WO2020003873A1

WO2020003873A1 - Joint body and production method for joint body

Info

Publication number: WO2020003873A1
Application number: PCT/JP2019/021429
Authority: WO
Inventors: 明寛昆野; 村山　利美; 浩幸佐藤
Original assignee: 株式会社クレハ
Priority date: 2018-06-28
Filing date: 2019-05-29
Publication date: 2020-01-02

Abstract

Provided are: a joint body that has a high peel strength when being bonded to another joint body through a vinylidene fluoride polymer; and a production method for the joint body. This joint body comprises: a molded article that is molded from a vinylidene fluoride polymer containing, as a main component, a vinylidene fluoride-derived constituent unit; and a joining partner body that is joined to the molded article, wherein the molded article and the joining partner body are joined together using a molecular bonding agent, the molecular bonding agent is a compound having -NX¹X² and an alkoxysilyl group or silanol group, where X¹ and X² each independently represent a hydrogen atom or an alkyl group having 1-5 carbon atoms, and the peel strength between the molded article and the joining partner body as measured by a 90° peel test is greater than 0.6 N/mm.

Description

Joint and method of manufacturing joint

The present invention relates to a conjugate and a method for producing the same, and more particularly, to a conjugate joined via a molecular bonding agent and a method for producing the same.

In recent years, especially in the field of automobiles, the use of multi-materials has been promoted in order to reduce the weight of products or to complicate their structures. As a material of a product, a resin-based material such as CFRP is increasingly used in addition to a high-strength steel sheet (high-tensile steel) or a lightweight metal such as Al. However, these cannot be sufficiently joined by conventional welding techniques.

に対し In response, various bonding methods are being studied. For example, Patent Literature 1 discloses a technique in which a ferroelectric material layer made of polyvinylidene fluoride resin and a metal layer are bonded using aminosilane as a primer. Patent Document 2 discloses a technique for bonding polyvinylidene fluoride using an adhesive.

Japanese Patent Laid-open Publication No. 2006-299007 Japanese Patent Laid-Open Publication No. 2012-056975

However, none of the techniques described in Patent Literature 1 and Patent Literature 2 has an insufficient peel strength of about 0.5 N / mm. In addition, when an adhesive is used, there is a problem that the selection of the adhesive is complicated and the thickness of the obtained structure is increased by the thickness of the adhesive layer.

Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide a bonded body having a high peel strength in which another bonded body is bonded to a vinylidene fluoride polymer, and a manufacturing method thereof. To provide.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a very strong bonding can be realized by covalently bonding a molecular bonding agent having an NH ₂ group to a vinylidene fluoride polymer. The invention has been completed.

That is, the present invention includes a molded article molded from a vinylidene fluoride polymer having a structural unit derived from vinylidene fluoride as a main component, and a joined body joined to the molded article, and the molded article The bonding with the object is via a molecular bonding agent. The molecular bonding agent is a compound having —NX ¹ X ² and an alkoxysilyl group or a silanol group, wherein X ¹ and X ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and have a peel strength of greater than 0.6 N / mm between the molded body and the bonded body in a 90 ° peel test. is there.

Further, the present invention includes a molecular bonding agent, one or both of a molded article molded from a vinylidene fluoride polymer having a structural unit derived from vinylidene fluoride as a main component and an object to be joined to the molded article. surface treatment solution surface treated with, and after the surface treatment step includes a contact step of contacting the shaped body and the object to be bonded at 80 ° C. or higher, the molecular bonding agent, -NX ¹ X ² and a compound having an alkoxysilyl group or a silanol group, wherein X ¹ and X ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. .

According to the present invention, it is possible to provide a bonded body having a high peel strength in which another bonded body is bonded to a vinylidene fluoride polymer, and a method for producing the same.

<Joint body>
In the joined body according to the present embodiment, a molded body molded from a vinylidene fluoride polymer and a joined body joined to the molded body are joined via a molecular joining agent.

(Molded body)
The molded article in the present embodiment is molded from a vinylidene fluoride polymer. The vinylidene fluoride polymer in the present embodiment has a structural unit derived from vinylidene fluoride as a main component. Here, “being the main component” means that the content is 50 mol% or more.

The vinylidene fluoride polymer may be a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride with a structural unit derived from a copolymerizable monomer.

