JP6263065B2 - Sliding material, sliding member, composite material, and method of manufacturing composite material - Google Patents

Description

  The present invention relates to a sliding material, a sliding member, a composite material, and a method for manufacturing the composite material.

  The weather strip attached to the sash of an automobile door holds the window glass firmly by sealing the outer peripheral edge of the window glass, and prevents intrusion of rain, wind, foreign objects, etc. into the vehicle, and the window glass. It is an automobile part used to smoothly open and close the door.

  In order to exert such a function, the weather strip is generally made of a sliding material containing an elastomer. Typical examples of the sliding material used in this case include a coating and curing type such as a urethane coating material, and a material obtained by adding various additives to an olefin resin or the like (see Patent Document 1).

  On the other hand, for the purpose of imparting slidability and the like, there is also a technique in which particles of a crosslinked body are added to a resin and an uneven shape is formed on the surface of the molded body based on the shape of the particles (see Patent Documents 2 and 3).

  Patent Document 4 discloses that two linear members are joined by a joining corner member so that the weather strip has a shape along the outer peripheral edge of the window glass (see Patent Document 4).

Japanese Patent Publication No. 7-73893 Japanese Patent No. 3693962 Japanese Patent Laid-Open No. 2002-20558 Japanese Patent Laid-Open No. 2003-253055

  The weather strip usually includes a weather strip main body portion made of a resin such as polypropylene and a sliding member made of a sliding material in sliding contact with the window glass. Here, as described in Patent Document 4, when two weather strips are bonded, a bonding material that ensures the bonding strength between the weather strip main body portions is used as the bonding member, and the weather strip main body portion is used. In general, the bonding member and the bonding member are bonded by resin fusion. As the bonding material, for example, a thermoplastic resin composition containing 15% by mass or more of a propylene polymer is suitably used.

  The weather strip main body is firmly bonded to the bonding member by fusion of the resin as described above. However, in the conventional weather strip, sufficient bonding strength is not necessarily obtained at the contact surface between the sliding member and the bonding member, and peeling of the contact surface may cause deterioration of the product.

  One of the objects of the present invention is to provide a sliding material that can be bonded with a bonding material for bonding a weather strip main body and the like with an excellent bonding strength, and a sliding member made of the sliding material. . Another object of the present invention is to provide a sliding member joined with excellent strength, a composite member including the joining member, and a method for manufacturing the same.

  One embodiment of the present invention contains a propylene-based polymer, an ethylene-based polymer, and a silicone compound, and at least a part of the ethylene-based polymer forms a crosslinked body, and 5-30% by mass of the propylene-based polymer. Relates to a sliding material wherein is an amorphous propylene-based polymer.

  The sliding material according to this aspect can be bonded with a bonding material (preferably a bonding material containing 15% by mass or more of a propylene-based polymer) used for bonding a weather strip main body or the like with excellent bonding strength. For this reason, the sliding member which consists of a sliding material of this aspect has the joining strength outstanding in the contact surface with a joining member. Moreover, according to the sliding material of this aspect, the weather strip excellent in the joining strength of the contact surface of a sliding member and a joining member, and excellent in refraction resistance and impact resistance is realizable.

  Based on the total amount of the sliding material, the content of the propylene polymer may be 15 to 40% by mass, the content of the ethylene polymer may be 20 to 55% by mass, and the content of the silicone compound The amount may be 5-25% by weight. When each component is contained in such a content, the required characteristics as a sliding material and excellent bonding strength with respect to the bonding material can be achieved at a higher level.

  The crosslinked body may be a crosslinked body formed by dynamic crosslinking. Further, the crosslinked body may be dispersed as a domain in the sliding material. The sliding material containing such a crosslinked body can maintain excellent slidability even by repeated sliding. The reason for this is not necessarily clear, but in a normal sliding material, the silicone compound on the material surface is removed, resulting in a decrease in slidability. In the above case, the interface between the cross-linked body that is a domain and the matrix This is considered to be because the silicone compound concentrated inside is gradually supplied to the surface of the sliding material by repeated sliding, and the amount of the silicone compound on the surface of the sliding material is sufficiently maintained.

  The sliding material of this aspect includes an elastomer obtained by kneading a composition containing a first propylene polymer and an ethylene polymer and dynamically crosslinking at least a part of the ethylene polymer, and a second propylene It may be obtained by kneading a base polymer and a silicone compound. At this time, it is preferable that the second propylene polymer contains the amorphous propylene polymer. The sliding material thus obtained can achieve the required characteristics as a sliding material and the excellent bonding strength with respect to the bonding material at a higher level.

The ethylene polymer includes a first ethylene polymer having a flexural modulus of 1.0 × 10 ² MPa or more and a second ethylene polymer having a flexural modulus of less than 1.0 × 10 ² MPa. You can leave. According to such an ethylene-based polymer, there is a tendency that more excellent slidability and flexibility as a weather strip sliding material can be easily obtained.

The mass ratio C ₁ / C ₂ of the content C _{1 of the first} ethylene polymer and the content C ₂ of the second ethylene polymer is 0.20 / 0.80 to 0.95 / 0.05. The JIS-A hardness of the sliding material can be 85 or more by setting the mass ratio C ₁ / C ₂ within this range. Normally, the higher the JIS-A hardness of the sliding material, the more difficult it is to obtain the bonding strength with the bonding material. However, in the sliding material of this aspect, even if the JIS-A hardness is 85 or more, Excellent bonding strength with the bonding material can be obtained. In addition, by setting the mass ratio C ₁ / C ₂ in the above range, the sliding material can be adjusted to have a JIS-A hardness of 85 or more and a Shore D hardness of less than 60, which balances rigidity and flexibility. A more excellent sliding member can be obtained. If the rigidity is high, the friction coefficient can be lowered. In addition, flexibility is important for ensuring followability to glass and sufficiently sealing the glass.

  Another aspect of the present invention relates to a sliding member formed by shaping the sliding material. Such a sliding member can be suitably used for applications such as a weatherstrip sliding member because it is excellent in fusibility with a polypropylene resin material.

  Still another aspect of the present invention relates to a weather strip including a sliding member that is in sliding contact with a window glass. In this aspect, the sliding member is formed by shaping the sliding material of the above aspect. Since such a weather strip can be joined to the joining member with excellent joining strength, the weather strip can realize excellent impact resistance and bending resistance, and can be mounted on the vehicle body or moved up and down the window glass. Sometimes the joint is less likely to break.

  Still another aspect of the present invention is joined to the sliding member formed by shaping the sliding material of the above aspect and the sliding member formed from a joining material containing 15% by mass or more of polypropylene. And a joining member. Since such a composite member uses a material obtained by shaping the sliding material of the above aspect as a sliding material, it has excellent bonding strength between the bonding member and the sliding member, and is suitable for applications such as weather strips. Can be used.

  Still another aspect of the present invention relates to a method for manufacturing the above composite member, and the manufacturing method of this aspect includes a melt containing 15% by mass or more of polypropylene in a sliding member formed by shaping the sliding material of the above aspect. Or it has the contact process which contacts the softened joining material. According to such a manufacturing method, the sliding member and the joining member can be easily joined with excellent joining strength.

  The contact step can be performed, for example, by injecting the bonding material into a mold in which the sliding member is inserted. According to such a contact process, the said sliding member and the said joining member can be joined easily.

  ADVANTAGE OF THE INVENTION According to this invention, the sliding material which can be joined with the joining material for joining a weatherstrip main-body part etc. with the outstanding joining strength, and the sliding member consisting of the said sliding material are provided. Moreover, according to this invention, the composite member provided with the sliding member joined by the outstanding intensity | strength and the joining member, and its manufacturing method are provided.

It is the schematic cross section which showed the suitable one aspect | mode of the sliding member which concerns on this invention. It is a schematic cross section of the sliding member which concerns on a prior art. It is a schematic cross section of the weather strip which concerns on 1st embodiment. It is a schematic cross section of the weather strip which concerns on 2nd embodiment.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the drawings are partially exaggerated for easy understanding, and dimensional ratios do not necessarily match those described.

