WO2020183583A1

WO2020183583A1 - Composition for forming barrier material, barrier material and method for producing same, and product and method for producing same

Info

Publication number: WO2020183583A1
Application number: PCT/JP2019/009785
Authority: WO
Inventors: 龍一郎福田; 崇之鈴木; 智彦小竹
Original assignee: 日立化成株式会社
Priority date: 2019-03-11
Filing date: 2019-03-11
Publication date: 2020-09-17
Also published as: JPWO2020183583A1; JP7447893B2

Abstract

The present invention provides a composition for forming a barrier material containing a silane oligomer and a silane monomer having a reactive functional group. At least part of the silane oligomer is modified by a metal alkoxide.

Description

Barrier material forming composition, barrier material and its manufacturing method, and product and its manufacturing method

The present invention relates to a composition for forming a barrier material, a barrier material and a method for producing the same, and a product and a method for producing the same.

Conventionally, it has been studied to seal an electronic component with a barrier film or the like in order to prevent moisture from entering the voids formed in the electronic component. For example, Patent Document 1 describes a barrier film laminate in which a barrier film having an inorganic oxide layer is laminated.

Japanese Unexamined Patent Publication No. 2011-093195

However, since the barrier film laminate described in Patent Document 1 is in the form of a film, the applicable objects are limited.

Therefore, an object of the present invention is to provide a barrier material having excellent moisture resistance, which can be applied to objects having various shapes. Another object of the present invention is to provide a composition for forming a barrier material for forming the barrier material. An object of the present invention is further to provide a method for producing the barrier material, a product provided with the barrier material, and a method for producing the product.

The present invention provides a composition for forming a barrier material, which comprises a silane oligomer and a silane monomer having a reactive functional group, and at least a part of the silane oligomer is modified with a metal alkoxide.

Such a composition can easily form a barrier material having excellent moisture resistance on the object by applying it to the object and heating it. Further, in the above composition, by containing a silane monomer having a reactive functional group, a barrier material having excellent followability and adhesion to an object is formed.

In one embodiment, the reactive functional group may be selected from the group consisting of a vinyl group, an epoxy group, a glycidyl group, a (meth) acryloyl group, an amino group, an isocyanate group, an isocyanurate group and a mercapto group.

In one embodiment, the reactive functional group may be an amino group.

In one embodiment, the silane oligomer may contain a silicon atom bonded to three oxygen atoms.

In one embodiment, the ratio of the total number of silicon atoms bonded to 3 oxygen atoms and the number of silicon atoms bonded to 4 oxygen atoms to the total number of silicon atoms in the silane oligomer may be 50% or more. ..

In one embodiment, the content of the silane monomer may be 0.01 to 5 parts by mass with respect to 100 parts by mass of the silane oligomer.

The composition according to one embodiment may further contain a second silane monomer selected from the group consisting of alkyltrialkoxysilanes, aryltrialkoxysilanes and tetraalkoxysilanes.

In one embodiment, the content of the second silane monomer may be 5 to 40 parts by mass with respect to 100 parts by mass of the silane oligomer.

In one embodiment, the metal alkoxide may be an aluminum alkoxide.

The present invention also comprises a first step of preparing a silane oligomer that is at least partially modified with a metal alkoxide, and a composition for forming a barrier material by mixing the silane oligomer with a silane monomer having a reactive functional group. Provided is a method for producing a composition for forming a barrier material, comprising a second step of obtaining the above.

In one aspect, the first step may include a step of reacting a silane oligomer with a metal alkoxide and modifying at least a part of the silane oligomer with a metal alkoxide.

In one aspect, the first step may include a step of reacting a silane monomer with a metal alkoxide to form a silane oligomer at least partially modified with a metal alkoxide.

The present invention also provides a method for producing a barrier material, which comprises a step of heating the composition for forming a barrier material to form the barrier material.

The present invention also provides a method for manufacturing a product having a moisture-proof treated member. In this production method, the first step of applying the barrier material forming composition on the member and the second step of heating the applied barrier material forming composition to form the barrier material on the member. The process may be provided.

The present invention also comprises a first member and a second member joined to the first member, and the joint portion between the first member and the second member is moisture-proofed. Provide a manufacturing method. In this manufacturing method, the barrier material is formed by heating the first step of arranging the barrier material forming composition between the first member and the second member and the barrier material forming composition. , The second step of joining the first member and the second member via the barrier material may be provided.