Specific examples of monomers copolymerizable with vinylidene fluoride include fluorine-containing monomers, hydrocarbon monomers such as ethylene and propylene, acrylic monomers such as alkyl (meth) acrylate compounds and carboxy group-containing acrylate compounds, and maleic monomers. Examples include acids, unsaturated dibasic acid derivative monomers such as monomethyl maleate and dimethyl maleate, and carboxylic acid anhydride group-containing monomers. Among them, fluorine-containing monomers are preferable from the viewpoint of weather resistance and chemical resistance. The other monomers may be used alone or in combination of two or more.

フッ素 Examples of the fluorinated monomer include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether represented by perfluoromethyl vinyl ether.

モノマー Examples of the unsaturated dibasic acid derivative monomer include maleic acid, citraconic acid, monomethyl maleate, dimethyl maleate and monomethyl citraconic acid.

Examples of the alkyl (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, 2- (hydroxy Methyl) methyl acrylate and 2- (hydroxyethyl) methyl acrylate.

Examples of the carboxy group-containing acrylate compound include (meth) acrylic acid, 2-carboxyethyl acrylate, (meth) acryloyloxypropyl succinic acid, (meth) acryloyloxyethyl succinic acid, 2-hydroxyethyl acrylate and hydroxypropyl acrylate. Is mentioned.

Further, the inherent viscosity of the vinylidene fluoride polymer according to the present embodiment is not particularly limited, but is preferably in a range of 0.5 to 7.0 dL / g, and is preferably 0.7 to 5.0 dL / g. The value is more preferably in the range of g, and even more preferably in the range of 1.0 to 4.0 dL / g. The inherent viscosity of the vinylidene fluoride polymer can be determined as the logarithmic viscosity at 30 ° C. of a solution obtained by dissolving 4 g of the resin in 1 liter of N, N-dimethylformamide.

ビ The vinylidene fluoride polymer according to the present embodiment can be manufactured by, for example, suspension polymerization, emulsion polymerization, or the like.

Further, the molded article molded from the vinylidene fluoride polymer according to the present embodiment may be prepared by injection molding, press molding, calender molding, extrusion molding, or melting in the same manner as in the production of a molded article of ordinary vinylidene fluoride polymer. It can be manufactured by a known method such as spinning. Further, the production method can be selected according to the desired form of the molded body.

形態 The form of the molded body is not particularly limited, and examples thereof include a plate, a rod, a sphere, a hemisphere, a fiber, a powder, a cloth, a net, a film, a sheet, and a laminate. In addition, the surface of the molded body is bonded to the body to be bonded by covalently bonding a molecular bonding agent to the surface. Therefore, from the viewpoint of the airtightness and design of the joined body, it is preferable that the surface is smooth. However, if the surface of the joined body is smooth, the surface may be rough.

(Joint)
The article to be joined in this embodiment is joined to the molded body via a molecular joining agent.

(5) Examples of the member to be joined include metal materials (including alloys), various resins, ceramic materials, and composite materials thereof, and are preferably formed from resin or metal.

Examples of the metal material include various metals and alloys thereof. Specific examples of metals include Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Rh, Ir, and Ni. , Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ge, Sn, Pb, Sb, Bi and Nd.

Examples of the resin include a thermoplastic resin, a thermosetting resin, a fiber reinforced plastic, a photocurable resin, a vulcanized rubber, and an uncrosslinked rubber. Examples thereof include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, or poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride or chlorinated vinyl resin; Acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, or acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, poly Polyester such as butylene terephthalate or polyethylene naphthalate; polyamide such as nylon 6, nylon 66 or nylon 610; polyacetal; polycarbonate; polyphenylene oxide; Polyimide (PPS); Polyetheretherketone (PEEK); Polysulfone; Polyethersulfone; Polyoxypendylene; Polyimide; Polyamideimide; Rubber such as ABS resin or ASA resin blended with polybutadiene rubber and acrylic rubber. And a polymer. Among them, a resin having a C ＝ O bond is preferable, and particularly, polycarbonate, polyethylene terephthalate, and polyimide are preferable.

Examples of the ceramic material include porcelain (such as kaolin, frog-eye clay, pottery stone, feldspar, quartzite, quartz, or alumina), glass, cement, gypsum, and enamel. From the viewpoint of composition, oxides, zirconia, hydroxides, carbides, carbonates, nitrides, halides, phosphates, and the like can be given.

形態 The form of the joined body is not particularly limited, and examples thereof include a plate, a rod, a sphere, a hemisphere, a fiber, a powder, a cloth, a net, a film, a sheet, and a laminate.

