JP6772581B2 - Manufacturing method of joint - Google Patents

Description

The present invention relates to a method for producing a bonded body using a thermoplastic elastomer.

A bonded body of an olefin-based vulcanized rubber molded product and an olefin-based thermoplastic elastomer is used for an automobile weather strip such as an exterior molding, a gasket for a wind seal, a gasket for a door seal, and a gasket for a trunk seal. In this method of manufacturing a bonded body, a thermoplastic elastomer is injected into the remaining cavity in a state where a pre-manufactured olefin-based vulcanized rubber molded product is set in a split mold of an injection molding machine, and the vulcanized rubber is manufactured. A method of fusing an injection molded product of a thermoplastic elastomer to a molded product is common.

In order to produce such a bonded body, various thermoplastic elastomers such as those described in Patent Documents 1 to 5 have been studied.

Japanese Unexamined Patent Publication No. 2011-152734 International Publication No. 2008/13083 U.S. Pat. No. 3,287,440 U.S. Pat. No. 3,709,840 Japanese Unexamined Patent Publication No. 2007-21184

However, the conventional bonded body using the thermoplastic elastomer has a poor appearance such as conspicuous seams at the joints, and the joint strength of the seams may be insufficient.

Therefore, in some aspects of the present invention, by solving at least a part of the above problems, a method for producing a bonded body capable of achieving both good molding processability and good appearance and joint strength at the joint portion. I will provide a.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

[Application example 1]
One aspect of the method for producing a bonded body according to the present invention is
After melting the thermoplastic elastomer in the mold on which the molded body (Ι) is placed, it is injected to integrate the molded body (II) derived from the thermoplastic elastomer and the molded body (Ι). In the manufacturing method of the bonded body
The molded product (I) has a cross section and has a cross section.
The arithmetic mean roughness (Ra) of the cross section is 0.1 to 5 μm.
The Kurtosis (Rku) of the roughness curve of the cross section is 1 to 30.
It is characterized in that the cross section of the molded body (I) and the molded body (II) are joined.

[Application example 2]
In the method for manufacturing a bonded body of Application Example 1,
The thermoplastic elastomer can contain 100 to 1000 ppm of water.

[Application example 3]
In the method for producing a bonded body of Application Example 1 or Application Example 2,
The cylinder temperature during injection molding can be 200-300 ° C.

[Application example 4]
In the method for manufacturing a bonded body of any one of Application Examples 1 to 3,
The mold temperature at the time of injection molding can be 20 to 100 ° C.

[Application example 5]
In the method for producing a bonded body of any one of Application Examples 1 to 4,
The injection rate of the thermoplastic elastomer at the time of injection molding can be 10 to 150 cm ³ / sec.

According to the method for producing a bonded body according to the present invention, the cross section of the molded product (I) is set to a predetermined arithmetic mean roughness (Ra) and a roughness curve curtosis (Rku), whereby a thermoplastic elastomer is produced by an anchor effect. Not only the bonding strength with the molded body (II) derived from the above is improved, but also the appearance is improved without silver streak occurring at the bonded portion with the molded body (II).

It is explanatory drawing which shows typically the manufacturing method of the bonded body which concerns on this embodiment. It is explanatory drawing which shows typically the manufacturing method of the bonded body which concerns on this embodiment. It is explanatory drawing which shows typically the manufacturing method of the bonded body which concerns on this embodiment. It is explanatory drawing which shows typically the manufacturing method of the bonded body which concerns on this embodiment.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented without changing the gist of the present invention. In addition, "(meth) acrylic-" in this specification is a concept including both "acrylic-" and "methacryl-". Further, "-(meth) acrylate" is a concept that includes both "-acrylate" and "-methacrylate".

1. 1. Method for manufacturing a bonded body The method for manufacturing a bonded body according to the present embodiment is derived from the thermoplastic elastomer by melting the thermoplastic elastomer in a mold on which a molded product (Ι) is placed and then injecting the thermoplastic elastomer. In the method for producing a bonded body in which the molded body (II) and the molded body (Ι) are integrated, the molded body (I) has a cross section, and the arithmetic average roughness (Ra) of the cross section is 0. It is 1 to 5 μm, the crutosis (Rku) of the roughness curve of the cross section is 1 to 30, and the cross section of the molded body (I) and the molded body (II) are joined. Hereinafter, the molded body (I) and the molded body (II) used in the method for manufacturing the joined body according to the present embodiment will be described in detail, followed by the method for manufacturing the joined body and the use of the joined body in this order.

1.1. Mold (I)
The material constituting the molded product (I) can be appropriately selected depending on the use and purpose of the bonded product and the bondability with the thermoplastic elastomer constituting the molded product (II). The material constituting the molded body (I) is not particularly limited, but for example, a thermoplastic elastomer (olefin-based, styrene-based, vinyl chloride-based, ester-based, urethane-based, amide-based, etc.), a thermoplastic resin ( Polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene, polyethylene terephthalate, nylon, polycarbonate, polybutylene terephthalate, etc.), vulture rubber (ethylene propylene rubber, natural rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, chloroprene rubber, etc. Isoprene rubber, acrylonitrile butadiene rubber, silicone rubber, fluorine rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, etc.), metals and the like can be mentioned. When the material constituting the molded product (I) is composed of a material containing the same components as the thermoplastic elastomer constituting the molded product (II), the mechanical strength of the joint surface can be further improved. preferable. Further, as the material constituting the molded body (I), a plurality of materials can be appropriately used depending on the use and purpose of the bonded body.

In the method for producing a bonded body according to the present embodiment, the molded body (II) derived from the thermoplastic elastomer and the molded body (Ι) are integrated. At this time, the molded body (I) and the molded body (II) are integrated. Has a joint surface. Here, as for the molded body (I), it is preferable to cut the unprocessed molded body (I) and use the cross section thereof as the joint surface. Further, it is considered that by cutting the molded body (I) that has not been exposed to the atmosphere and using its cross section as a joint surface, it is possible to suppress joint defects due to adsorption of pollutants such as moisture from the atmosphere, for example.