The present invention also provides a method for manufacturing a product including a moisture-proof member. This manufacturing method includes a first step of heating the composition for forming a barrier material to produce a moisture-proof member having the barrier material, and a second step of assembling a plurality of members including the moisture-proof member. You can.

The present invention also provides a barrier material which is a cured product of the above-mentioned composition for forming a barrier material.

Barrier material according to one embodiment, the water vapor transmission rate per 25μm thick (40 ℃, 95% RH) may be less 4000g ^/ m 2 · day.

The barrier material according to one embodiment may have a transmittance of 90% or more with respect to light at 550 nm per 1 mm in thickness.

The present invention also provides a product comprising the member and the barrier material formed on the member.

The present invention also includes the first member, the second member, and the barrier material provided between the first member and the second member, and the first member and the first member. Provided is a product in which the second member is joined via the barrier material.

The present invention further provides a product which is an assembly of a plurality of members including the moisture-proof member having the barrier material.

According to the present invention, a barrier material having excellent moisture resistance that can be applied to objects having various shapes is provided. The present invention can also provide a composition for forming a barrier material for forming the barrier material. The present invention can further provide a method for producing the barrier material, a product provided with the barrier material, and a method for producing the product.

Hereinafter, preferred embodiments of the present invention will be described. In the present specification, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. The term "A or B" may include either A or B, and may include both. Unless otherwise specified, the materials exemplified in this embodiment may be used alone or in combination of two or more.

<Composition for forming barrier material>
The composition for forming a barrier material according to the present embodiment contains a silane oligomer and a silane monomer having a reactive functional group (hereinafter, also referred to as a first silane monomer), and at least a part of the silane oligomer is contained. It is modified with a metal alkoxide.

The composition for forming the barrier material may be in the form of a liquid or a paste, and is preferably in the form of a liquid from the viewpoint of facilitating application to the object.

A silane oligomer is a polymer of a silane monomer and has a structure in which a plurality of silicon atoms are linked via oxygen atoms. In the present specification, the silane oligomer represents a polymer having a molecular weight of 100,000 or less.

In the present specification, the silane oligomer modified with a metal alkoxide is a compound formed by the reaction of the silane oligomer and the metal alkoxide, and a silicon atom derived from the silane oligomer and a metal atom derived from the metal alkoxide are interposed via an oxygen atom. It can also be said that the compound has a bonded structure.

The silane oligomer modified with the metal alkoxide (hereinafter, sometimes referred to as “modified silane oligomer”) may be a reaction product of the silane oligomer and the metal alkoxide, or may be a reaction product of the silane monomer and the metal alkoxide. Good. In the latter case, the silane monomer that has reacted with the metal alkoxide may further react with another silane monomer to form a silane oligomer structure, and the silane oligomer formed by the reaction between the silane monomers reacted with the metal alkoxide. It may be a thing.

In the composition according to the present embodiment, it is not necessary that all the silane oligomers contained in the composition are modified with a metal alkoxide, and at least a part of the silane oligomers may be modified with a metal alkoxide.

The silicon atom contained in the silane oligomer is a silicon atom bonded to one oxygen atom (M unit), a silicon atom bonded to two oxygen atoms (D unit), and a silicon atom bonded to three oxygen atoms (M unit). It can be distinguished into a silicon atom (Q unit) bonded to four oxygen atoms (T unit). Examples of the M unit, the D unit, the T unit, and the Q unit include the following equations (M), (D), (T), and (Q), respectively.

In the above formula, R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) other than the oxygen atom bonded to silicon. Information on the content of these units can be obtained by Si-NMR.

In the silane oligomer, the ratio of the total number of T units and Q units to the total number of silicon atoms is preferably 50% or more, more preferably 70% or more, further preferably 90% or more. It may be 100%. According to such a silane oligomer, a barrier material having more excellent moisture resistance can be obtained.

In a preferred embodiment, the silane oligomer preferably contains T units. The content of T units in the silane oligomer is, for example, 10% or more, preferably 20% or more, 30% or more, 40% or more, 50% or more, 70% or more, 80% or more with respect to the total number of silicon atoms. Alternatively, it is 90% or more, and may be 100%. Such silane oligomers tend to be more flexible.

In another preferred embodiment, the content of Q units in the silane oligomer is, for example, 50% or more, preferably 70% or more, and more preferably 80% or more, based on the total number of silicon atoms. It is preferably 90% or more, and may be 100%. Such silane oligomers tend to have better moisture resistance and transparency.