The surface of the joined body is preferably a smooth surface, but may be a rough surface if the molded body is a smooth surface.

いずれ All of the above-mentioned joined bodies can be manufactured by a method well known to those skilled in the art.

(Molecular bonding agent)
The molecular bonding agent in the present embodiment is a compound that bonds a molded body molded from a vinylidene fluoride polymer and a body to be bonded. The molecular bonding agent according to the present embodiment has —NX ¹ X ² and an alkoxysilyl group or a silanol group. Here, X ¹ and X ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Note that X ¹ is preferably a hydrogen atom. The number of carbon atoms in the alkoxy moiety of the alkoxysilyl group is not particularly limited, but is preferably 1 to 5 carbon atoms.

Further, the molecular bonding agent in the present embodiment is preferably a compound represented by the following general formula (I).

In formula (I), ^{R 1} represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, represented by C 1-5 aminoalkyl groups or the following general formula carbons (II), ^{R 2} is C 1 - And R ³ to R ⁵ are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and at least one of R ³ to R ⁵ One is a hydroxy group or an alkoxy group having 1 to 5 carbon atoms.

In the formula (II), R ⁶ is an alkylene group having 1 to 10 carbon atoms, R ⁷ is —NH—R ⁸ —NH ₂ or —NR ⁹ R ¹⁰ , and R ⁸ has 1 to ¹⁰ carbon atoms. And R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. The symbol * represents a bonding site to the nitrogen atom to which R ¹ in the formula (I) is bonded.

R ¹ is preferably a hydrogen atom, an aminoalkyl group having 1 to 3 carbon atoms or a group represented by the general formula (II), and is preferably a hydrogen atom or a group represented by the general formula (II). More preferably, it is more preferably a group represented by the general formula (II).

Among them, R ² is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 2 to 5 carbon atoms. .

Among them, R ³ to R ⁵ are preferably a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.

Among them, R ⁶ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms. .

Among them, R ⁷ is preferably —NH—R ⁸ —NH ₂ . R ⁸ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. More preferably, it is particularly preferably an alkylene group having 1 to 2 carbon atoms.

More preferred molecular bonding agents are those wherein R ¹ is represented by the general formula (II), R ² is an alkylene group having 1 to 5 carbon atoms, and R ³ to R ⁵ are an alkoxy group having 1 to 3 carbon atoms; A compound in which R ⁶ is an alkylene group having 1 to 3 carbon atoms, R ⁷ is —NH—R ⁸ —NH ₂ , and R ⁸ is an alkylene group having 1 to 3 carbon atoms. The most preferred molecular conjugating agent is N, N'-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine (hereinafter, referred to as N, N'-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine). A-TES).

In another embodiment, R ¹ may be a hydrogen atom or an aminoalkyl group having 1 to 5 carbon atoms, R ² may be an alkylene group having 1 to 10 carbon atoms, and R ³ to R ⁵ May be an alkoxy group having 1 to 5 carbon atoms.

[Characteristics of the joined body]
In the joined body according to the present embodiment, a molded body and a joined body are joined via a molecular joining agent.

Although the molded body and the object to be bonded are interposed through the molecular bonding agent, the distance between the molded body and the object to be bonded is extremely small and substantially directly in contact with each other. More specifically, the molded body is covalently bonded to the molecular bonding agent, and the body to be bonded is covalently bonded to the molecular bonding agent.

The molded article and the molecular bonding agent are covalently bonded to each other at —NX ¹ X ² of the molecular bonding agent. The covalent bond between the bonded object and the molecular bonding agent is different depending on whether the surface of the bonded object is a metal or ceramic or a resin.

場合 When the surface of the object to be bonded is metal or ceramic, the molecular bonding agent covalently bonds to the metal or ceramic at the alkoxysilyl group or silanol group of the molecular bonding agent. At this time, the bonded object is covalently bonded to a molecular bonding agent that is (or is) covalently bonded to the molded body. As a result, the molded body and the joined body are joined.

In the case where the surface of the joined body is a resin having reactivity with -NX ¹ X ² such as a vinylidene fluoride polymer, the molecular bonding agent and the joined body are different from each other in -NX ¹ X ² of the molecular joining agent. Covalently bond. Then, the molded article and the article to be joined are joined by condensation of alkoxysilyl groups or silanol groups of the molecular joining agent covalently bonded to both. In addition, in each molecular bonding agent, there may be a plurality of alkoxy groups or hydroxy groups in the alkoxysilyl group or silanol group, and it is sufficient that at least one of these groups is condensed. In addition, an example of the molecular bonding agent when one is condensed is shown in the following general formula (III).