(Sliding material)
The sliding material according to the present embodiment contains a propylene-based polymer, an ethylene-based polymer, and a silicone compound, and at least a part of the ethylene-based polymer forms a crosslinked body, and 5-30 mass of the propylene-based polymer. % Is an amorphous propylene-based polymer.

  According to the sliding material which concerns on this embodiment, the outstanding joining strength is implement | achieved by melt | fusion with a polypropylene resin material. Therefore, according to the sliding material which concerns on this embodiment, the sliding member which can be joined with joining material and the outstanding joining strength can be obtained.

  Based on the total amount of the sliding material, the content of the propylene-based polymer is preferably 15 to 40% by mass, the content of the ethylene-based polymer is preferably 20 to 55% by mass, and the content of the silicone compound is It is preferable that it is 5-25 mass%. When each component is contained in such a content, the required characteristics as a sliding material and excellent bonding strength with respect to the bonding material can be achieved at a higher level.

  The content of the propylene-based polymer is more preferably 20 to 40% by mass, and further preferably 20 to 35% by mass, based on the total amount of the sliding material. Further, the content of the ethylene-based polymer is more preferably 30 to 50% by mass, and further preferably 35 to 45% by mass, based on the total amount of the sliding material.

  Further, the content of the silicone compound is more preferably 6 to 20% by mass, and further preferably 7 to 15% by mass, based on the total amount of the sliding material. When the content of the silicone compound is not less than the above lower limit, the sliding durability is further improved, the water removal performance is further improved, and the generation of abnormal noise during sliding is further reduced. Further, when the content is less than or equal to the above upper limit value, the moldability of the sliding material is further improved, and the appearance deterioration due to the occurrence of bleeding is further suppressed.

  For example, the propylene-based polymer can be referred to as a polymer having a propylene unit content of 50% by mass or more, and can also be referred to as a polymer having a propylene unit in a proportion of 55% by mass or more.

  The polypropylene-based polymer may be polypropylene (that is, a homopolymer of propylene) or a copolymer of propylene and another monomer. Examples of the other monomer that forms a copolymer with propylene include ethylene and α-olefin.

  Examples of the α-olefin that forms a copolymer with propylene include ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 1-hexene, 3-methyl-1-pentene, and 4-methyl-1-pentene. , 1-heptene, 5-methyl-1-hexene, 1-octene, 1-decene, etc., and an α-olefin having 2 to 20 carbon atoms.

  Specific examples of the propylene polymer include polypropylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 4-methyl-pentene copolymer, propylene / 1-hexene copolymer, And propylene / ethylene / 1-butene copolymer.

  In the sliding material according to the present embodiment, 5-30% by mass of the propylene-based polymer is an amorphous propylene-based polymer, and the balance is a crystalline propylene-based polymer.

  In the present specification, the crystalline propylene-based polymer is a propylene-based polymer having a melting temperature and a crystallization temperature in the range of 70 to 170 ° C. in a differential scanning calorimeter (DSC) measurement result. The heat of transition indicates that both the heat of fusion and the heat of crystallization exceed 60 mJ / mg. The amorphous propylene-based polymer has a melting temperature and a crystallization temperature in the range of 10 to 170 ° C. in the measurement result of the differential scanning calorimeter (DSC) among the propylene-based polymers, The heat of fusion and the heat of crystallization are both 60 mJ / mg or less.

  The amorphous propylene polymer preferably has a transition heat amount of at least one of a heat of fusion and a heat of crystallization of 5 to 60 mJ / mg, and more preferably 5 to 55 mJ / mg. By using an amorphous propylene-based polymer having such a heat of transition, a sliding material with even better fusion with the joining member can be obtained.

  Melting temperature, crystallization temperature, amount of transition heat during melting, and amount of transition heat during crystallization are ascending / descending rate 10 ° C./min, 0 ° C. → 200 ° C. → 0 ° C., raised from 0 ° C. Then, it is folded at 200 ° C., cooled, and cooled to 0 ° C. for measurement. The melting temperature and the heat of transition at the time of melting are measured at the time of temperature rise, and the crystallization temperature and the heat of transition at the time of crystallization are measured at the time of cooling.

  One or a plurality of behaviors of melting and crystallization of the propylene polymer are observed at an observation temperature of 0 to 200 ° C. For example, when a plurality of endothermic transition heat quantities are observed at the time of temperature rise, this means that there are a plurality of melting temperatures.

  When measured under the above conditions, the amorphous propylene-based polymer has all melting temperatures in the range of 10 to 170 ° C. when the temperature is raised, and the total amount of transition heat measured at each melting temperature is 60 mJ / mg or less. And a propylene-based polymer in which all crystallization temperatures are in the range of 10 to 170 ° C. when the temperature is lowered, and the total amount of transition heat measured at each crystallization temperature is 60 mJ / mg or less.

  In addition, when measured under the above conditions, the crystalline propylene-based polymer has all melting temperatures in the range of 70 to 170 ° C. when the temperature is raised, and the total amount of transition heat measured at each melting temperature is 60 mJ / mg. In addition, a propylene-based polymer in which all crystallization temperatures are in the range of 70 to 170 ° C. when the temperature is lowered and the total amount of transition heat measured at each crystallization temperature exceeds 60 mJ / mg.

  Examples of the amorphous propylene-based polymer include a polypropylene homopolymer and a propylene / α-olefin copolymer from the viewpoint that the effects of the present invention can be more remarkably obtained. Among these, a propylene / ethylene copolymer, Propylene / 1-butene copolymer and propylene / ethylene / 1-butene copolymer are more preferable. Examples of the propylene-ethylene copolymer include “Prime TPO” manufactured by Prime Polymer Co., “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” “TAFMER XM” manufactured by Mitsui Chemicals, Inc., and the like. Examples of the propylene-ethylene-1-butene copolymer include “TAFMER XM” manufactured by Mitsui Chemicals. For example, a crystal nucleating agent may optionally be added to the amorphous propylene-based polymer.

  The hardness of the amorphous propylene-based polymer is not particularly limited from the viewpoint of the fusion property with the joining member, but the weather strip sliding material such as suppression of increase in sliding resistance, improvement in wear resistance, flexibility, etc. From the viewpoint of more excellent characteristics, the JIS-A hardness is preferably 60 or more, and the JIS-A hardness is more preferably 70 or more. An amorphous propylene-based polymer having a Shore D hardness of less than 60 is preferable in that the hardness of a sliding material described below can be easily adjusted to a preferable range described below.

The amorphous propylene-based polymer preferably has a flexural modulus of 0.5 × 10 ² MPa or more, and more preferably 1.0 × 10 ² MPa or more. Further, the flexural modulus of the amorphous propylene-based polymer may be less than 5 × 10 ² MPa. Such a joining member tends to be more excellent in properties as a weather strip sliding material such as suppression of an increase in sliding resistance, improvement in wear resistance, and flexibility.

Amorphous propylene-based polymer is preferably density of 0.855 g / cm ³ or more, and more preferably 0.86 g / cm ³ or more. The density of the amorphous propylene-based polymer may be less than 0.90 g / cm ³ . Such a joining member tends to be more excellent in properties as a weather strip sliding material such as suppression of an increase in sliding resistance, improvement in wear resistance, and flexibility. The hardness, the flexural modulus and the density are relatively correlated with each other, and by adjusting any value of the hardness, the flexural modulus and the density to the preferred range, other values can be easily set to the preferred values. Can be adjusted to the range.

  The amorphous propylene-based polymer preferably has a transition heat amount of 5 mJ / mg or more at the time of melting and at the time of crystallization. When the amount of heat of transition is 5 mJ / mg or more, the bonding strength with the bonding material, particularly the bonding material containing 15% by mass or more of the propylene polymer, is further improved, and the bleeding of the silicone compound from the sliding material is further increased. It is suppressed. From the viewpoint of preventing silicone bleed, the amount of transition heat is more preferably 10 mJ / mg or more, and further preferably 13 mJ / mg or more.