The molded body (I) can be produced by using a material containing a filler or the like in order to further improve the mechanical strength of the bonded body according to the required purpose of use of the bonded body. When the molded product (I) contains a filler, the arithmetic average particle size of the filler is preferably 0.001 to 5 μm, more preferably 0.01 to 3 μm. When the arithmetic mean particle size of the filler is within the above range, it is possible to easily produce a bonded body that satisfies both mechanical strength and good appearance. The arithmetic mean particle size is calculated from, for example, the particle size distribution measured by a laser scattering type particle size distribution measuring method.

When the molded product (I) contains a filler, the material of the filler includes a carbon material and an inorganic material, and carbon black, calcium carbonate and the like can be preferably used. By using a carbon material or an inorganic material as the filler, not only the mechanical strength of the bonded body can be further improved, but also flame retardancy can be imparted to the bonded body. When carbon black is used as the filler, the arithmetic average particle size of carbon black is preferably 0.02 to 1 μm. When calcium carbonate is used as the filler, the arithmetic mean particle size of calcium carbonate is preferably 0.5 to 3 μm.

The arithmetic mean roughness (Ra) in the cross section of the molded product (I) needs to be 0.1 to 5 μm, preferably 0.5 to 4 μm. Here, the arithmetic mean roughness (Ra) is a kind of index indicating the surface roughness, and is obtained by calculating the average of the absolute values of the heights at the reference length. When the arithmetic mean roughness is small, it means that the height value of the uneven shape of the surface is small (the undulations are small), and when the arithmetic average roughness is large, it means that the height difference of the uneven shape of the surface is small. Means that is large (large undulations). When the arithmetic mean roughness (Ra) in the cross section of the molded body (I) is within the above range, silver streak does not occur at the joint with the molded body (II) and the appearance tends to be good, and due to the anchor effect, The joint strength of the seam can be made good.

The Kurtosis (Rku) of the roughness curve in the cross section of the molded product (I) needs to be 1 to 30, preferably 5 to 24. Here, Kurtosis (Rku) is a kind of index showing the surface roughness, and is an index showing the degree of sharpness of the uneven shape formed on the surface. Specifically, Kurtosis is obtained by dividing the fourth power of the height at the reference length by the fourth power of the root mean square, which means the standard deviation of the surface roughness. When the cultosis is small, it means that the uneven shape of the surface is smooth, and when the cultosis is large, it means that the uneven shape of the surface is sharply pointed. When the Kurtosis (Rku) of the roughness curve in the cross section of the molded body (I) is within the above range, silver streak does not occur at the joint with the molded body (II) and the appearance tends to be good, and the anchor effect is obtained. Therefore, the joint strength of the seam can be improved.

The arithmetic mean roughness (Ra) in the cross section of the molded body (I) and the Kurtosis (Rku) of the roughness curve are the arithmetic average particle size and content of the filler when the molded body (I) contains the filler. Can be controlled by adjusting. It can also be controlled by polishing the cross section of the molded product (I) with the molded product (II) with a file or the like.

1.2. Mold (II)
The molded product (II) is produced by injection molding a thermoplastic elastomer melted in a mold on which the molded product (Ι) is placed. In this way, the molded body (II) and the cross section of the molded body (I) are joined and integrated.

The thermoplastic elastomer, which is the raw material of the molded product (II), preferably contains 100 to 1000 ppm of water, more preferably 100 to 800 ppm, and particularly preferably 100 to 600 ppm. When the water content is within the above range, when the thermoplastic elastomer is injection-molded, it is possible to produce a bonded body having a bonded portion having excellent molding processability and excellent both appearance and bonding strength. If the water content exceeds the above range, the water is heated in the cylinder of the injection molding machine and becomes bubbles in the thermoplastic elastomer, which may cause bubbles to burst on the surface of the molded product, resulting in poor appearance (siriburst leak). .. Further, when the joint body is manufactured, the joint portion may cause a joint failure with the other molded body, or air bubbles may remain in the joint portion to reduce the joint strength. In addition, in the measurement process of injection molding, the fluctuation of the measurement time for each molding may be large, so that the productivity decreases when the measurement time becomes long, and the thermoplasticity when the measurement time becomes short. The plasticization of the elastomer may be poor. On the other hand, if the water content is less than the above range, excessive heat treatment (temperature x time) is required because the material is too dry, so that the material itself is deteriorated (deterioration, bleed-out, etc.) and the bonding strength is increased. May decrease.

In the present invention, the "moisture content of the thermoplastic elastomer" is synonymous with the water content of the pellet of the thermoplastic elastomer.

The water content of the thermoplastic elastomer in the present invention is a value measured in accordance with JIS K7251 "Plastic-How to determine the water content".

The water content of the thermoplastic elastomer is controlled by heat-treating the thermoplastic elastomer at a temperature and time suitable for the thermoplastic elastomer to be used using a pellet dryer such as a dehumidifying dryer, a vacuum dryer, or a hot air dryer. can do. A high drying temperature and a long drying time can significantly reduce the amount of water, but the pellets of the thermoplastic elastomer may cause blocking or deterioration such as bleed-out. Further, when the drying temperature is low and the drying time is short, the water content tends to increase. In any case, the water content can be controlled by controlling the drying temperature and the drying time in this way.

The thermoplastic elastomer that is the raw material of the molded product (II) is not particularly limited, but is, for example, a styrene-based hydrogenated block copolymer described in JP-A-2005-272528, etc .; (A) ethylene / α- Elastomers (hereinafter, also referred to as "specific elastomers") produced from raw material compositions containing olefin / non-conjugated polyene copolymers, (B) α-olefin thermoplastic resins, and (C) cross-linking agents, vinyl chloride. Examples thereof include based thermoplastic elastomers, ester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and amide-based thermoplastic elastomers, and specific elastomers are particularly preferable. Hereinafter, the raw material composition used for producing the specific elastomer will be described.