In the formula (III), R ¹ to R ⁴ are the same as those described for the general formula (I) shown above.

When the molecular bonding agent has a plurality of —NX ¹ X ² , the object to be bonded may be covalently bonded to the molecular bonding agent that is (or is) bonded to the molded body.

On the other hand, when the surface of the object is a resin that does not have reactivity with —NX ¹ X ² , the molecular bonding is performed by performing a pre-treatment for binding the molecular bonding agent to the object, which will be described later. The bonding agent and the object to be bonded are covalently bonded at the alkoxysilyl group or silanol group of the molecular bonding agent.

The bonded body according to the present embodiment is bonding via a molecular bonding agent, whereby the distance between the molded body and the body to be bonded is within the range of one to several molecular bonding agents. Can be. Therefore, the distance between the molded object and the object to be joined may be 0.1 μm or less, may be 0.05 μm or less, and may be 10 nm or less. As described above, in the joined body according to the present embodiment, the distance between the molded body and the joined body is extremely small, and the joined body is substantially directly in contact with and joined. Therefore, stress, heat, and the like are transmitted without interruption at the joining surface between the molded body and the joined body. Thereby, it is possible to impart new physical properties to the joined body according to the present embodiment. Further, non-covalent bonding occurs between the molded body and the joined body, and the joining between the molded body and the joined body is further strengthened.

As described above, in the joined body according to the present embodiment, the joining between the molded body and the joined body is very strong, and the molded body and the joined body are separated from each other by the 90 ° peel test at room temperature. The strength is greater than 0.6 N / mm. Here, the 90 ° C. peeling test is based on JIS @ K6584-1. The larger the peel strength is, the better. The bonded body according to the present embodiment may be 0.7 N / mm or more, may be 1.0 N / mm or more, and may be 2.0 N / mm or more.

成形 As described above, the molded article and the article to be joined in the present embodiment are bonded by a covalent bond via a molecular joining agent. For this reason, stronger bonding is enabled as compared with bonding using a conventional adhesive utilizing non-bonding force such as hydrogen bonding. Therefore, even if the contact area is small, for example, the contact surface is smooth, a strong connection is possible. Further, unlike the adhesive, the bonded portion does not deteriorate even under severe environments such as high temperature and high pressure. Therefore, high joining reliability can be obtained.

When joining materials whose contact surfaces are rough surfaces, a material having a smooth surface and a thickness sufficient to absorb the surface roughness is sandwiched between the materials, and the materials are brought into contact by pressing or melting. In addition, materials having rough surfaces can be joined. The material whose surface is smooth and has a thickness capable of absorbing the surface roughness may be any of resin, metal, and ceramic, but is preferably resin from the viewpoint of contacting the rough surface.

The object to be joined in the present embodiment can be made of various materials as listed above, but the object to be joined can be any material by covalently bonding the molecular joining agent as described above. Can be bonded to the molded body in the same manner. Also, the bonding is strong.

Furthermore, there is no need to select an adhesive according to the material of the object to be joined as in the conventional case. In addition, since the molecular bonding agent has almost no thickness, it is possible to prevent the thickness of the obtained structure from being increased by the amount of the adhesive layer as compared with the case where an adhesive is used.

<Method of manufacturing bonded body>
Hereinafter, a method for manufacturing the joined body according to the present embodiment will be described.

The method for manufacturing a joined body according to this embodiment includes a surface treatment in which one or both of the above-described molded body and the joined body are subjected to a surface treatment using a solution containing a molecular joining agent (hereinafter, also referred to as a molecular joining agent solution). And a contact step of contacting the molded body and the object to be joined at 80 ° C. or higher after the surface treatment step.

(Surface treatment step)
The surface treatment step in the method for manufacturing a joined body according to the present embodiment is a step of subjecting one or both of the molded body and the joined body to a surface treatment using a molecular bonding agent solution. Hereinafter, the molded body and the joined body are collectively referred to as “joining material”.

表面 The surface treatment step according to the present embodiment includes an immersion treatment of immersing the bonding material in a molecular bonding agent solution. The content of the molecular bonding agent in the solution is preferably at most 1 wt%, more preferably at most 0.5 wt%, even more preferably at most 0.1 wt%. The solvent of the molecular bonding agent solution is preferably water, but may be, for example, an alcohol solvent such as ethanol, an ether solvent, a ketone solvent or a mixed solvent thereof.