The silane oligomer preferably has an alkyl group or an aryl group as R in the above formulas (M), (D), (T) and (Q).

As the alkyl group, an alkyl group having 6 or less carbon atoms is preferable, and an alkyl group having 4 or less carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, of which a methyl group, an ethoxy group and a propyl group are preferable, and a methyl group is more preferable.

Examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group and a cyano group. As the aryl group, a phenyl group is preferable.

The weight average molecular weight of the silane oligomer may be, for example, 400 or more, preferably 600 or more, and more preferably 1000 or more. The weight average molecular weight of the silane oligomer may be, for example, 30,000 or less, preferably 10,000 or less, and more preferably 6000 or less. A large weight average molecular weight of the silane oligomer tends to improve flexibility, and a small weight average molecular weight tends to improve moisture resistance and transparency. In the present specification, the weight average molecular weight of the silane oligomer indicates the value of the weight average molecular weight expressed in polystyrene conversion measured by gel permeation chromatography (GPC).

The metal alkoxide can be represented by, for example, M (OR ¹ ) _n . M represents an n-valent metal atom and R ¹ represents an alkyl group. n represents a positive number of 1 or more.

N is preferably 2 to 5, and more preferably 3 to 4.

Examples of M include aluminum, titanium, zirconium, niobium and the like, of which aluminum, titanium and zirconium are preferable, and aluminum is more preferable. That is, examples of the metal alkoxide include aluminum alkoxide, titanium alkoxide, zirconium alkoxide, niobium alkoxide and the like, of which aluminum alkoxide, titanium alkoxide and zirconium alkoxide are preferable, and aluminum alkoxide is more preferable.

As R ¹ , an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 2 to 4 carbon atoms is more preferable. Specific examples of the alkyl group of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group and the like, of which an ethyl group, a propyl group and a butyl group are preferable, and a propyl group and a butyl group are more preferable.

The composition according to the present embodiment may contain a modified silane oligomer in which a silane oligomer is modified with 0.001 to 30 parts by mass of a metal alkoxide with respect to 100 parts by mass of the silane oligomer. The amount of the metal alkoxide is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the silane oligomer. Is. Higher amounts of metal alkoxides tend to result in better curability, and lower amounts of metal alkoxides tend to improve transparency.

Examples of the reactive functional group contained in the first silane monomer include a vinyl group, an epoxy group, a glycidyl group, a (meth) acryloyl group, an amino group, an isocyanate group, an isocyanurate group, a mercapto group and the like. From the viewpoint of further improving the flexibility of the barrier material and the adhesion to the member, the reactive functional group includes a vinyl group, an epoxy group (more preferably a glycidyl group), a (meth) acryloyl group, an amino group, and an isocyanate group. It is preferably selected from the group consisting of an isocyanurate group and a mercapto group, and an amino group is more preferable.

The first silane monomer preferably has a silicon atom bonded to three oxygen atoms.

As the first silane monomer, for example, a silane monomer represented by the following formula (A-1) can be preferably used.

^{Wherein, R A1} represents a reactive functional group, ^{L 1} is alkanediyl group or an oxy alkanediyl group - indicates (-OL ^2. Group, ^{L 2} represented by the showing the alkanediyl group), p is It represents an integer greater than or equal to 0 (preferably an integer of 0 to 3), where ^RA2 represents an alkyl or aryl group.

When ^RA1 is a vinyl group, p is preferably 0 to 3, and more preferably 0.

When ^RA1 is an epoxy group, a glycidyl group, a (meth) acryloyl group, an amino group, an isocyanate group, an isocyanurate group or a mercapto group, p is preferably an integer of 1 or more, and preferably 1 to 3. More preferably, it is further preferably 1.

When R ^A1 is a vinyl group, a glycidyl group, or (meth) acryloyl group, it is preferred that L ¹ is oxy alkanediyl group.

When R ^A1 is an amino group, isocyanate group, isocyanurate group or a mercapto group, it is preferred that L ¹ is alkanediyl group.

As the alkanediyl group in L ¹ and L ^{2, an} alkane diyl group having 2 to 10 carbon atoms is preferable, and an alkane diyl group having 2 to 8 carbon atoms is more preferable.

As the alkyl group in ^RA2, an alkyl group having 6 or less carbon atoms is preferable, and an alkyl group having 4 or less carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, sec-butyl group, isobutyl group, tert-butyl group) and the like. Be done.

The aryl group in R ^A2, a phenyl group is preferable.