<(A) Ethylene / α-olefin / non-conjugated polyene copolymer>
The (A) ethylene / α-olefin / non-conjugated polyene copolymer (hereinafter, also referred to as “component (A)”) is a component used mainly for the purpose of imparting flexibility to the thermoplastic elastomer. , Ethylene, α-olefin and non-conjugated polyene, respectively, preferably a copolymer having a repeating unit.

As the α-olefin, an α-olefin having 3 to 10 carbon atoms is preferable. The α-olefin has more preferably 3 to 8 carbon atoms, further preferably 3 to 6 carbon atoms, and particularly preferably 3 to 4 carbon atoms. It is preferable to use an α-olefin having 3 to 10 carbon atoms because the copolymerizability of the α-olefin with another monomer is improved. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. .. Of these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene and 1-butene are more preferable. The component (A) may contain a repeating unit derived from only one α-olefin among these α-olefins, or may contain a repeating unit derived from two or more kinds of α-olefins. It may be one.

Examples of the non-conjugated polyene include a linear acyclic diene, a branched acyclic diene, and an alicyclic diene. Examples of the linear acyclic diene include 1,4-hexadiene, 1,5-hexadiene, and 1,6-hexadiene. Examples of the acyclic diene having the above branch include 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, and 3,7-. Examples thereof include dimethyl-1,7-octadiene, 7-methylocta-1,6-diene and dihydromilsen. Examples of the alicyclic diene include tetrahydroinden, methyltetrahydroinden, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene, and 5-ethylidene-2. -Norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and the like can be mentioned. Of these, 1,4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene are preferable. The component (A) may contain a repeating unit derived from only one non-conjugated polyene among these non-conjugated polyenes, or may contain a repeating unit derived from two or more non-conjugated polyenes. It may be a thing.

The content of ethylene units in the component (A) is preferably 50 to 90 mol% when the total of the ethylene units and the α-olefin units constituting the component (A) is 100 mol%. The content of the α-olefin unit in the component (A) is preferably 5 to 50 mol% when the total of the ethylene units and the α-olefin units constituting the component (A) is 100 mol%. The content of the non-conjugated polyene unit in the component (A) is preferably 3 to 10 mol% when the total of all the repeating units constituting the component (A) is 100 mol%.

The raw material composition for producing the specific elastomer is a total of 100 (A) ethylene / α-olefin / non-conjugated polyene copolymer, (B) α-olefin thermoplastic resin, and (C) cross-linking agent. When it is set to mass%, the component (A) is preferably contained in an amount of 10 to 95% by mass.

The component (A) may be a substituted copolymer or a graft copolymer having an ethylene / α-olefin / non-conjugated polyene copolymer as a basic skeleton. Examples of the substituted copolymer include a halogenated copolymer in which a part of hydrogen atoms contained in the copolymer is substituted with halogen atoms such as chlorine atom and bromine atom. Examples of the graft copolymer include a graft copolymer obtained by graft-polymerizing an unsaturated monomer on the polymer or the like. Examples of the unsaturated monomer include vinyl chloride, vinyl acetate, (meth) acrylic acid, maleic acid, methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, maleic anhydride, maleimide, and dimethyl maleate. Conventionally known unsaturated monomers such as butadiene, isoprene, and chloroprene can be used.

The component (A) can be synthesized by a known method, and can be synthesized by, for example, the method described in JP-A-2014-193999.

<(B) α-olefin thermoplastic resin>
(B) The α-olefin-based thermoplastic resin (hereinafter, also referred to as “component (B)”) can be used mainly for the purpose of imparting mechanical strength and heat resistance to the thermoplastic elastomer. In such a case, the component (B) is preferably a resin composed of a polymer containing an α-olefin unit as a main component. For example, when the total amount of the polymer is 100 mol%, it is preferable that the resin is made of a polymer containing 80 mol% or more of α-olefin units.

Further, the component (B) can be used mainly for the purpose of lowering the melt viscosity of the thermoplastic elastomer to impart fluidity and preventing solidification in the flow process in the mold. In such a case, the component (B) is a homopolymer of α-olefin or a copolymer of two or more kinds of α-olefins, or an unsaturated monomer other than α-olefin and α-olefin. It is preferably a copolymer with. Two or more of these components (B) can be used in a timely manner depending on the purpose of addition.

The term "α-olefin" as used herein is a concept including ethylene. As the α-olefin that derives the α-olefin unit in the component (B), ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, and for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3- Examples thereof include methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, 1-undecene and the like. Among these, using at least one selected from the group consisting of organic peroxide-disintegrating propylene and 1-butene as at least a part of α-olefin is a viewpoint of maintaining processability at the time of molding. Is preferable.

Examples of the component (B) include a propylene homopolymer, a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / 1-pentene copolymer, and a propylene / 3-methyl-1-butene copolymer. , Propropylene / 1-hexene copolymer, propylene / 3-methyl-1-pentene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 3-ethyl-1-pentene copolymer, propylene -Examples include 1-octene copolymer, propylene / 1-decene copolymer, propylene / 1-undecene copolymer and the like. Of these, propylene homopolymers and propylene / ethylene copolymers are preferable.

The raw material composition for producing the specific elastomer preferably contains 3 to 65% by mass of the component (B) when the total of the components (A) and (B) is 100% by mass.

Further, the gel fraction of the rubber in the specific elastomer composition is preferably 95% or more, more preferably 96% or more, and when the gel fraction is in the above range, the bonding strength of the bonded body becomes better. .. The method for measuring the gel fraction is as follows.