１０ 10 seconds is sufficient for the immersion time, but it is preferably 30 seconds or more, and more preferably 60 seconds or more.

The joining material is not limited to the immersion treatment, and the solution to be joined may be directly applied to only the portion to be joined, or a sprayer or the like, since the portion to be joined only needs to be treated with the solution of the molecular bonding agent. May be used to spray the solution.

When the surface of the object to be joined is metal or ceramic, any one of the molded body and the object to be joined may be subjected to surface treatment, but from the viewpoint of covalently bonding more joining agent to the surface of the joining material, It is preferable to subject the object to be surface-treated.

When the article to be joined is a resin having reactivity with —NX ¹ X ² such as a vinylidene fluoride polymer, it is preferable to subject both the molded article and the article to surface treatment. As described above, a resin having reactivity with -NX ¹ X ² such as a vinylidene fluoride polymer is covalently bonded to -NX ¹ X ² of the molecular bonding agent. The molded article and the article to be joined are joined by condensing the alkoxysilyl groups or silanol groups of the molecular joining agent covalently bonded to both.

The surface treatment step may include other treatments in addition to the immersion treatment described above. For example, when the article does not contain a C ＝ O bond but contains a CH bond, it is preferable to perform a pretreatment for binding the molecular joining agent to the article before the immersion treatment.

As the pretreatment, for example, a method of bonding a compound having both a functional group that binds to the bond and a functional group that binds to the molecular bonding agent to the surface of the bond is used. More specifically, it is preferable to bond a compound having an azide group and an alkoxysilyl group or a silanol group. Examples of such a compound include those represented by the following general formula (IV).

In the formula (IV), R ¹¹ is an alkylene group having 1 to 10 carbon atoms, and R ¹² to R ¹⁴ are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. An alkyl group, at least one of R ¹² to R ¹⁴ is a hydroxy group or an alkoxy group having 1 to 5 carbon atoms, and R ¹⁵ is an azide group or an alkyl group having 1 to 10 carbon atoms.

Among them, R ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

R ¹² to R ¹⁴ are preferably a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.

More preferably an azide group as R ^15.

The most preferred compound is 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol (hereinafter, P-TES).

The method for bonding such a compound to the surface of the object is not particularly limited. For example, a method in which the object is immersed in a solution containing the compound and a radical generation reaction is performed by irradiation with ultraviolet light is exemplified.

At this time, it is preferable to perform a corona treatment or the like on the article to be joined in advance to increase the wettability of the article. Before and after the reaction, it is preferable to perform ultrasonic cleaning using acetone or ethanol or the like in order to remove stains on the object to be bonded or unreacted substances and by-products. The order of these processes can be determined as appropriate.

In the case of performing the pretreatment using the compound of the formula (IV), the solution containing the compound of the formula (IV) may contain a molecular bonding agent in advance. By treating with a solution containing both the compound of the formula (IV) and the molecular bonding agent, a step of immersing the compound of the formula (IV) in a molecular bonding agent solution after the treatment with the compound and the ultraviolet irradiation, or a molecular bonding The step of applying the agent solution can be omitted.

(Contact process)
The contacting step in the method for manufacturing a joined body according to the present embodiment is a step of bringing the joining materials into contact at 80 ° C. or higher after the surface treatment step.

(4) Examples of the contacting method include, but are not limited to, a pressing method, and a method of performing injection molding after inserting a processing substrate.

The temperature at which the contact is performed is 80 ° C. or higher, and a more preferable temperature is mp−50 ° C. or higher and mp + 50 ° C. or lower, where mp is the higher of the melting points of the bonding materials. It is -30 ° C or more and mp + 30 ° C or less. Thereby, it is possible to join the joining materials close to a distance at which they can react with each other.

Alternatively, assuming that the higher of the softening points of the joining materials is sp, the more preferable contact temperature is sp-50 ° C or more and sp + 50 ° C or less, and further preferably sp-30 ° C or more and sp + 30 ° C or less. Here, the “softening point” in the present specification refers to a workable temperature at which the amorphous resin can flow and deform.

させる By bringing the joining materials into contact with each other near the melting point or the softening point, the joining materials can be joined at a shorter distance.