  In the sliding material of the present embodiment, the silicone compound is concentrated in the interface between the crosslinked domain obtained by dynamically crosslinking at least a part of the ethylene-based polymer and the matrix, or in the matrix. Since it is arranged at a concentration, it has a structure in which silicone bleeding is unlikely to occur. However, according to the knowledge of the present inventors, when a large amount of the amorphous propylene-based polymer having a transition heat amount of less than 5 mJ / mg is present in the sliding material, silicone bleeding tends to occur easily. This is because the amorphous propylene-based polymer having a strong amorphous property (having a transition heat amount of less than 5 mJ / mg) is easy to dissolve and impregnate the silicone compound, so that the silicone compound is easily diffused in the sliding material. Conceivable.

  Examples of crystalline propylene-based polymers include propylene homopolymers and propylene / α-olefin copolymers, and homopolymers, block copolymers, and random copolymers can be used. As the crystalline propylene-based polymer, homopolymers and block copolymers are preferable from the viewpoints of adhesive strength with the bonding material, sliding property of the sliding material, and suppression of silicone bleeding in the sliding member. For example, a crystal nucleating agent may optionally be added to the crystalline propylene polymer.

  As described above, the crystalline propylene-based polymer has a heat of transition exceeding 60 mJ / mg at the time of melting and crystallization, and the heat of transition is 70 mJ from the viewpoint of adhesive strength, slidability, and silicone bleed suppression. / Mg or more.

  The ratio of the amorphous propylene polymer in the propylene polymer is 5 to 30% by mass, preferably 6 to 20% by mass, and more preferably 7 to 19% by mass. If the proportion of the amorphous propylene-based polymer is less than 5% by mass, sufficient adhesive strength with the bonding material may not be obtained, and if it exceeds 30% by mass, excessive silicone bleed may be generated from the sliding member. Occurring, there are concerns about deterioration of the product appearance and contamination of the surroundings.

  The content of the amorphous propylene-based polymer is preferably 0.75 to 12% by mass, more preferably 1.4 to 7.6% by mass, based on the total amount of the sliding material. More preferably, it is 4 to 6.65% by mass. Thereby, the sliding material which is further excellent in the adhesive force with the bonding material and can further suppress the silicone bleed can be obtained.

  Examples of the silicone compound include polysiloxanes such as silicone oil and silicone gum (also referred to as silicone rubber); a copolymer of siloxane and another monomer, or a reaction product obtained by bonding siloxane and another polymer. Silicone copolymer; and the like.

  Polysiloxane is a high molecular compound having a linear structure composed of siloxane bonds, and an oily silicone is called silicone oil, and a rubbery is called silicone gum (or silicone rubber).

  Examples of the polysiloxane include dimethyl polysiloxane, diphenyl polysiloxane, methylphenyl polysiloxane, and modified products thereof. Here, as the modified product, for example, a part of the methyl group or phenyl group of the polysiloxane is substituted with a vinyl-modified silicone substituted with a vinyl group, a hydrogen polysiloxane substituted with a hydrogen atom, or an alkyl group. Alkyl-modified silicone, higher fatty acid ester-modified silicone substituted with higher fatty acid ester group, fluorine-modified silicone substituted with fluorine atom or fluorinated alkyl group, polyether-modified silicone substituted with polyether group, group having amino group Amino-modified silicone substituted with hydroxyl group, carbinol-modified silicone substituted with hydroxylalkyl group, epoxy-modified silicone substituted with group having oxirane ring, carboxy-modified silicone substituted with group having carboxyl group, etc. .

  The silicone copolymer is obtained by copolymerizing silicone and another resin. As this silicone copolymer, a commercially available copolymer may be used, or a copolymer may be prepared. As a specific example, a silicone-acrylic copolymer “Charine” (Nisshin Chemical Co., Ltd.) Manufactured, trade name), silicone-acrylic copolymer “X-22-8171” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), silicone-olefin copolymer “EXFOR” (manufactured by Mitsui Chemicals, trade name), Partially crosslinked product of dimethyl vinyl polysiloxane containing 0 to 1 mol% of vinyl group and EPDM, SBS or SIS containing 0 to 5% by weight of unsaturated group, amino-modified silicone or carboxyl-modified silicone And a reaction product of maleic anhydride-modified olefin polymer or oligomer (polypropylene, polyethylene, ethylene / propylene copolymer, etc.), etc. It is. Moreover, pellets obtained by making these into a master batch with a resin, “X-22-2101”, “X-222-147” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), “BY27-001S” (Toray Dow Corning) And “BY27-201” (trade name, manufactured by Toray Dow Corning Co., Ltd.), which is a partially graft-polymerized pellet with resin.

  The content of the silicone compound is preferably 5 to 25% by mass, more preferably 6 to 20% by mass, and further preferably 7 to 15% by mass based on the total amount of the sliding material. In addition, the higher the concentration of the silicone compound, the longer the sliding life of the sliding material, but the bonding strength with the bonding member tends to be weakened.

The weight average molecular weight of the silicone compound is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , more preferably 1 × 10 ⁴ to 2 × 10 ⁵ . . When the weight average molecular weight is within the above range, good slidability can be exhibited even when the content of the silicone compound is 20% by mass or less, 15% by mass or less, or 10% by mass or less.

  As the silicone compound, a silicone compound selected from the group consisting of silicone oil, silicone gum, and a silicone copolymer containing 40% by mass or more of silicone is preferable. Moreover, in this embodiment, as a silicone compound, these can be used individually or in combination of multiple types, and it can adjust to the above-mentioned suitable weight average molecular weight.

The silicone compound adjusted to the above preferred weight average molecular weight tends to have a kinematic viscosity at 25 ° C. based on JIS Z8803 in the range of 1 × 10 ¹ to 1 × 10 ⁷ mm ² / sec (MPa · s). is there.

  In this embodiment, the weight average molecular weight is measured as a comparative conversion value with standard polystyrene using GPC (gel permeation chromatography) equipped with a differential refraction detector (RI). Specifically, “Alliance” (product name) manufactured by Watres is used, the detector is RI, the injection amount is 100 μl, the moving bed is toluene, the flow rate is 1.0 ml / min, and the column is Shodex GPC manufactured by Showa Denko. KF-806 × 2, column temperature is 40 ° C., detection sensitivity is 4, standard materials are 8 kinds of polystyrene standards, sample and standard concentration is 7 mg / 10 toluene. However, when the silicone copolymer does not dissolve in toluene, an appropriate solvent capable of dissolving the silicone copolymer is selected. For example, when the acrylic unit is 15% by mass or more in the silicone-acrylic copolymer, THF is used instead of toluene.

  The ethylene-based polymer can be referred to as a polymer having an ethylene unit content exceeding 50% by mass, for example, and can also be referred to as a polymer having an ethylene unit in a proportion of 55% by mass or more.

  The ethylene-based polymer may be polyethylene (that is, a homopolymer of ethylene), or may be a copolymer of ethylene and another monomer. Other monomers that form a copolymer with ethylene include α-olefins, non-conjugated polyenes, and the like.

  Examples of the α-olefin that forms a copolymer with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and 1-heptene. Examples of the non-conjugated polyene that forms a copolymer with ethylene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decandiene, and 3,6-dimethyl. -1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nanodiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2 , 5-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene and the like.

  Preferable examples of the ethylene polymer include polyethylene (ethylene homopolymer), ethylene / α-olefin copolymer, ethylene / α-olefin / non-conjugated polyene copolymer, and the like.

  More specific examples of the ethylene-based polymer include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (L-LDPE, LDPE), ethylene plastomer, and ethylene estomer. .

  In the present specification, high density polyethylene is a polyethylene polymer having a density of 0.94 or more (less than 0.98), medium density polyethylene is a polyethylene polymer having a density of 0.93 or more and less than 0.94, and low density polyethylene is a density. Polyethylene polymer having a density of 0.91 to less than 0.93, ethylene plastomer having a density of 0.89 to less than 0.91, and polyethylene elastomer having a density of less than 0.89 (0.85 or more) Indicates polymer.

