group C]
(Examples C-1 to C-3, Comparative Examples C-1 to C-9)
Except having changed "INFUSE 9817" into the raw material of Table 10, it carried out similarly to Example B-3, and produced the pellet of each Example and the comparative example.

  Moreover, adhesiveness evaluation and slidability evaluation were performed in the same manner as in Examples A and B. Further, compression set was evaluated under conditions of 70 ° C. and 23 hours in accordance with ASTM D395. The evaluation results are shown in Table 11, Table 12, Table 13, and Table 14.

The details of the raw materials listed in Table 9 are as follows.
・ "INFUSE 9807"
Ethylene / butene block copolymer, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 190 ° C., ASTM D1238): 15 g / 10 min, DSC melting point: 118 ° C., Shore A hardness (ASTM D2240): 55 Maximum tensile elongation (ASTM D638): 1200%, density (23 ° C., ASTM D792): 0.866 g / cm ³ , compression set (70 ° C., 23 hours, ASTM D395): 76%.
・ "INFUSE 9500"
Ethylene / butene block copolymer, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 190 ° C., ASTM D1238): 5 g / 10 min, DSC melting point 122 ° C., Shore A hardness (ASTM D2240): 69, Maximum tensile elongation (ASTM D638): 1150%, density (23 ° C., ASTM D792): 0.877 g / cm ³ , compression set (70 ° C., 23 hours, ASTM D395): 55%.
・ "INFUSE 9530"
Ethylene / butene block copolymer, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 190 ° C., ASTM D1238): 5 g / 10 min, DSC melting point 119 ° C., Shore A hardness (ASTM D2240): 83, Maximum tensile elongation (ASTM D638): 1000%, density (23 ° C., ASTM D792): 0.887 g / cm ³ , compression set (70 ° C., 23 hours, ASTM D395): 45%.
・ "INFUSE 9010"
Ethylene / butene block copolymer, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 190 ° C., ASTM D1238): 0.5 g / 10 min, DSC melting point: 122 ° C., Shore A hardness (ASTM D2240) : 77, Maximum tensile elongation (ASTM D638): 770%, Density (23 ° C, ASTM D792): 0.877 g / cm ³ (ASTM D1238), Compression set (70 ° C, 23 hours, ASTM D395): 67% .
・ "VERSIFY4301"
Ethylene / propylene copolymer having a high propylene ratio, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 230 ° C., ASTM D1238): 25 g / 10 min, DSC melting point: 55 ° C., Shore A hardness (ASTM D2240) ): 86, maximum tensile elongation (ASTM D638): 42%, density (23 ° C., ASTM D792): 0.868 g / cm ³ .
・ "VERSIFY2300"
Propylene / ethylene copolymer having a high propylene ratio, manufactured by Dow (Dow Chemical company), MFR (load 2.16 kg, 230 ° C., ASTM D1238): 2 g / 10 min, DSC melting point: 66 ° C., Shore A hardness (ASTM D2240) ): 86, density (23 ° C., ASTM D792): 0.866 g / cm ³ .
・ "H3712D"
Propylene / α-olefin copolymer having a high propylene ratio, manufactured by Sumitomo Chemical Co., Ltd., trade name: Tough Selenium H3712D, DSC melting point: 133 ° C., density (23 ° C., ASTM D792): 0.87 g / cm ³ .
・ "R110MP"
Propylene-ethylene block copolymer. Copolymer of hard segment made of polypropylene and soft segment made of ethylene / propylene. Product name: Prime TPO R110MP, DSC melting point: 155 ° C., density (23 ° C., ASTM D792): 0.88 to 0.90 g / cm ³ .
・ "EG8407"
Ethylene / octene random copolymer, manufactured by Dow (Dow Chemical company), trade name: ENGAGE8407, MFR (load 2.16 kg, 190 ° C., ASTM D1238): 30 g / 10 min, DSC melting point: 65 ° C., Shore A hardness ( ASTM D2240): 72, maximum tensile elongation (ASTM D638): 650%, density (23 ° C., ASTM D792): 0.877 g / cm ³ .
・ "A-4085S"
Ethylene / butene random copolymer, manufactured by Mitsui Chemicals, Inc., trade name: TAFMER A-4085S, MFR (load 2.16 kg, 190 ° C., ASTM D1238): 3.6 g / 10 min, DSC melting point: 66 ° C., Shore A hardness (ASTM D2240): 86, maximum tensile elongation (ASTM D638): 1100%, density (23 ° C., ASTM D792): 0.885 g / cm ³ .
・ "GA1950"
Ethylene / α copolymer, manufactured by Dow (Dow Chemical company), trade name: AFFINITY GA1950, MFR (load 2.16 kg, 190 ° C., ASTM D1238): about 500 g / 10 min, DSC melting point: 70 ° C., Shore A hardness (ASTM D2240): 70, maximum tensile elongation (ASTM D638): 1100%, density (23 ° C., ASTM D792): 0.874 g / cm ³ .