Approximately 200 mg of the thermoplastic elastomer composition is weighed and cut into small pieces. Then, the obtained strips are immersed in 100 ml of cyclohexane in a closed container at 23 ° C. for 48 hours. Next, this sample is taken out on a filter paper and dried in a vacuum dryer at 105 ° C. for 1 hour under reduced pressure. The value obtained by subtracting (1) the mass of cyclohexane insoluble components other than rubber and the thermoplastic resin and (2) the mass of the thermoplastic resin in the sample before immersion in cyclohexane from the mass of this dry residue was "corrected." Final mass (p) ”.

On the other hand, from the mass of the sample, (3) the mass of the cyclohexane-soluble component other than the rubber and the thermoplastic resin, (1) the mass of the cyclohexane insoluble component other than the rubber and the thermoplastic resin, and (4) the mass of the thermoplastic resin. The value obtained by subtracting the mass is defined as the "corrected initial mass (q)". Here, the gel fraction (cyclohexane insoluble matter) is calculated by the following formula (1).
Gel fraction [mass%] = [{corrected final mass (p)} ÷ {corrected initial mass (q)}] × 100 (1)
In order to increase the gel fraction, a method of using a rubber having a high iodine value as a raw material in the thermoplastic elastomer composition, and when the rubber is an ethylene / α-olefin rubber, the ethylene unit or the non-conjugated diene unit is contained. Examples include a method of increasing the ratio, a method of increasing the blending amount of the cross-linking material and the cross-linking auxiliary material, and the like.

The component (B) can be synthesized by a known composition and production method, and can be synthesized by, for example, the composition and production method described in JP-A-2014-193969.

<(C) Crosslinking agent>
The (C) cross-linking agent (hereinafter, also referred to as “component (C)”) is subjected to heat treatment to transfer at least a part of the component (A) and the component (B) between components of the same type or components of different types. It has a function of cross-linking.

Examples of such component (C) include phenolic cross-linking agents, organic peroxides, sulfur, sulfur compounds, p-quinone, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, and amino resins. , Polyphenol cross-linking agent, polyamine, triazine compound, metal soap and the like. Of these, it is preferable to use a phenolic cross-linking agent or an organic peroxide. When a phenolic cross-linking agent is used as the component (C), it is preferable to use a cross-linking accelerator in combination. When an organic peroxide is used as the component (C), it is preferable to use a cross-linking aid in combination.

Examples of the phenolic cross-linking agent include an o-substituted phenol / aldehyde condensate, an m-substituted phenol / aldehyde condensate, a brominated alkylphenol / aldehyde condensate, and a compound represented by the following general formula (2). it can. Of these, the compound represented by the following general formula (2) is preferable.

In the above formula (2), a plurality of Rs are independently saturated hydrocarbon groups having 1 to 15 carbon atoms, m is an integer of 0 to 10, and X and Y are independently hydroxyl groups. Or it is a halogen atom.

The compound represented by the general formula (2) is generally used as a cross-linking agent for rubber, as described in, for example, US Pat. No. 3,287,440 and US Pat. No. 3,709,840. It is a compound. This compound can be produced by polycondensation of a substituted phenol and an aldehyde in the presence of an alkaline catalyst.

When a phenolic cross-linking agent is used as the component (C), the raw material composition contains 0.2 to 10 parts by mass of the phenol-based cross-linking agent when the total of the components (A) and (B) is 100 parts by mass. It is preferable to contain a portion.

The phenolic cross-linking agent may be used by itself, but it is preferable to use a cross-linking accelerator in combination in order to adjust the cross-linking rate. As the cross-linking accelerator, for example, metal halides such as stannous chloride and ferric chloride; organic halides such as chlorinated polypropylene, butyl rubber bromide, and chloroprene rubber can be used. In addition to the cross-linking accelerator, it is more preferable to further use a metal oxide such as zinc oxide and a dispersant such as stearic acid in combination.

Examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3,2,5-. Dimethyl-2,5-bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy) ) -P-Isopropylbenzene, dicumylperoxide, di-t-butyl peroxide, t-butyl peroxide, p-menthamper oxide, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, benzoyl peroxide, di (t-butyl peroxy) perbenzoate , N-Butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxyisopropyl carbonate and the like.

When an organic peroxide is used as the component (C), the raw material composition contains 0.05 to 10 parts by mass of the organic peroxide when the total of the components (A) and (B) is 100 parts by mass. It is preferable to contain a part.

The organic peroxide may be used by itself, but it is preferable to use a cross-linking aid in combination in order to proceed the cross-linking reaction gently and form a uniform cross-link. Examples of the cross-linking aid include sulfur, sulfur compounds, p-quinone oximes, oxime compounds such as p, p'-dibenzoylquinone oxime, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di. (Meta) Acrylate, Tetraethylene Glycol Di (Meta) Acrylate, Polyethylene Glycol Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Dialyl Futarate, Tetraallyl Oxyethane, Triallyl Cyanurate, N, N'-m Examples thereof include polyfunctional monomers such as −phenylene bismaleimide, N, N'-toluylene bismaleimide, maleic anhydride, divinylbenzene, and zinc di (meth) acrylate.

<Other ingredients>
The raw material composition for producing the thermoplastic elastomer may further contain (D) spreading oil (hereinafter, also referred to as “component (D)”). The component (D) is used mainly for the purpose of imparting fluidity to the obtained thermoplastic elastomer. Examples of the component (D) include mineral oil-based hydrocarbons and low molecular weight hydrocarbons, but favorite oil-based hydrocarbons are preferable.

Examples of the mineral oil-based hydrocarbons include Diana process oils PW90, PW100, and PW380 (all manufactured by Idemitsu Kosan Co., Ltd.) under trade names. Examples of low molecular weight hydrocarbons include low molecular weight polybutene and low molecular weight polybutadiene.

The content of the component (D) in the raw material composition for producing the thermoplastic elastomer is preferably 300 parts by mass or less when the component (A) is 100 parts by mass. As the component (D), at least one of the component (A) and the component (B) may be used as an oil-extended product and added to the raw material composition in the form contained in the oil-extended product (A). ) And component (B) may be added to the raw material composition in a separated form, or both.