  The ethylene polymer is preferably selected from the group consisting of polyethylene, ethylene / α-olefin copolymer, and ethylene / α-olefin / non-conjugated diene copolymer. These ethylene-based polymers can easily form domains by, for example, dynamically crosslinking together with a propylene-based polymer and an organic peroxide. In addition, as long as it is an ethylene-α olefin-nonconjugated diene copolymer, a domain can be formed not only by an organic peroxide but also by a sulfur vulcanizing crosslinking agent, a resin crosslinking crosslinking agent, or a hydrosilyl crosslinking agent. Can do.

  As a crosslinking agent for forming a domain, an organic peroxide is preferable in that it can crosslink all of polyethylene, ethylene / α-olefin copolymer, and ethylene / α-olefin / nonconjugated diene copolymer. In addition, it is also preferable to use an organic peroxide in combination with an organohydrogenpolysiloxane that is a hydrosilyl-based crosslinking agent.

  The shape of the ethylene-based polymer before kneading is arbitrary, and may be a pellet, an amorphous powder, a spherical powder, a fiber, a chopped strand, or the like. The size is arbitrary as long as it can be put into a kneader, and may be, for example, an average particle diameter of 15 mm to 0.5 μm.

The ethylene-based polymer includes a hard first ethylene-based polymer having a flexural modulus of 1.0 × 10 ² MPa or more (Shore D hardness of 20 or more) and a flexural modulus of less than 1.0 × 10 ² MPa (Shore D hardness). Less than 20) and a relatively soft second ethylene polymer. The combined use not only provides excellent bonding strength with a bonding material (particularly, a bonding material containing 15% by mass or more of a polypropylene-based polymer), but also gives rigidity and flexibility to the sliding member. The effect of becoming a suitable sliding material is exhibited.

The flexural modulus of the first ethylene-based polymer is 1.0 × 10 ² MPa or more, preferably 3.0 × 10 ² MPa or more, more preferably 1.0 × 10 ³ MPa or more. . The first ethylene polymer is cross-linked to form a hard (high elastic modulus) domain, and the domain is not easily worn or melted even when the sliding material is rubbed. By using, a sliding material excellent in repeated sliding can be obtained. Moreover, the bending elastic modulus of the first ethylene-based polymer may be 2.0 × 10 ³ MPa or less.

The bending elastic modulus of the second ethylene-based polymer is less than 1.0 × 10 ² MPa, preferably less than 0.5 × 10 ² MPa, more preferably less than 0.3 × 10 ² MPa. The second ethylene-based polymer is cross-linked to form a soft (low modulus) domain, giving the sliding material flexibility, cold resistance and rubber elasticity. Further, according to the domain formed by the second ethylene-based polymer, the adhesion of the sliding material to the bonding material is further improved, and the sliding resistance and the wear amount on the sliding surface of the sliding member are further reduced. Tend to be.

  The first ethylene polymer is preferably a polymer selected from the group consisting of high density polyethylene (HDPE), medium density polyethylene (MDPE), and low density polyethylene (L-LDPE, LDPE). Such a first ethylene-based polymer may be a polymer selected from the group consisting of polyethylene and an ethylene / α-olefin copolymer. The first ethylene polymer is more preferably a polymer selected from the group consisting of high density polyethylene (HDPE) and medium density polyethylene (MDPE).

  The second ethylene polymer is preferably a polymer selected from the group consisting of ethylene plastomers and ethylene elastomers. Such a second ethylene-based polymer may be a polymer selected from an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer.

  Here, as the ethylene / α-olefin copolymer used as the second ethylene polymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer are used. Etc. The ethylene / α-olefin / non-conjugated diene copolymer is selected from the group consisting of an ethylene / propylene / diene copolymer (EPDM or EPT) and an ethylene / butene / diene copolymer (EBDM or EBT). Polymers to be used. Among these, an ethylene / propylene / diene copolymer and an ethylene / butene / diene copolymer are more preferable in view of high crosslinking efficiency, excellent rubber elasticity, and slidability.

The mass ratio C ₁ / C ₂ of the content C ₁ of the _first ethylene polymer and the content C ₂ of the second ethylene polymer is 0.20 / 0.80 to 0.95 / 0.05 (that is, 0.25-19), and more preferably 0.40 / 0.60-0.80 / 0.20 (that is, 0.67-4). The mass ratio _C 1 / _{C 2} With the above-mentioned range, it is possible to make the JIS-A hardness of sliding material for example 85 or more. Normally, the higher the JIS-A hardness of the sliding material, the more difficult it is to obtain the bonding strength with the bonding material. However, in the sliding material according to this embodiment, the JIS-A hardness is set to 85 or more. In addition, excellent bonding strength with a bonding material (particularly, a bonding material containing 15% by mass or more of a propylene-based polymer) can be obtained.

The JIS-A hardness of the sliding material can be adjusted by changing the mass ratio C ₁ / C ₂ as described above. For example, to increase the mass ratio C _{1 /} C ₂ (first proportion of the ethylene polymer is increased) and the JIS-A hardness tends to be higher, to reduce the mass ratio C _{1 /} C ₂ (first JIS-A hardness tends to be low.

  The JIS-A hardness of the sliding material is preferably 85 or more, more preferably 90 or more. The upper limit of the hardness of the sliding material may be about 99 in JIS-A hardness, and is preferably less than Shore D hardness 60. When the hardness of the sliding material is in the above range, it is effective in that the sliding member is excellent in balance between rigidity and flexibility.

  In this embodiment, at least a part of the ethylene-based polymer forms a crosslinked body, and the crosslinked body preferably forms a domain (island phase) and is dispersed in the sliding material. That is, in the sliding material according to the present embodiment, preferably, a domain formed from a cross-linked body of an ethylene-based polymer is dispersed.

  According to the sliding material in which such domains are dispersed, a sliding member having excellent sliding durability that can withstand repeated sliding is obtained. Although the reason for this is not necessarily clear, the conventional sliding member usually removes the silicone compound on the surface of the material, resulting in a decrease in slidability. In the sliding member using the above sliding material, The silicone compound disposed in the interface between the domain and the matrix formed from the matrix or the matrix is gradually supplied to the surface of the sliding member by repeated sliding, so that the amount of the silicone compound on the surface of the sliding member is sufficient. This is thought to be maintained.

  Further, according to the sliding material in which such domains are dispersed, for example, during molding such as extrusion molding, the silicone compound is prevented from being unevenly distributed in the sliding material, resulting in poor appearance due to excessive bleeding of the silicone compound. Occurrence and non-uniformity of the sliding member can be avoided.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the sliding member according to the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a sliding member according to the prior art.

  2 is a sliding member formed by extruding a sliding material containing a matrix 16 and a silicone compound 14 dispersed in the matrix 16. In the sliding member 2, a part of the silicone compound 14 is dispersed in the matrix 16, but the other part is unevenly distributed in the extrusion direction to form a layer made of the silicone compound 14.

  In the sliding member 2, when the layer made of the silicone compound 14 is formed near the surface, or when the material is worn to the vicinity of this layer as a result of sliding, the appearance is poor due to bleeding of the silicone compound 14 forming the layer. May be caused. Further, in the sliding member 2, since the silicone compound 14 is not supplied to the surface of the sliding member 2 unless the layer of the silicone compound 14 is abraded, the silicone compound 14 having sufficient sliding property is obtained. It is difficult to maintain on the surface of the sliding member 2, and the sliding durability tends to be inferior, for example, the sliding resistance becomes high or the wear proceeds greatly.

  On the other hand, the sliding member 1 shown in FIG. 1 is a sliding member formed by extruding a suitable sliding material of the present embodiment. In the sliding member 1, a domain 12 formed from a crosslinked ethylene polymer is dispersed in a matrix 10 containing a propylene polymer. Further, the sliding member 1 contains a silicone compound 14, and a large amount of the silicone compound 14 exists at the interface between the matrix 10 and the domain 12. Further, in the sliding member 1, the uneven distribution of the silicone compound 14 is prevented by the domain 12.

  Thus, the silicone compound 14 present at the interface between the matrix 10 and the domain 12 tends to move to the surface of the sliding member 1 along the interface more easily than the silicone compound 14 dispersed in the matrix. Therefore, in the sliding material 1, even when sliding is repeatedly performed, the amount of the silicone compound on the surface of the sliding member 1 is sufficiently maintained, and excellent slidability is maintained.