  The injection moldability was good in Examples C-1 to C-3. On the other hand, in Comparative Example C-1 and Comparative Example C-5, problems such as multilayer flow separation, occurrence of large silver and depression, and jetting occurred. In Comparative Examples C-2 and C-3, multilayer peeling was observed. In Comparative Example C-4, the occurrence of cracks was observed near the surface. In Comparative Examples C-6 to C-9, multilayer flow separation occurred, and it was difficult to obtain a sufficient molded product.

[Example group D]
(Preparation of dynamic cross-linked product MR-6)
Except for changing the composition of the mixture 1 and the mixture 2 to the composition shown in Table 15, the dynamic cross-linked product MR-6 was prepared in the same manner as in the production method of the dynamic cross-linked product MR-3 of Example Group B. Produced.

Details of the raw materials described in Table 15 are as follows.
(I) Ethylene / Polar monomer copolymer / "NUC-6940"
Ethylene / ethyl acrylate copolymer, manufactured by NUC, MFR (JIS K7210): 20 g / 10 min, DSC melting point: 83 ° C., Shore A hardness (ASTM D2240): 68, maximum tensile elongation (JIS K7162): 800% , Density (23 ° C., ASTM D792): 0.95 g / cm ³ .
(Ii) Propylene copolymer “E203GV”
Product name: Prime Polypro E-203GV, MFR (230 ° C., JIS K7210): 2 g / 10 min, DSC melting point: 169 ° C.
・ "MA3H"
Product name: NOBATET PP MA3H, MFR (JIS K7210, 230 ° C.): 2 g / 10 min, DSC melting point: 167 ° C., density (23 ° C., ASTM D792): 0.95 g / cm ³ .
(Iii) Ethylene / α-olefin copolymer / “A-1085S”
Ethylene / butene random copolymer, manufactured by Mitsui Chemicals, Inc., trade name: TAFMER A-1085S, MFR (load 2.16 kg, 190 ° C., ASTM D1238): 1.2 g / 10 min, DSC melting point: 66 ° C., Shore A hardness (ASTM D2240): 87, maximum tensile elongation (ASTM D638): 1200%, density (23 ° C., ASTM D792): 0.885 g / cm ³ .

(Examples D-1 to D-5, Comparative Examples D-1 to D-5)
Resin composition pellets were produced in the same manner as in Example Group B except that the composition of Mixture 3 was changed to the composition described in Table 16 and Table 17.

  As raw materials, a commercially available olefinic thermoplastic elastomer, 15 to 25% by mass of a propylene polymer, 25 to 35% by mass of an ethylene / propylene / ethylidene norbornene terpolymer, and 30 to 50 mass of paraffinic process oil. % Miralastomer 5030NF and Exelink 1300B were used.

  Moreover, adhesiveness evaluation and slidability evaluation were performed in the same manner as in Examples A and B. Further, compression set was evaluated under conditions of 70 ° C. and 23 hours in accordance with ASTM D395. The evaluation results are shown in Table 18, Table 19, Table 20, and Table 21. In Table 21, the compositions of Comparative Examples D-4 and D-5 described the values when the cross-linked polymer derived from “Miralastomer 5030NF” and “Excellin 1300B” was converted as the content (b). .