The raw material composition for producing the thermoplastic elastomer may further contain other components in addition to the above components. Other components include, for example, polymer compounds, oligomers, antibacterial / antifungal agents, plasticizers, graphite nucleating agents, flame retardants, tackifiers, foaming aids, antioxidants, antioxidants, blocking agents, seals. Sex improvers, lubricants, stabilizers (eg anti-aging agents, heat stabilizers, weather-resistant agents, metal deactivators, UV absorbers, light stabilizers, copper damage inhibitors, etc.), colorants / pigments (eg titanium oxide, Carbon black etc.), metal powder (eg ferrite etc.), inorganic fiber (eg glass fiber, metal fiber etc.), organic fiber (eg carbon fiber, aramid fiber etc.), composite fiber, inorganic whisker (eg potassium titanate whisker etc.) , Fillers as fillers (eg glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, wet silica, dry silica, alumina, alumina silica, calcium silicate, hydrotalcite, kaolin, diatomaceous soil, Graphite, prickly stone, evo powder, cotton floc, cork powder, barium sulfate, fluororesin, polymer beads, polyolefin wax, cellulose powder, rubber powder, wood powder, carbon black, etc.), carbon-based materials as conductive fillers (for example, Ket Furness black such as chain black, acetylene black, channel black, carbon black such as gas black; carbon fibers such as PAN-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber; spheroidal graphite, scaly graphite, lump graphite, soil Graphite such as graphite; fullerene, carbon microcoil, carbon nanotube, etc.), metal-based materials (for example, silver powder, gold powder, copper powder, iron powder, stainless steel powder, nickel powder, aluminum powder, platinum powder, etc.); zinc oxide , Antimon oxide, metal oxide powder such as indium oxide; metal fiber such as copper fiber, stainless fiber, aluminum fiber, nickel fiber, etc.), ceramic material (for example, alumina-titanium carbide type ceramic, zirconia type ceramic, silicon carbide type) A composite material whose surface is coated with a conductive material (such as glass, silica, polymer particles coated with the above carbon-based material, metal-based material, or ceramic-based material) can be mentioned as an example of a conductive ceramic such as ceramic). it can.

The raw material composition for producing a thermoplastic elastomer may further contain a polymer compound or an oligomer as long as the effects of the present invention are not impaired. For example, thermoplastic elastomers (olefin-based, styrene-based, vinyl chloride-based, ester-based, urethane-based, amide-based, etc.), thermoplastic resins (polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene styrene, polyethylene terephthalate, nylon, polycarbonate, etc.) , Polybutylene terephthalate, etc.), rubber (ethylene propylene rubber, natural rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, chloroprene rubber, isoprene rubber, acrylonitrile butadiene rubber, silicone rubber, fluorine rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, etc. ) Etc. can be mentioned.

1.3. Method for manufacturing a bonded body Hereinafter, one aspect of the method for manufacturing a bonded body according to the present embodiment will be described in detail with reference to the drawings.

1 to 4 are explanatory views schematically showing a specific example of a method for manufacturing a bonded body according to the present embodiment. First, an injection molding die 100 as shown in FIG. 1 is prepared. As shown in FIG. 1, the injection molding die 100 includes a fixed die 10 and a movable die 12 that can slide relative to the fixed die 10 in the direction of contact with the fixed die 10. The facing surfaces of the fixed mold 10 and the movable mold 12 are formed with cavities having the shape of the desired joint body in a state where the injection molding die 100 is completely molded. Further, a nozzle 14 for injecting the thermoplastic elastomer 20 is provided in the movable mold 12, and the nozzle 14 and the cavity communicate with each other.

In the present embodiment, the fixed mold 10 has a substantially concave shape, and the movable mold 12 has a substantially convex shape. Therefore, when the injection molding die 100 is molded, the fixed die 10 is molded so as to cover the convex portion of the movable die 12.

Next, as shown in FIG. 2, a prefabricated molded body 30 (molded body (I)) is placed on the fixed mold 10. After that, the movable mold 12 is slid in the fixed mold 10 direction to mold the injection molding mold 100.

The material of the molded product 30 is not particularly limited, and for example, vulcanized rubber, thermoplastic elastomer, thermoplastic resin, metal and the like can be preferably used. These materials can also be used in combination of two or more, if necessary. Further, the molded body 30 may be foamed.

Examples of the vulcanized rubber include vulcanized rubber obtained from EPDM. Examples of the thermoplastic elastomer include an olefin-based elastomer (TPO), a dynamically crosslinked thermoplastic elastomer (Thermoplastic. Vulcanizers; TPV), a styrene-based thermoplastic elastomer (TPS), and the like. Examples of the thermoplastic resin include olefin-based thermoplastic resins such as PP.

The molded body 30 can be manufactured by a known method such as extrusion molding or injection molding.

Next, as shown in FIG. 3, after molding the injection molding die 100, the molten thermoplastic elastomer 20 is injected to form the molded body 32 (molded body II) and the molded body 30 (molded body (I)). To be integrated with. At this time, the arithmetic mean roughness (Ra) of the cross section of the molded body 30 (molded body (I)) to be the joint surface 34 is 0.1 to 5 μm, and the roughness curve curtosis (Rku) is 1 to 1. When it is 30, a bonded body 40 having excellent bonding strength can be obtained on the joint surface 34 between the molded body 30 and the molded body 32 without causing an appearance defect due to a siliburst leak. Further, when the water content of the thermoplastic elastomer 20 to be injected is 100 to 1000 ppm,
In the measurement process of injection molding, the variation in the measurement time for each molding is small, so that the molding processability is improved. As the thermoplastic elastomer 20, the thermoplastic elastomer described in the above section "1.2. Molded product (II)" can be preferably used.