  The average particle size of the domain 12 is preferably 0.5 to 150 μm. When the average particle size of the domain 12 is within this range, the uneven distribution of the silicone compound is sufficiently suppressed, and the silicone compound can be sufficiently supplied to the surface of the sliding member. A more excellent sliding member can be obtained. The average particle size of the domain 12 is more preferably 1 to 100 μm, and more preferably 3 to 70 μm.

  In this specification, the average particle diameter of the domain 12 is a value obtained by taking an electron micrograph of the cross section of the sliding member 12, calculating the particle diameter corresponding to each domain 12 by image processing, and calculating the average of the whole. Indicates. In addition, let the diameter calculated | required by perfect circle conversion about the area of the measured domain 12 be a particle size.

  In the present embodiment, the crosslinked body may be formed by, for example, dynamic crosslinking. According to dynamic cross-linking, a cross-linked body that easily forms a domain as described above can be formed. 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 a propylene-based polymer, an ethylene-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 organic peroxide and organohydrogenpolysiloxane are used in combination, the cross-linked domain has a more uniform particle size than when organic peroxide is used alone, and tends to be a sliding member with excellent appearance (fewer lumps). There is.

  The ethylene-based polymer forms a crosslinked body so that the residual ratio of the sliding material due to the reflux of hot xylene is 20 to 80% by mass (preferably 20 to 70% by weight) based on the total amount of the sliding material. It is preferable. Thus, the effect of this invention can be acquired more notably by forming a crosslinked body. Here, the “residual ratio by hot xylene reflux” refers to a value obtained by the following method.

That is, about 3 g of the sliding material sample is weighed to obtain an accurate weight (W ₁ ). The sample is put into a cylindrical filter paper, set in a Soxhlet extractor, and refluxed with xylene for 6 hours. After extraction, the filter paper containing the sample is taken out, xylene is sufficiently evaporated, and the sample is allowed to cool, and then the exact weight (W ₂ ) of the sample is measured. When the weight of an inorganic component such as a filler insoluble in hot xylene is W ₃ , the “residual ratio by refluxing hot xylene” is obtained by 100 × (W ₂ −W ₃ ) / W ₁ .

  From the viewpoint of further improving the sliding durability, the residual ratio due to the reflux of hot xylene is more preferably 30 to 70% by mass, and further preferably 35 to 65% by weight.

  Various additional components other than the above can be contained in the sliding material. Such additives include reinforcing agents such as pigments, silica and carbon black, antioxidants, weathering improvers, thermoplastic resins, elastomers, antifungal agents, antibacterial agents, flame retardants, paraffinic softeners, etc. , Lubricants, fluorine-based lubricants, and the like.

  The sliding material according to the present embodiment includes, for example, an elastomer obtained by kneading a resin composition containing a first propylene-based polymer and an ethylene-based polymer and dynamically crosslinking at least a part of the ethylene-based polymer, It may be obtained by kneading the second propylene-based polymer and the silicone compound.

The ethylene polymer in the resin composition preferably includes the first ethylene polymer and the second ethylene polymer, and the content C ₁ of the first ethylene polymer in the resin composition and As described above, the mass ratio C ₁ / C ₂ of the content C ₂ of the second ethylene polymer is 0.20 / 0.80 to 0.95 / 0.05 (0.25 to 19). preferable.

  In order to form a domain having a suitable particle size and to further increase the adhesive strength with the bonding material, the propylene-based polymer is divided into two parts, a first propylene-based polymer and a second propylene-based polymer. It is preferred to produce the material.

  For example, in one aspect of the method for producing a sliding material, a composition containing a first propylene polymer and an ethylene polymer is kneaded to form a domain by dynamic crosslinking, and then a second propylene polymer is added. It can be kneaded. At this time, it is preferable to use a crystalline propylene-based polymer as the first propylene-based polymer and most of the amorphous propylene-based polymer as the second propylene-based polymer. That is, it is preferable that the first propylene-based polymer includes a crystalline propylene-based polymer and the second propylene-based polymer includes an amorphous polymer.

  In the above embodiment, the first propylene-based polymer used at the time of dynamic crosslinking is a crystalline propylene-based polymer as described above, but a small amount of an amorphous propylene-based polymer can be used at the same time. The content of the amorphous propylene polymer in the first propylene polymer is preferably 0 to 15% by mass, and preferably 0 to 6% by mass. By reducing the content of the amorphous propylene polymer in the first propylene polymer, it is easy to obtain a suitable domain particle size.

  The second propylene-based polymer that is added and kneaded after the domain formation by dynamic crosslinking is completed is the remaining propylene-based polymer that has not been added in the first propylene-based polymer, and includes an amorphous propylene-based polymer. The amount of the propylene polymer added as the second propylene polymer is preferably 0.75% by mass or more, more preferably 1.4% by mass or more, based on the total amount of the sliding material. Moreover, it is preferable that it is 12 mass% or less, and it is more preferable that it is 6.65 mass% or less.

  In the above aspect, the composition for dynamic crosslinking is 3 to 40% by mass of propylene-based polymer (more preferably 13.35 to 33.6% by mass) and 20 to 55% by mass based on the total amount of the sliding material. % Ethylene-based polymer (more preferably 35 to 45% by mass). By performing dynamic crosslinking at such a ratio, it becomes easier to obtain a suitable domain particle size.

  When forming a domain by dynamic cross-linking, it is necessary to add a cross-linking agent in order to advance cross-linking of the ethylene-based polymer in addition to the first propylene-based polymer and the ethylene-based polymer. The addition amount of the crosslinking agent varies slightly depending on the crosslinking system, but can be in the range of 0.05 to 15% by mass. In the case of dynamic crosslinking, a crosslinking aid may be further added.

  In the organic peroxide crosslinking system, it is preferable to use 0.01 to 10 parts by mass of the organic peroxide with respect to 100 parts by mass in total of the first propylene polymer and the ethylene polymer. A more preferable addition amount is 0.3 to 4 parts by mass, and further preferably 0.7 to 3 parts by mass. In addition, said more preferable addition amount is comparatively larger than the time of manufacturing the olefin type thermoplastic elastomer which is generally TPV marketed. If the amount of the crosslinking agent added is too small, the domain system may be small, resulting in poor slidability or silicone bleed failure. On the other hand, if the amount is excessively large, the domain system becomes large, and the fluidity of the sliding material may be lowered, or the surface of the sliding member may be roughened to deteriorate the appearance. In addition to organic peroxides, the following polyfunctional unsaturated compounds: (meth) acrylic monomers and oligomers, vinyl monomers such as divinylbenzene, allyl monomers such as triallyl cyanurate, and bismaleimide are added to the organic peroxide. 0 to 5 parts by weight can be added as a sulfur assistant.

  In the case of a sulfur vulcanizing crosslinking agent, 0.1 to 10 parts by mass of a sulfur compound such as sulfur or dithiodimorpholine is added as a crosslinking agent with respect to a total of 100 parts by weight of the first propylene polymer and ethylene polymer. can do. In addition, 0.1 to 10 parts by mass of a vulcanization aid may be added to perform dynamic crosslinking. As the vulcanization aid, a thiazole compound, a disulfide compound, a dithiocarbamate compound, a thiourea compound, zinc oxide, or the like can be used in combination.

  Examples of the crosslinking agent for resin crosslinking include bromides of alkylphenol resins and mixed crosslinking systems containing halogen donors such as tin chloride and chloroprene and alkylphenol resins. For example, the first propylene polymer and ethylene polymer About 1 to 20 parts by mass can be used with respect to 100 parts by mass in total.

  As a hydrosilyl type crosslinking agent, 0.01 to 10 parts by mass of the organohydrogenpolysiloxane with respect to a total of 100 parts by mass of the first propylene polymer and ethylene polymer, a platinum catalyst and a palladium catalyst. Dynamic crosslinking can be performed by adding 0.001 to 10 parts by mass of a platinum group element catalyst such as a rhodium catalyst.