It is known that a vinylidene fluoride polymer can be partially substituted with an amino group by reacting with an amine. Therefore, some molecular bonding agents may bond to the molded body without going through the contacting step. However, in the present embodiment, by applying heat of 80 ° C. or more, a covalent bond with a molded body is formed in many molecular bonding agents. As a result, it is possible to obtain a bonded body that is very strongly bonded.

<Summary>
As apparent from the above, the present invention includes the following.

A molded article molded from a vinylidene fluoride polymer having a constitutional unit derived from vinylidene fluoride as a main component, and a joined body joined to the molded article, including the molded article and the joined article. The bonding is through a molecular bonding agent, and the molecular bonding agent is a compound having —NX ¹ X ² and an alkoxysilyl group or a silanol group, wherein X ¹ and X ² are each independently A joined body, which is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and has a peel strength of greater than 0.6 N / mm between the molded body and the joined body in a 90 ° peel test.

In addition, it is preferable that the object to be joined is formed of resin or metal.

Further, X ¹ is preferably a hydrogen atom.

Further, the molecular bonding agent is preferably a compound represented by the following general formula (I).

In the formula, R ¹ is represented by a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aminoalkyl group having 1 to 5 carbon atoms or the following general formula (II), and R ² is an alkylene having 1 to 10 carbon atoms. R ³ to R ⁵ are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and at least one of R ³ to R ⁵ is a hydroxy group Or an alkoxy group having 1 to 5 carbon atoms, R ⁶ is an alkylene group having 1 to 5 carbon atoms, R ⁷ is —NH—R ⁸ —NH ₂ or —NR ⁹ R ¹⁰ , and R ⁸ Is an alkylene group having 1 to 5 carbon atoms, and R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. In the formula (II), an asterisk (*) indicates a bonding site to the nitrogen atom to which R ^{1 in} the formula (I) is bonded.

Further, R ¹ is preferably represented by the general formula (II).

Further, the molecular bonding agent is —NN′-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine. Is preferred.

Alternatively, it is preferable that the R ¹ is a hydrogen atom.

距離 Further, it is preferable that the distance between the molded body and the object to be joined is 0.1 μm or less.

A surface on which one or both of a molded article molded from a vinylidene fluoride polymer having a structural unit derived from vinylidene fluoride as a main component and an object to be joined to the molded article are subjected to surface treatment using a molecular bonding agent solution After the treatment step and the surface treatment step, the method includes a contact step of contacting the molded body and the article to be joined at 80 ° C. or higher, wherein the molecular joining agent comprises —NX ¹ X ² , and an alkoxysilyl group or A method for producing a conjugate, which is a compound having a silanol group, wherein X ¹ and X ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the surface treatment step, it is preferable to perform a surface treatment on both the molded body and the joined body.

Preferably, the method further includes, before the surface treatment step, a treatment for binding the molecular bonding agent to the object.

In addition, the contacting step is preferably a pressing step.

Alternatively, it is preferable that the contacting step is a step of injection molding.

The content of the molecular bonding agent in the solution is preferably 1 wt% or less.

Examples are shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Furthermore, the present invention is not limited to the above-described embodiment, and various changes can be made within the scope shown in the claims. It is included in the technical scope of the invention. In addition, all of the documents described in this specification are incorporated by reference.

[Production of PVDF bonded body]
(Example 1)
A polyvinylidene fluoride (PVDF) film (# 1000, manufactured by Kureha Corporation) having a width of 25 mm, a length of 60 mm and a thickness of 79 μm was ultrasonically washed with ethanol for 10 minutes. After drying, a corona treatment was performed using a table type surface treatment device (manufactured by Kasuga Electric Co., Ltd.) under the conditions of an output power of 150 W, a gap length of 2 mm, a moving speed of 4 m / min, and a moving frequency of 4 times. Thereafter, the sample was immersed in a 0.1 wt% A-TES aqueous solution (manufactured by Io Chemical Laboratory Co., Ltd.) to obtain a sample A-1.

ＰＶ A 25 mm wide, 60 mm long, 1 mm thick PVDF sheet (# 2300, manufactured by Kureha Corporation) was ultrasonically washed with ethanol for 10 minutes to obtain a sample B-1.

In order to obtain a handle portion at the time of the peeling test, a polyimide tape was attached to the upper end of the treated surface of sample B-1, and sample A-1 was placed thereon with the A-TES treated surface inside, and placed at 135 ° C., 2 MPa By performing hot press molding for 5 minutes, a joined body of the PVDF film and the PVDF sheet was obtained. AYSR-5 (manufactured by Shindo Metal Industry Co., Ltd.) was used for press molding.