When the thermoplastic elastomer 20 is supplied to the injection molding die 100, it is preferably supplied in the form of pellets, and more preferably spherical pellets. By using the spherical pellets, it is possible to suppress blocking due to mutual adhesion between the pellets at the supply port of the injection molding die 100. The particle size of the pellet is preferably 2 to 5 mm. If the particle size of the pellets is too large or too small, the supply to the injection molding die 100 may be poor.

As the conditions for injection molding, the cylinder temperature is preferably 200 ° C. to 300 ° C., more preferably 240 ° C. to 260 ° C. Injection of the thermoplastic elastomer is preferably 10~150cm ³ / sec, more preferably 20~90cm ³ / sec. The mold temperature is preferably 20 ° C. to 100 ° C., more preferably 45 ° C. to 60 ° C. Injection molding under such conditions is preferable in that the bonding strength between the molded body 30 (molded body (I)) and the molded body 32 (molded body II) becomes larger.

Finally, as shown in FIG. 4, the movable mold 12 is slid away from the fixed mold 10 to obtain the bonded body 40.

The injection molding machine is not particularly limited, and examples thereof include a vertical mold clamping / vertical injection type injection molding machine, a vertical mold clamping / horizontal injection type injection molding machine, a horizontal mold clamping / horizontal injection injection molding machine, and the like. A mold clamping / vertical injection type injection molding machine is particularly suitable.

1.4. Uses of joints The joints obtained as described above can be used for various purposes such as automobile bumpers; exterior moldings; wind seal gaskets; door seal gaskets; trunk seal gaskets; roof side rails; emblems; inners. Interior / exterior skin materials for panels, door trims, console boxes, etc .; Weather strips; Leather seats that require scratch resistance; Seal materials for aircraft / ships and interior / exterior skin materials; Seal materials for civil engineering / construction, interior / exterior Skin material, waterproof sheet material, etc .; Seal material for general machinery / equipment; Light electrical parts / water packing; Seal material, skin material, housing, etc. in fuel cell stack; Railroad track pad; Roll for information equipment; Cleaning Blades; Films for electronic parts; Protective films in semiconductor and flat panel display (FPD) manufacturing processes; Image protective films for photographs, etc .; Medical equipment parts; Electric wires; Daily miscellaneous goods; Widely applied to general processed products such as sporting goods can do.

2. Examples Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Parts” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

2.1. Example 1
<Manufacturing of joints>
Ethylene / propylene / 5-ethylidene-2-norbornene ternary copolymer (trade name "EP 57C", manufactured by JSR Co., Ltd.) 100 parts by mass, carbon black (trade name "Seast SO", manufactured by Tokai Carbon Co., Ltd.) ) 120 parts by mass, calcium carbonate (trade name "Super SSS", arithmetic average particle size 1.8 μm, manufactured by Maruo Calcium Co., Ltd.) 50 parts by mass, paraffin-based process oil (trade name "PW90", Idemitsu Kosan Co., Ltd.) 70 parts by mass, 5 parts by mass of active zinc flower (manufactured by Sakai Chemical Industry Co., Ltd.) and 1 part by mass of stearic acid (manufactured by ADEKA Co., Ltd.) at 50 ° C., 70 rpm, 2.5 minutes using a Banbury mixer. The mixture was obtained under the conditions of.

To the total amount (346 parts by mass) of the obtained mixture, 10 parts by mass of a dehydrating agent (trade name "Vesta PP", manufactured by Inoue Lime Industry Co., Ltd.), and as a vulcanization accelerator, trade name "Noxeller MP" 0. 6 parts by mass, product name "Noxeller CZ-G" 0.5 parts by mass, product name "Noxeller TT-P" 1.2 parts by mass and product name "Noxeller BZ-P" 2 parts by mass (all of which are Ouchi) Shinko Kagaku Kogyo Co., Ltd. and 2 parts by mass of sulfur were added, kneaded at 50 ° C using an open roll, and then vulcanized at 170 ° C for 10 minutes to 120 mm × 120 mm × 2 mm (length × width × thickness). The vulcanized rubber sheet was used. This sheet was punched to a length of 60 mm and a width of 50 mm using a dumbbell cutter to obtain a molded product (I).

The arithmetic mean roughness Ra of the cross section of the obtained molded body (I) and the Kurtosis Rku of the roughness curve were measured with a laser microscope (LEXT OLS4000 manufactured by Olympus Corporation) at a magnification of 432 times. It was 9 μm and Rku = 16.2.

As the thermoplastic elastomer, EXCELINK1805B (manufactured by JSR, durometer hardness A80, MFR 20 g / 10 min (230 ° C. / 2.16 kg), spherical pellet with a particle size of 3 mm) was used. The water content of EXCELINK1805B was measured according to JIS K7251 (Method B) and found to be 4080 ppm.

In order to reduce the water content of the pellets of EXCELINK1805B, a dryer (trade name "parallel flow batch dryer", manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.) was used to set the drying temperature to 80 ° C and the drying time in a timely manner. Was changed and dried. As a result, it was found that the water content of the pellets of EXCELINK1805B can be controlled by the drying time. Therefore, when the drying temperature was set to 80 ° C. and the drying time was set to 420 minutes using the above dryer, the water content of the pellets of EXCELINK1805B was 180 ppm.

Next, the olefin-based vulcanized rubber adherend obtained above is preliminarily pasted in a split mold of an injection molding machine (trade name "J-110AD", manufactured by Japan Steel Works, Ltd.) having a mold clamping force of 110 tons. Attached.

Next, the EXCELINK1805B whose water content was controlled to 180 ppm by drying as described above was placed in the missing portion (inside the split mold to which the molded product (I) was attached) at a cylinder temperature of 250 ° C. and a mold temperature. A bonded body (120 mm × 120 mm) in which a molded product (II) derived from the thermoplastic elastomer and the molded product (I) are joined by injection molding in the split mold under the conditions of 50 ° C. and an injection rate of 50 cm ³ / sec. × 2 mm (length × width × thickness)) was obtained.