  In a combined system of an organic peroxide and an organohydrogenpolysiloxane, which is a preferred crosslinking system, for example, 0.01% of the organic peroxide is added to 100 parts by mass of the first propylene-based polymer and the ethylene-based polymer. 10 mass parts (preferably 0.3-4 mass parts, more preferably 0.7-3 mass parts), 0.01-10 mass parts (preferably 0.05-5 mass parts) of organohydrogenpolysiloxane. Part, more preferably 0.1 to 3 parts by weight).

  The sliding material can be manufactured using a kneader. Examples of the kneader include batch kneaders such as a Banbury mixer and a kneader, and continuous kneaders such as a single screw or twin screw extruder.

  The kneading conditions are not particularly limited, and in the formation of the domain, the first propylene polymer, the ethylene polymer, and the crosslinking agent may be kneaded at one time, but the first propylene polymer and the ethylene polymer are 120 to 120. After kneading at 230 ° C. in a semi-molten or molten state, it is preferable to add a crosslinking agent and knead at 100 to 260 ° C. for dynamic crosslinking. Then, a sliding material can be obtained by adding a 2nd propylene polymer and a silicone compound to resin in which the domain obtained by dynamic crosslinking was formed, and knead | mixing at 100-260 degreeC. In addition, the manufacturing method of a sliding material is not limited to the said aspect, It can carry out with the various method which can form a domain.

(Sliding member, composite member, weather strip)
The sliding member which concerns on this embodiment is a sliding member formed by shaping the sliding material which concerns on the said embodiment. The molding method of the sliding member is not particularly limited, and for example, the sliding member may be molded by a method such as extrusion molding, injection molding, blow molding, compression molding, transfer molding, or calendar molding.

  Since the sliding member which concerns on this embodiment is a member which consists of a sliding material which concerns on the said embodiment, it has the outstanding sliding durability and can be used suitably as a sliding member for weather strips.

  Since the sliding member is also a member made of the sliding material according to the above-described embodiment, it can be bonded to the bonding material with excellent bonding strength. Here, the joining material is, for example, a resin material containing 15% by mass or more of a propylene polymer, and preferably a resin material containing 20% by mass or more of a propylene polymer.

  Moreover, the sliding member which concerns on this embodiment maintains the outstanding joint strength with a joining member, even if the number of days passes after cutting out a joining surface with a joining member. For this reason, in the sliding member which concerns on this embodiment, the storage time after a cut-out process can be earned, and there exists a tendency for the manufacturing efficiency of molded articles, such as a weather strip, to improve.

  The composite member according to this embodiment includes a sliding member formed by shaping the sliding material according to the above-described embodiment, and may further include a joining member that joins the sliding member.

  The composite member includes, for example, a first structure having a first sliding member and a first support member that supports the first sliding member, and a second structure having a second sliding member and a second support member that supports the first sliding member. You may provide a 2nd structure and the joining member which joins a 1st structure and a 2nd structure mutually. At this time, the joining member may have a contact surface with the first sliding member and / or the second sliding member, and even in this case, the joining member and the sliding member are joined with excellent strength. Therefore, the composite member according to the present embodiment is excellent in impact resistance and bending resistance.

  The joining member is preferably made of a joining material containing 15% by mass or more (preferably 20% by mass or more) of a propylene-based polymer. Such a joining member is joined to the sliding member with an excellent joining strength.

  The bonding between the sliding member and the joining member is performed by, for example, inserting the sliding member (or a structure composed of the sliding member and the support member) into a cooled mold and cooling the bonding material melted by injection molding. It can be performed by pouring into the mold, bringing the sliding member and the bonding material into contact or pressure contact, and then removing from the mold. The bonding material is cooled by flowing through the cooling mold before contacting or press-contacting the sliding member, and also when the bonding material contacts or press-contacts the sliding member, the sliding member is cooled. It is cooled at the contact surface. Usually, when the bonding material is cooled and the resin temperature is lowered, it becomes difficult to obtain sufficient bonding strength. However, in this embodiment, since the sliding material contains an amorphous propylene-based polymer, the bonding surface temperature is low. However, it is considered that excellent fusion performance is exhibited and good bonding is realized.

  The bonding material forming the bonding member may contain various components in addition to the propylene-based polymer depending on the use of the composite member. For example, the bonding material contains an elastomer component such as an ethylene / α-olefin copolymer, an ethylene / α-olefin / non-conjugated diene copolymer, a styrene block copolymer, and a water-added styrene block copolymer. May be. The elastomer component may be partially or wholly crosslinked. As the propylene-based polymer in the bonding material, polypropylene is preferable.

  Below, the one aspect | mode of the process of the manufacturing method of a composite member is shown.

  The manufacturing method of the composite member of this aspect includes a contact step of bringing a molten or softened bonding material containing 15% by mass or more of a propylene polymer into contact with a sliding member formed by shaping the sliding material according to the embodiment. Have According to such a contact process, since the bonding material exhibits excellent fusion properties with respect to the sliding member, it is possible to form the bonding member bonded to the sliding member with excellent bonding strength.

  The molten or softened bonding material is cooled or the like after the contact step and solidifies to form a bonding member. In order to easily form the joining member, the contact step can be performed, for example, by injecting a joining material into a mold in which the sliding member is inserted. According to such a method, it is possible to easily obtain a composite material in which the sliding member and the bonding member are bonded with excellent bonding strength.

  In the contacting step, the bonding material is heated to such an extent that it melts or softens. The degree of heating can be appropriately adjusted depending on the bonding material, but for example, it can be 180 to 250 ° C. before contact, or 220 to 270 ° C.

  In the contacting step, the sliding member before the bonding material comes into contact does not need to be heated, and may be, for example, 0 to 120 ° C. or 10 to 80 ° C. In the conventional sliding member, when the bonding material melted or softened is brought into contact with the sliding member having such a low temperature, sufficient fusion is not achieved and sufficient bonding strength cannot be obtained. There was a case. In contrast, in the present embodiment, even when the molten or softened bonding material is brought into contact with the sliding member at such a low temperature, the sliding member has excellent fusion properties with respect to the bonding material. As shown, excellent bonding strength can be obtained.

  The composite member which concerns on this embodiment is applicable to various uses as a composite member provided with a sliding member. For example, the composite member can be suitably used as a weather strip including a sliding member that is in sliding contact with the window glass.

  Hereinafter, preferred embodiments of the weather strip of the present invention will be described in detail with reference to the drawings.

  The weather strip according to the present embodiment is a weather strip including a sliding member that is in sliding contact with the window glass, and the sliding member is formed by shaping the sliding material according to the above-described embodiment.

  FIG. 3 is a schematic cross-sectional view of a weather strip according to the first embodiment. A weather strip 50 according to the first embodiment shown in FIG. 3 includes a weather strip body (support member) 20 and a sliding member 30 made of the sliding material according to the above-described embodiment. The weather strip main body 20 includes a base portion 20a, side wall portions 20b on both sides, and a lip portion 20c extending inward from the front ends of the both side wall portions 20b, and the sliding member 30 is a lip portion 20c in sliding contact with the window glass 18. It forms on these so that the surface of the base part 20a which slidably contacts with a sliding contact part and the outer-periphery edge surface of the window glass 10 may be coat | covered.

  FIG. 4 is a schematic cross-sectional view of a weather strip according to the second embodiment. A weather strip 60 according to the second embodiment shown in FIG. 4 includes a weather strip main body 120 and a sliding member 30 made of the sliding material according to the above-described embodiment. The weather strip main body 120 includes a core member 110, and includes a mounting portion 120d attached to the vehicle and a lip portion 120c in sliding contact with the window glass. The sliding member 30 covers the sliding contact portion of the lip portion 120c. , Formed on the lip 120c.

  The weather strip according to the present embodiment may be obtained by joining the two weather strips described above with a joining member. That is, the weather strip may further include a support member that supports the sliding member, and the weather strip includes a first sliding member and a first supporting member that supports the first sliding member. A structure, a second sliding member having a second sliding member and a second supporting member that supports the second sliding member, and a joining member that joins the first structure and the second structure together. It may be a thing.