(Example 2)
A PPS plate (1130TX1, manufactured by Polyplastics) having a width of 30 mm, a length of 50 mm, and a thickness of 3 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, the resultant was dipped in a 0.1 wt% P-TES ethanol solution (manufactured by Io Chemical Laboratory Co., Ltd.) and dried. After drying, UV irradiation was performed under the condition that the integrated light amount was 200 mJ / cm ² . After UV irradiation, the sample was ultrasonically washed with ethanol, dipped again in a P-TES ethanol solution, irradiated with UV, ethanol ultrasonically washed, and the sample was dried. Thereafter, the sample was immersed in a 0.1 wt% A-TES aqueous solution to obtain a sample A-2.

ＰＶ A 30 mm wide, 50 mm long, 79 μm thick PVDF film (# 1000, manufactured by Kureha Corporation) was ultrasonically washed with ethanol for 10 minutes to obtain a sample B-2.

Same as Example 1 except that a polyimide tape was stuck on the upper end of the treated surface of sample A-2, and sample B-2 was placed thereon, and the temperature was set to 180 ° C. in order to obtain a handle portion during the peeling test. To obtain a bonded body of a PVDF film and a PPS plate.

(Example 3)
The same processing as in Example 2 was performed except that the PPS plate was changed to a PEEK plate (450 G, manufactured by Victrex), and a sample A-3 was obtained instead of the sample A-2. Next, the same process as in Example 2 was performed except that Sample A-2 was changed to Sample A-3, to obtain a joined body of the PVDF film and the PEEK plate.

(Example 4)
A sample A-4 was obtained in place of the sample A-2, except that the PPS plate was changed to a 9T polyamide plate (Kuraray Co., Genestar TA-112). Next, the same process as in Example 2 was performed except that Sample A-2 was changed to Sample A-4, to obtain a joined body of a PVDF film and a 9T polyamide plate.

(Example 5)
A steel plate (SPCC, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, it was immersed in a 0.1 wt% A-TES aqueous solution to obtain a sample A-5.

ＰＶ A 25 mm wide, 100 mm long and 79 μm thick PVDF film (# 1000, manufactured by Kureha Corporation) was ultrasonically washed with ethanol for 10 minutes to obtain a sample B-3.

Same as Example 1 except that a polyimide tape was attached to the upper end of the treated surface of sample A-5, and sample B-3 was placed thereon, and the temperature was set to 180 ° C. in order to obtain a handle portion during the peeling test. To obtain a bonded body of a PVDF film and a steel sheet.

(Example 6)
A sample A-6 was obtained in place of the sample A-5, except that the steel plate was a ceramic plate having a thickness of 1.0 mm (alumina ceramics manufactured by Testpiece Co., Ltd.). . Next, the same process as in Example 5 was performed except that Sample A-5 was changed to Sample A-6, to obtain a joined body of the PVDF film and the ceramics plate.

(Example 7)
An aluminum plate (A5052P, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, it was immersed in a 5 wt% aqueous solution of SK-144 (manufactured by JCU Corporation) at 70 ° C. for 1 minute, and then ultrasonically washed with ion-exchanged water for 3 minutes. After drying, the sample was immersed in a 0.1 wt% A-TES aqueous solution to obtain a sample A-7.

(4) The same processing as in Example 5 was performed to obtain a sample B-3.

Same as Example 1 except that a polyimide tape was attached to the upper end of the treated surface of sample A-7, and sample B-3 was placed thereon, and the temperature was set to 180 ° C. in order to obtain a handle portion during the peeling test. To obtain a bonded body of a PVDF film and an Al plate.

(Example 8)
The same treatment as in Example 7 was performed, except that the A-TES aqueous solution was changed to an aqueous solution of 3-aminoprolyltriethoxysilane (hereinafter, APS, manufactured by Tokyo Chemical Industry Co., Ltd.). 8 was obtained. Next, the same process as in Example 7 was performed except that Sample A-7 was changed to Sample A-8, to obtain a joined body of the PVDF film and the Al plate.

(Example 9)
In this example, unlike Example 8, a treatment using a molecular bonding agent was performed on a PVDF film instead of an Al plate.

(5) An Al plate (A5052P, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. After drying, the sample was immersed in a 5 wt% aqueous solution of SK-144 (manufactured by JCU Corporation) at 70 ° C. for 1 minute, and then ultrasonically washed with ion-exchanged water for 3 minutes to obtain a sample A-9.