<Appearance evaluation>
Visually observe the obtained joint, and silver streak (silver) of the molded product (ΙΙ).
The presence or absence of streak (a glittering streak pattern on the surface of the joint) was examined. It is ideal and can be judged to be good when the series burst leak does not occur. However, from a practical point of view, the evaluation is judged as "○" when the injection molding appearance is not visible when the series burst leak is not visible, and when the series burst leak is severe and cannot be used practically, it is regarded as an injection molding appearance defect. “X” is shown in Table 1.

<Evaluation of joint strength>
The obtained bonded body was punched out with a JIS-3 dumbbell cutter to obtain a test piece (dumbbell-shaped test piece) for evaluating vulcanized rubber adhesiveness. At this time, in the flat plate, the injection fusion surface (the surface where the thermoplastic elastomer and the olefin vulcanized rubber adherend are injection fusion) is located between the marked lines and is perpendicular to the tensile direction. A sample piece for evaluation of joint strength was prepared by punching so as to be.

Using a tensile tester (model name "AG-2000", manufactured by Shimadzu Corporation), pull the sample piece for joint strength evaluation at a load speed of 200 mm / min, and obtain the value of breaking strength (unit: MPa). It was used as an index of vulcanized rubber adhesiveness. It can be judged that the larger the value of the bonding strength, the better the bonding property. It can be said that the larger the value of the breaking strength is, the better it is, but practically, when it is 3 MPa or more, it can be judged that the joint strength is good. If it is less than 3 MPa, the joint strength is poor.

<Evaluation of molding processability>
Injection molding is repeated 50 times by the same method as in the above section <Manufacturing of bonded body>, and the measurement required for the injection molding machine to measure a certain amount of pellets required for injection molding of the same molded product. The time was totaled. The difference between the longest time and the shortest time of the totaled weighing time was used as an index of molding processability. It is preferable that the smaller the fluctuation of the weighing time is, the more stable mass production can be performed. However, when the difference between the longest time and the shortest time is 2 seconds or less, practically stable mass production is possible and the molding process is performed. Table 1 shows "○" as the property is judged to be good, and "×" as the molding processability is poor because the fluctuation range of the weighing time is large and stable mass production is difficult and difficult if it exceeds 2 seconds. Indicated.

2.2. Examples 2-4, 7-9, Comparative Examples 1-5, 10
A bonded body was prepared and evaluated in the same manner as in Example 1 except that the water content of the pellets of EXCELINK1805B was as shown in Tables 1 and 2 below and the injection molding conditions shown in Tables 1 and 2 below were used. .. As described above, the moisture content of the pellets of EXCELINK1805B was set to a drying temperature of 80 ° C. using a dryer (trade name "parallel flow circulation type dryer", manufactured by Satake Chemical Machinery Co., Ltd.), and the drying time was timely. Adjusted by changing.

2.3. Example 5
A molded product (I) was produced in the same manner as in Example 1 above, except that the composition was changed to that shown in Table 2 below. The cross section of the produced molded product (I) to be the joint surface with the molded product (II) is polished with a sheet paper having a particle size of 600 (trade name "GBS-600", manufactured by TRUSCO NAKAYAMA Co., Ltd.), and the arithmetic mean roughness A molded product (I) having a cross section (planned bonding surface) of 1.8 μm for (Ra) and 8.3 for Kurtosis (Rku) was produced.

Next, using a dryer (trade name "parallel flow batch dryer", manufactured by Satake Chemical Machinery Co., Ltd.), the drying temperature was set to 80 ° C., and the drying time was changed in a timely manner to increase the water content of the pellets to 140 ppm. A bonded body was prepared and evaluated in the same manner as in Example 1 above, except that the injection molding conditions shown in Table 1 below were used.

2.4. Example 6, Comparative Examples 6-9
Using a sheet paper having the following particle size, the cross section of the molded body (I) to be the joint surface with the molded body (II) is shown in Table 2 below with the arithmetic mean roughness (Ra) and Kurtosis (Rku). A molded product (I) was produced in the same manner as in Example 5 above, except that the mixture was adjusted to. Next, using a dryer (trade name "Parallel flow batch dryer", manufactured by Satake Chemical Machinery Co., Ltd.), the drying temperature was set to 80 ° C, and the moisture content of the pellets was lowered by changing the drying time in a timely manner. A joined body was prepared and evaluated in the same manner as in Example 1 above, except that the conditions were as shown in Table 2 and the injection molding conditions shown in Table 2 below were used.
<Sheet paper used>
Example 6: Sheet paper with a particle size of 800 (trade name "GBS-800", manufactured by TRUSCO NAKAYAMA Co., Ltd.)
Comparative Example 6: Sheet paper with a particle size of 180 (trade name "GBS-180", manufactured by TRUSCO NAKAYAMA Co., Ltd.)
Comparative Example 7: Sheet paper with a particle size of 220 (trade name "GBS-220", manufactured by TRUSCO NAKAYAMA Co., Ltd.)
Comparative Example 8: Sheet paper with a particle size of 320 (trade name "GBS-320", manufactured by TRUSCO NAKAYAMA Co., Ltd.)
Comparative Example 9: Sheet paper with a particle size of 1200 (trade name "GBS-1200", manufactured by TRUSCO NAKAYAMA Co., Ltd.)