  Such a weatherstrip is excellent in impact resistance and bending resistance because the joining member is in contact with the sliding member even when the joining member is in contact with the sliding member. Can be sufficiently prevented from being broken (peeled), and can be easily assembled to the vehicle body.

  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.

The raw materials used in Examples and Comparative Examples are indicated by the following abbreviations.
(1) Crystalline propylene polymer MA3H (polypropylene homopolymer, manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP (grade: MA3H))
E203GV (polypropylene homopolymer, manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro E-203GV)
・ H700 (polypropylene homopolymer, manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro H700)

(2) Amorphous propylene-based polymer / R110MP (propylene-ethylene block copolymer, propylene ratio 55 to 65% by mass, manufactured by Prime Polymer Co., Ltd., trade name: Prime TPO (soft block system R110MP))
PN2060 (propylene / α-olefin copolymer, propylene ratio 65 to 75% by mass, manufactured by Mitsui Chemicals, trade name: Notio PN2060)
V2300 (propylene / ethylene copolymer, propylene ratio 75 to 95% by mass, manufactured by Dow Chemical Co., Ltd., trade name: Versify 2300)
V3000 (propylene / ethylene copolymer, propylene ratio 85-98% by mass, manufactured by Dow Chemical Co., Ltd., trade name: Versify 3000)
V3300 (propylene / ethylene copolymer, propylene ratio 80 to 90% by mass, manufactured by Dow Chemical Co., Ltd., trade name: Versify 3300)
V3401 (propylene / ethylene copolymer, propylene ratio 75 to 90% by mass, manufactured by Dow Chemical Co., Ltd., trade name: Versify 3401)
-XM-7070 (propylene / 1-butene copolymer, propylene ratio 65-75% by mass, manufactured by Mitsui Chemicals, Inc., trade name: TAFMER XM-7070)
-H3522D (70% by mass of propylene / α-olefin copolymer raw material sandwiched by 30% by mass of polypropylene homopolymer, propylene ratio of propylene / α-olefin copolymer raw material of 90-100% by mass, Sumitomo Chemical Co., Ltd. (Product name: Tough selenium H3522D)
・ H3712D (85% by mass of propylene / α-olefin copolymer raw material sandwiched by 15% by mass of polypropylene random polymer, 90-100% by mass of propylene / α-olefin copolymer raw material, Sumitomo Chemical Co., Ltd.) (Product name: Tough selenium H3712D)

(3) Ethylene polymer: 520 MB (high density polyethylene, manufactured by Prime Polymer Co., Ltd., trade name: Hi-Zex (grade: 520 MB))
・ K9720 (ethylene butene / 5-ethylidene-2-norbornene terpolymer, manufactured by Mitsui Chemicals, trade name: Mitsui Elastomer K-9720)
・ 601F (oil-extended ethylene / propylene / 5-ethylidene-2-norbornene terpolymer, oil-extended ratio of paraffin oil 41.2% by mass, ethylene / propylene / 5-ethylidene-2-norbornene terpolymer The propylene ratio in the active ingredient is 33 to 43% by mass, the ethylene ratio is 56 to 62% by mass, manufactured by Sumitomo Chemical Co., Ltd., trade name: Esprene 601F)

(4) Silicone compound X-22-2101 (silicone master pellet, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-2101)
・ X93-1295 (organohydrogenpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X93-1295)
・ KF-99 (organohydrogenpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-99)
・ 100cs (silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96 (grade: 100cs))
・ 1000cs (silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96 (grade: 1000cs))
10,000 cs (silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96 (grade: 10000 cs))
50,000 cs (silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96 (grade: 50000 cs))
R-127E (acrylic modified silicone, manufactured by Nissin Chemical Industry Co., Ltd., trade name: Charine R (grade: 127))

(5) Others LA-63P (Light stabilizer, manufactured by ADEKA Corporation, trade name: ADK STAB (grade: LA-63P))
LA-36 (light stabilizer, manufactured by ADEKA Corporation, trade name: ADK STAB (grade: LA-36))
-WL (Antioxidant, Goodyear Tire & Rubber Company, trade name: Wingstay (grade: L))
・ HP-10 (phosphorus antioxidant, manufactured by ADEKA Corporation, trade name: ADK STAB (grade: HP-10))
I-1010 (phenolic antioxidant, manufactured by BASF, trade name: IRGANOX 1010)
・ F30940MM (pigment, containing 40% by weight of carbon black, manufactured by DIC Corporation, trade name: PEONY BLACK F-30940MM)
PW-90 (paraffinic process oil, manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process Oil PW (grade: 90))
A-DCP (Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DCP)
Perhexa 25B (2,5-dimethyl-2,5-di (t-butylperoxy) hexane, manufactured by NOF Corporation, trade name)
・ 200V (dry silica, manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 200V)
25B40 (2,5-dimethyl-2,5-di (t-butylperoxy) hexane diluted with silica, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane base Is 40% by mass, manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhexa 25B40)

(Production Example 1: Production of Elastomer E1)
Each component described in Formulation 1 in Table 1 below was kneaded to obtain resin pellets. Specifically, after mixing MA3H and 601F with a blender to obtain a premix, the premix is charged using a weight feed into a high-speed co-directional twin-screw extruder set at a cylinder temperature of 130-170 ° C. By injecting PW-90 using a liquid injection machine provided in the middle of the twin-screw extruder, the premix and PW-90 were kneaded to obtain resin pellets.

  Subsequently, the resin pellets and the crosslinking agent mixture described in Formulation 2 were heated and kneaded to perform dynamic crosslinking to obtain an elastomer E1. Specifically, resin pellets, perhexa 25B and 200V are uniformly dispersed with a blender, and the mixture is placed in a high-speed co-directional twin-screw extruder with a cylinder temperature set to 130 to 170 ° C. By injecting PW-90 using a liquid injection machine, the resin pellets and each component described in Formulation 2 were kneaded to obtain elastomer E1.

(Production Example 2: Production of Elastomer E2)
As described in Table 1 below, dynamic crosslinking was carried out in the same manner as in Example 1 except that the blending ratio (mass ratio) of each component was changed to obtain elastomer E2.

  In Table 1, the compounding ratio of each component is shown as a mass ratio when the total amount of each component of compounding 1 and compounding 2 is 100.

(Production Example 3: Production of Elastomer E3)
The components described in Formulation 1 and Formulation 2 in Table 2 below were kneaded and subjected to dynamic crosslinking to obtain elastomer E3. Specifically, after each component described in Formulation 1 in Table 2 below was uniformly dispersed with a blender to obtain a premix, the weight was applied to a high-speed co-directional twin-screw extruder set at a cylinder temperature of 130 to 150 ° C. Feed the premix using a feed, inject KF-99 using a liquid feeder provided in the middle of the twin screw extruder, and use H700 and 25B40 using a side feeder provided in the middle of the twin screw extruder. Each component was kneaded by adding a mixture (curing agent made into a masterbatch) to obtain an elastomer E3.

(Production Example 4: Production of Elastomer E4)
As shown in Table 2, dynamic crosslinking was carried out in the same manner as in Example 3 except that the compositions and blending ratios of Formulation 1 and Formulation 2 were changed, and elastomer E4 was obtained.

  In Table 2, the blending ratio of each component is shown as a mass ratio when the total amount of each component of blending 1 and blending 2 is 100.

(Production Example 5: Production of elastomer E5)
Each component described in Formulation 1 in Table 3 below is uniformly dispersed with a blender, and charged into a high-speed co-directional twin-screw extruder set at a cylinder temperature of 130 to 150 ° C. using a weight feed to obtain a pre-kneaded product. It was. This pre-kneaded material and each component described in Formulation 2 were uniformly mixed with a blender. Further, each component described in Formulation 3 was uniformly dispersed with a blender to obtain a curing agent master batch.