Details of the raw materials described in Tables 16 and 17 are as follows.
・ Miralastomer 5030NF
Commercially available olefinic thermoplastic elastomer. MFR (load 10 kg, 230 ° C., ASTM D1238): 30 g / 10 min, DSC melting point: 154 ° C., Shore A hardness (ASTM D2240): 51, maximum tensile elongation (ASTM D638): 480% Compression set (70 ° C., 23 hours, ASTM D395): 45%.
・ "Excellink 1300B"
JSR Corporation, MFR (load 10 kg, 230 ° C., ASTM D1238): 200 g / 10 min, DSC melting point: 134 ° C., Shore A hardness (ASTM D2240): 39, maximum tensile elongation (ASTM D638): 670%, compression Permanent set (70 ° C., 23 hours, ASTM D395): 35%.
・ "F-30940MM"
Product name: Peony Black F-30940MM manufactured by DIC Corporation, carbon black master batch pellet (polyethylene dispersed in carbon).
・ "HP-10"
Product name: ADK STAB HP-10, phosphite antioxidant, manufactured by ADEKA Corporation.

  In Examples D1 to D5, the injection moldability was good. On the other hand, in Comparative Examples D-2 to D-5, multilayer peeling occurred during injection molding.

[Example group E]
(Preparation of dynamic cross-linked product MR-7)
Except that the composition of the mixture 1 and the mixture 2 was changed to the composition shown in Table 22, the dynamic cross-linked product MR-7 was prepared in the same manner as in the production method of the dynamic cross-linked product MR-3 of Example Group B. Produced.

(Examples E-1 to E-8, Comparative Examples E-1 to E-3)
Resin composition pellets were prepared in the same manner as in Example Group B except that the composition of Mixture 3 was changed to the compositions shown in Table 23, Table 24, and Table 25.

  Moreover, adhesiveness evaluation and slidability evaluation were performed in the same manner as in Examples A and B. Further, compression set was evaluated under conditions of 70 ° C. and 23 hours in accordance with ASTM D395. The evaluation results are shown in Table 26, Table 27, and Table 28.

  In Examples E1 to E8, the injection moldability was good. On the other hand, in Comparative Example E-1, the gloss became sparse and the appearance was poor. In Comparative Examples E-2 to E-3, the gloss was sparse and multiple peeling was also observed.

Claims (7)

An adhesive composition containing an ethylene / α-olefin block copolymer, a propylene-based polymer, a crosslinked polymer and a silicone compound,
A matrix containing the ethylene / α-olefin block copolymer;
A domain comprising the cross-linked polymer dispersed in the matrix;
Have
The ethylene / α-olefin block copolymer has a hard block containing 95% by mass or more of ethylene monomer units, and a soft block containing more than 5% by mass of α-olefin monomer units,
The melt flow rate (ASTM D-1238, temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin block copolymer is 3 g / 10 min or more,
The crosslinked polymer is a crosslinked product obtained by crosslinking one or more polymers including an ethylene / polar monomer copolymer,
The content of the ethylene / α-olefin block copolymer is 60 to 95% by mass based on the total amount of the ethylene / α-olefin block copolymer, the propylene polymer and the crosslinked polymer, and the propylene polymer. The content of is 1.5 to 15% by mass, the content of the crosslinked polymer is 3.5 to 32% by mass,
The adhesive composition whose content of the said silicone compound is 1-10 mass parts with respect to 100 mass parts of total amounts of the said ethylene-alpha-olefin block copolymer, the said propylene-type polymer, and the said crosslinked polymer.   The crosslinked polymer contains the ethylene / polar monomer copolymer and at least one selected from the group consisting of an ethylene / α-olefin block copolymer and an ethylene / α-olefin / non-conjugated diene copolymer. The adhesive composition according to claim 1, which is a crosslinked polymer.   The adhesive composition according to claim 1, further comprising a paraffinic oil.   The adhesive composition according to any one of claims 1 to 3, wherein the silicone compound includes a gum-like or solid first silicone compound and an oily second silicone compound. A joining member for joining two or more members,
The joining member formed from the adhesive composition as described in any one of Claims 1-4. Two or more members;
The joining member according to claim 5, wherein the member is joined between the members.
A molded product comprising   The molded article according to claim 6, wherein at least one of the members includes a rubber material and / or a thermoplastic resin material on a contact surface with the joining member.