The abbreviations or trade names of each component in Tables 1 and 2 above mean the following components, respectively. In addition, the numerical values of each component in the composition of the molded product (I) in Tables 1 and 2 above represent parts by mass.
<EPDM>
EP103AF: Ethylene / propylene / 5-ethylidene-2-norbornene ternary copolymer (trade name "EP 103AF", manufactured by JSR Corporation, ethylene unit content 59% by mass, propylene unit content 36.5% by mass, Mooney viscosity) 91)
-EP57C: Ethylene-propylene-5-ethylidene-2-norbornene ternary copolymer (trade name "EP 57C", manufactured by JSR Corporation)
<Natural rubber>
・ RSS3: RSS3 <BR>
BR01: Polybutadiene rubber (trade name "JSR BR01", manufactured by JSR Corporation, cis 1,4 bond amount 95% by mass, Mooney viscosity 45)
<SBR>
SL552: Solution-polymerized styrene-butadiene rubber (trade name "JSR SL552", manufactured by JSR Corporation, bound styrene amount 23.5% by mass, vinyl bonding amount 33.5% by mass, Mooney viscosity 55)
<Olefin resin>
VESTROPLAST 508: Ethylene propylene 1-butene copolymer (trade name "VESTOPLAST 508", manufactured by Evonik Degussa, ethylene unit content 16 mol%, propylene unit content 24 mol%, melt viscosity (190 ° C., ASTM-D3236) 8,000 MPa・ S, density 0.87 g / cm ³ )
<Paraffin-based process oil>
-PW380: Product name "Diana Process Oil PW380", manufactured by Idemitsu Kosan Co., Ltd.-PW90: Product name "Diana Process Oil PW90", manufactured by Idemitsu Kosan Co., Ltd. <Naften-based process oil>
-NM280: Product name "Diana Process Oil NM280", manufactured by Idemitsu Kosan Co., Ltd. <Aroma-based process oil>
・ Aromax 3: Product name "Aromax 3", manufactured by Fuji Kosan Co., Ltd. <Processing aid>
-Hitanol 1501: Product name "Hitanol 1501", manufactured by Hitachi Chemical Co., Ltd. <Release agent>
-Stractol WB212: Product name "Stractol WB212", manufactured by Schill + Seilacher GmbH <Anti-aging agent>
-Nocrack 6C: Product name "Nocrack 6C", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.-Nocrack 810NA: Product name "Nocrack 810NA", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
-Vesta PP: Product name "VESTA-PP", manufactured by Inoue Lime Industry Co., Ltd., calcium oxide <vulcanization accelerator>
・ Noxeller MP: Product name “Noxeller MP”, manufactured by Ouchi Shinko Chemical Industry Co., Ltd. ・ Noxeller PX: Product name “Noxeller PX”, manufactured by Ouchi Shinko Chemical Industry Co., Ltd. ・ Noxeller TT-P: Product name "Noxeller TT-P", manufactured by Ouchi Shinko Chemical Industry Co., Ltd., Noxeller D: Product name "Noxeller D", manufactured by Ouchi Shinko Chemical Industry Co., Ltd., Noxeller CZ-G: Product name "Noxeller CZ-G", large Noxeller BZ-P manufactured by Uchishin Kagaku Kogyo Co., Ltd .: Product name "Noxeller BZ-P", Noxeller NS-P manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd .: Product name "Noxeller NS-P", Ouchi Shinko Chemical Industry Co., Ltd. Noxeller DM-P manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. <Carbon Black>
-Seast 116: Product name "Seast 116", manufactured by Tokai Carbon Co., Ltd., arithmetic mean particle size 0.038 μm
-Seast SO: Product name "Seast SO", manufactured by Tokai Carbon Co., Ltd., arithmetic mean particle size 0.043 μm
・ Seest 3: Product name “Seest 3”, manufactured by Tokai Carbon Co., Ltd., arithmetic mean particle size 0.028 μm
<Calcium carbonate>
-Super SSS: Product name "Super SSS", arithmetic mean particle diameter 1.8 μm, manufactured by Maruo Calcium Co., Ltd.-Super S: product name "Super S", arithmetic mean particle diameter 2.7 μm, manufactured by Maruo Calcium Co., Ltd.-NS # 2300: Product name "NS # 2300", arithmetic mean particle diameter 1 μm, Nitto Flour Processing Co., Ltd., heavy coal N-35: Product name "heavy coal N-35", arithmetic mean particle diameter 6.3 μm, Maruo Made by Calcium Co., Ltd.

2.5. Evaluation Results According to Examples 1 to 9 shown in Table 1 above, the molding processability was improved by the method for producing a bonded body according to the present invention, and the obtained bonded body was obtained in terms of molding appearance and bonding strength. It was found to show good properties. On the other hand, when the method not applicable to the present invention, that is, when the cross section of the molded body (I) does not satisfy the predetermined arithmetic mean roughness (Ra) or the Kurtosis of the roughness curve, the obtained bonded body is obtained. It was found to be poor in terms of moldability, molding appearance or joint strength.

The present invention is not limited to the above embodiment, and various modifications are possible. The present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Further, the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

10 ... Fixed type, 12 ... Movable type, 14 ... Nozzle, 20 ... Thermoplastic elastomer, 30 ... Molded body (molded body (I)), 32 ... Molded body (molded body (II)), 34 ... Joint surface, 40 … Joined body, 100… Injection molding mold

Claims (4)

After melting the thermoplastic elastomer in the mold on which the molded body (Ι) is placed, it is injected to integrate the molded body (II) derived from the thermoplastic elastomer and the molded body (Ι). In the manufacturing method of the bonded body
The thermoplastic elastomer contains 130 to 330 ppm of water and
The molded product (I) has a cross section and has a cross section.
The arithmetic mean roughness (Ra) of the cross section is 0.5 to 1.8 μm.
The Kurtosis (Rku) of the roughness curve of the cross section is 7.0 to 16.2 .
A method for producing a bonded body, which comprises joining a cross section of the molded body (I) and the molded body (II). The method for manufacturing a bonded body according to claim 1, wherein the cylinder temperature at the time of injection molding is 200 to 300 ° C. The method for producing a bonded body according to claim 1 or 2, wherein the mold temperature at the time of injection molding is 20 to 100 ° C. The method for producing a bonded body according to any one of claims 1 to 3, wherein the injection rate of the thermoplastic elastomer at the time of injection molding is 10 to 150 cm ³ / sec.

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