  A mixture of the pre-kneaded product and each component described in Formulation 2 is charged into a high-speed co-directional twin-screw extruder having a cylinder temperature set to 130 to 150 ° C. using a weight feed, and is provided in the middle of the twin-screw extruder. A cured master batch was charged using the side feeder, and kneading and dynamic crosslinking were performed to obtain elastomer E.

  In Table 3, the blending ratio of each component is shown as a mass ratio when the total amount of each component of blending 1, blending 2, and blending 3 is 100.

(Examples 1-20 and Comparative Examples 1-8)
Each component shown in the following table was uniformly dispersed with a blender, and charged into a high-speed co-directional twin-screw extruder set at a cylinder temperature of 130 to 190 ° C. using a weight feed and kneaded. The strand discharged from the die was cut with a pelletizer to obtain a uniformly shaped pellet made of a sliding material.

(Fusion test)
Using the pellets made of the sliding material obtained in Examples and Comparative Examples, a fusion test was performed by the following method. First, using a parallel two-roll heated to 200 ° C., a joining sheet made of 1.5 mm thick Miralastomer W700B (olefinic thermoplastic elastomer, polypropylene ratio 20 to 45 mass%, trade name, manufactured by Mitsui Chemicals, Inc.) Was made. Next, a test sheet having a thickness of 1.5 mm was similarly produced for the sliding material.

A two-part mold consisting of a digging surface and a flat surface was prepared. A rectangular recess having a thickness of 2.0 mm × width 50 mm × length 190 mm is provided on the digging surface, and a shallow digging having a thickness of 0.15 mm is provided on the outer periphery of the rectangular recess, and a depth of 3 mm is provided on the outer periphery thereof. Digging in. The size of the mold was 250 mm × 300 mm, and the contact area when the mold was closed together was about 505 cm ² .

  The mold was fixed to a heated 80 ton press and kept at 230 ° C. Open the mold, insert a commercially available PET sheet (width 50 mm x length 190 mm) with a thickness of 0.075 mm into the rectangular recess, place the bonding sheet on the PET sheet, and heat for 10 minutes. W700B was melted.

  Next, a commercially available PET sheet (width 50 mm × length 60 mm) having a thickness of 0.075 mm is stacked on the molten bonding sheet together with the three sides, and the test sheet and the thickness 0.075 mm are further stacked thereon. A commercially available PET sheet (width 50 mm × length 190 mm) was placed in order, the press was operated, and the test sheet was pressurized to the maximum pressure within 10 seconds after loading, and brought into close contact at 230 ° C. for 40 seconds. The PET sheet on the two outer layers is for facilitating the removal of the fused product from the mold, and the PET sheet interposed between the joining sheet and the test sheet is used as a chuck for a tensile tester during the peeling evaluation. This is because a pinch is provided.

  The laminated body was taken out from the mold, and rapidly cooled with water at 10 to 20 ° C. (water amount: 18 L) until the temperature of the laminated body became 40 ° C. or lower. The laminate was allowed to stand at 23 ° C. and a humidity of 50% RH for 1 day, and then the PET sheet was peeled off and cut into strips having a width of 25 mm and a length of 100 mm. This strip-shaped test piece had a 40 mm pinch and had a maximum peel evaluation length of 60 mm.

  Using the strip test piece obtained as described above, according to the T-type peel test method of JIS K6854, the test piece was pulled at a rate of 200 mm / min until it was broken, and the peeled length was measured. . The evaluation results are as shown in the following table.

(Injection melting test)
Test sheets having a thickness of 3 mm were prepared from the sliding material pellets of Example 9, Comparative Example 1 and Comparative Example 7, respectively. Specifically, a sheet is prepared using parallel two rolls in which pellets are heated to 200 ° C., inserted into a 3 mm thick plate frame, and heated at 200 ° C. using a press capable of heating and cooling. By forming and cooling to 40 ° C., a test sheet having a thickness of 3 mm was produced. The test sheet was cut to 65 × 103 mm using an NT cutter for insertion into an injection mold.

  This test sheet was inserted into an injection mold, and Miralastomer 7030BS (olefinic thermoplastic elastomer containing 15% by mass or more of polypropylene, trade name, manufactured by Mitsui Chemical Co., Ltd.) was melt-injected. Specifically, an 80 ton injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., molding machine name: FS80S12ASE) is mounted with a sheet molding die having a thickness of 3 mm, a width of 103 mm, and a length of 130 mm, and the insert test sheet is set to 40 ° C. The Miralastomer 7030BS, which was inserted into the held mold and melted, was injected. The cylinder temperature of the injection molding machine when melting 7030BS is 230 ° C, 210 ° C and 190 ° C at the nozzle front, middle and rear (hopper side), injection speed 80-60%, holding pressure 30%, injection Injection welding was performed under conditions of a time of 10 seconds and a cooling time of 40 seconds to obtain a two-color molded product.

  The above injection welding was performed on the test sheet on the day when the surface to be the weld surface of the test sheet was cut out, 1 day, 3 days, 1 week, 2 weeks, and 3 weeks after cutting.

  The obtained two-color molded product was punched into a JIS K6251 No. 3 dumbbell with the joint surface as the center, a tensile test was performed based on JIS K6251, and the breaking strength and breaking elongation were measured. The results are shown in the table below.

  DESCRIPTION OF SYMBOLS 1 ... Sliding member, 10 ... Matrix, 12 ... Domain, 14 ... Silicone compound, 2 ... Sliding member, 16 ... Matrix, 18 ... Window glass, 20 ... Weather strip main-body part, 30 ... Sliding member, 50 ... Weather Strip, 60 ... Weather strip, 110 ... Core material, 120 ... Weather strip body.

Claims (11)

A sliding material containing a propylene polymer, an ethylene polymer and a silicone compound ,
At least a part of the ethylene-based polymer forms a crosslinked body,
Based on the total amount of the sliding material, the content of the propylene polymer is 15 to 40% by mass,
Ri is amorphous propylene-based polymers der 5 to 30 mass% of the propylene polymer,
An elastomer obtained by kneading a composition containing a first propylene polymer and an ethylene polymer and dynamically crosslinking at least a portion of the ethylene polymer, and a second propylene containing an amorphous propylene polymer A sliding material obtained by kneading a polymer and a silicone compound . Based on the total amount of the sliding material, the content of the previous SL ethylene-based polymer is 20 to 55% by weight, is 5 to 25 mass% content of the silicone compound, a sliding material according to claim 1 .   The sliding material according to claim 1, wherein the crosslinked body is a crosslinked body formed by dynamic crosslinking, and is dispersed as a domain in the sliding material. The ethylene polymer is
A first ethylene polymer having a flexural modulus of 1.0 × 10 ² MPa or more;
A second ethylene-based polymer having a flexural modulus of less than 1.0 × 10 ² MPa;
The sliding material according to any one of claims 1 to 3 , comprising: The mass ratio C ₁ / C ₂ of the content C _{1 of the first} ethylene polymer and the content C ₂ of the second ethylene polymer is 0.20 / 0.80 to 0.95 / 0.05. Yes,
The sliding material according to claim 4 , wherein the sliding material has a JIS-A hardness of 85 or more. The amorphous propylene-based polymer is
The JIS-A hardness includes at least one selected from the group consisting of a polypropylene having a hardness of less than 90 and a propylene-α-olefin copolymer having a JIS-A hardness of less than 90, according to any one of claims 1 to 5 . Sliding material. The sliding member formed by shaping the sliding material as described in any one of Claims 1-6 . A weather strip comprising a sliding member in sliding contact with the window glass,
The weatherstrip which the said sliding member shapes the sliding material as described in any one of Claims 1-6 . A sliding member formed by shaping the sliding material according to any one of claims 1 to 6 , and the sliding member formed by shaping a joining material containing 15% by mass or more of a propylene-based polymer; A composite member comprising: a joined member joined. It is a manufacturing method of the composite member according to claim 9 ,
It has a contact process which makes the sliding member formed by shape | molding the sliding material as described in any one of Claims 1-6 contact the molten or softened joining material containing 15 mass% or more of propylene-type polymers. ,Production method. The manufacturing method according to claim 10 , wherein the contacting step is performed by injecting the bonding material into a mold in which the sliding member is inserted.

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