２５ A 25 mm wide, 100 mm long, 79 μm thick PVDF film (# 1000, manufactured by Kureha Corporation) was ultrasonically cleaned with ethanol for 10 minutes. After drying, a corona treatment was performed under the same conditions as in Example 1. Thereafter, a 1.0 wt% APS aqueous solution was applied to obtain a sample B-4.

In order to obtain a handle portion during the peeling test, a polyimide tape was attached to the upper end of the treated surface of sample A-9, sample B-4 was placed thereon, and hot press molding was performed as in Example 7, and a PVDF film was formed. And an Al plate were obtained.

(Comparative Example 1)
An aluminum plate (A5052P, manufactured by Testpiece Co., Ltd.) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was ultrasonically cleaned with acetone for 10 minutes. Thereafter, drying was performed to obtain a sample A-10.

(4) The same processing as in Example 5 was performed to obtain a sample B-3.

In order to obtain the handle portion during the peeling test, a polyimide tape was attached to the upper end of sample A-10, and sample B-3 was placed thereon, and hot pressed at 180 ° C., 2 MPa, and 5 minutes. Was peeled off, and a joined body of the PVDF film and the Al plate could not be obtained.

(Peeling strength evaluation)
Each of the joined bodies obtained in Examples 1 to 7 was evaluated by performing a 90 ° peel strength test. The 90 ° peel strength was measured at room temperature using AUTOGRAPH AGS-1kNJ (manufactured by Shimadzu Corporation). Table 1 shows the results.

As shown in Table 1, in each of the obtained joined bodies, high peel strength was confirmed.

Claims

A molded article molded from a vinylidene fluoride polymer having a structural unit derived from vinylidene fluoride as a main component,
A joined body joined to the molded body,
Bonding of the molded body and the body to be bonded is through a molecular bonding agent,
The molecular bonding agent is a compound having —NX 1 X 2 and an alkoxysilyl group or a silanol group, wherein X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Yes,
A joined body having a peel strength of greater than 0.6 N / mm between the molded body and the joined body in a 90 ° peel test.
接合 The joined body according to claim 1, wherein the joined body is formed of resin or metal.
The conjugate according to claim 1, wherein X 1 is a hydrogen atom.
The conjugate according to any one of claims 1 to 3, wherein the molecular bonding agent is a compound represented by the following general formula (I).

(Wherein, R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aminoalkyl group having 1 to 5 carbon atoms, or the following general formula (II), and R 2 is a group having 1 to 10 carbon atoms. R 3 to R 5 are each independently a hydroxy group, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and at least one of R 3 to R 5 is a hydroxy group; A group or an alkoxy group having 1 to 5 carbon atoms, R 6 is an alkylene group having 1 to 10 carbon atoms, R 7 is —NH—R 8 —NH 2 or —NR 9 R 10 ; 8 is an alkylene group having 1 to 10 carbon atoms, and R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms. Is the bonding site with the nitrogen atom to which R 1 is bonded.)
The conjugate according to claim 4, wherein the R 1 is represented by the general formula (II).
The method according to claim 1, wherein the molecular bonding agent is NN'-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine. 6. The conjugate according to any one of items 5 to 5.
The conjugate according to claim 4, wherein said R 1 is a hydrogen atom.
(8) The joined body according to any one of (1) to (7), wherein a distance between the molded body and the joined body is 0.1 μm or less.
Surface treatment of one or both of a molded article molded from a vinylidene fluoride polymer having a structural unit derived from vinylidene fluoride as a main component and an object to be joined to the molded article using a solution containing a molecular bonding agent Surface treatment step, and after the surface treatment step, including a contact step of contacting the molded body and the object to be bonded at 80 ° C. or more,
The molecular bonding agent is a compound having —NX 1 X 2 and an alkoxysilyl group or a silanol group, wherein X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A method for manufacturing a joined body.
The method for manufacturing a joined body according to claim 9, wherein in the surface treatment step, both the molded body and the joined body are subjected to surface treatment.
The method for producing a joined body according to claim 9, further comprising a treatment for binding the molecular joining agent to the joined body before the surface treatment step.
The method for producing a joined body according to any one of claims 9 to 11, wherein the contacting step is a pressing step.
The method for producing a joined body according to any one of claims 9 to 11, wherein the contacting step is an injection molding step.
The method for producing a joined body according to any one of claims 9 to 13, wherein the content of the molecular joining agent in the solution is 1 wt% or less.