^RA2 is preferably an alkyl group.

The content of the first silane monomer may be, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the silane oligomer. is there. As a result, the followability and the adhesion tend to be further improved. The content of the first silane monomer may be, for example, 5 parts by mass or less, preferably 4 parts by mass or less, and more preferably 2 parts by mass or less. This tends to further improve the thermal stability of the cured product.

In the present specification, "100 parts by mass of silane oligomer" does not include the mass of the metal alkoxide that modifies the silane oligomer, and the total amount of the silane oligomer portion of the modified silane oligomer and the unmodified silane oligomer is 100 parts by mass. Means that.

The composition according to the present embodiment may further contain a silane monomer other than the first silane monomer. For example, the composition according to this embodiment may further contain a second silane monomer selected from the group consisting of alkyltrialkoxysilanes, aryltrialkoxysilanes and tetraalkoxysilanes.

By blending the second silane monomer, for example, the contents of T unit and Q unit in the barrier material can be adjusted, and the barrier material can be imparted with effects such as transparency and flexibility depending on the application. Can be done. Further, by blending the second silane monomer, a barrier material having more excellent moisture resistance tends to be obtained.

The content of the second silane monomer is not particularly limited, but may be, for example, 5 parts by mass or more, preferably 8 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the silane oligomer. This tends to further improve the flexibility of the cured product. The content of the first silane monomer may be, for example, 40 parts by mass or less, preferably 35 parts by mass or less, and more preferably 30 parts by mass or less. As a result, the volatility of the coating liquid is reduced, and the workability tends to be further improved.

Alkoxytrialkoxysilane is a silane compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom.

As the alkyl group of the alkyltrialkoxysilane, an alkyl group having 6 or less carbon atoms is preferable, and an alkyl group having 4 or less carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, of which a methyl group, an ethyl group and a propyl group are preferable, and a methyl group is more preferable. Further, as the alkoxy group of the alkyltrialkoxysilane, an alkoxy group having 6 or less carbon atoms is preferable, and an alkoxy group having 4 or less carbon atoms is more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Of these, a methoxy group, an ethoxy group and a propoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

Aryltrialkoxysilane is a silane compound in which one aryl group and three alkoxy groups are bonded to a silicon atom.

Examples of the aryl group of the aryltrialkoxysilane include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group and a cyano group. The aryl group is preferably a phenyl group. Further, as the alkoxy group of the aryltrialkoxysilane, an alkoxy group having 6 or less carbon atoms is preferable, and an alkoxy group having 4 or less carbon atoms is more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Of these, a methoxy group, an ethoxy group and a propoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

Tetraalkoxysilane is a silane compound in which four alkoxy groups are bonded to a silicon atom.

As the alkoxy group of tetraalkoxysilane, an alkoxy group having 6 or less carbon atoms is preferable, and an alkoxy group having 4 or less carbon atoms is more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Of these, a methoxy group, an ethoxy group and a propoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

Specific examples of the second silane monomer include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetra. Examples thereof include propoxysilane and tetrabutoxysilane.

The composition according to this embodiment may further contain a liquid medium. Examples of the liquid medium include water and an organic solvent.

Examples of the organic solvent include alcohols, ethers, ketones, esters, hydrocarbons and the like. In addition to these, acetonitrile, acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can also be used.

In a preferred embodiment, the composition may contain water and alcohols as a liquid medium. By using such a liquid medium, it becomes easy to obtain a barrier material having excellent transparency.

As the alcohols, those that can be vaporized by heating at the time of forming the barrier material are preferable. As the alcohols, for example, alcohols having 6 or less carbon atoms are preferable, and alcohols having 1 to 4 carbon atoms are more preferable.

As the alcohols, for example, alcohols corresponding to the alkoxy group of the metal alkoxide may be used. That is, for example, when the metal alkoxide has a tert-butoxy group, tert-butyl alcohol may be used as the alcohol. This tends to further improve transparency.

The content of the liquid medium is not particularly limited, and may be, for example, a content having a viscosity suitable for coating the composition. The viscosity of the composition is not particularly limited, and may be appropriately adjusted according to the thickness of the barrier material to be produced, the coating method, the shape of the object, and the like.

The viscosity of the composition at 25 ° C. may be, for example, 1 to 6000 mPa · s, preferably 5 to 3000 mPa · s. According to such a composition, it becomes easier to apply the composition to the object and to form a barrier material on the object.

In the composition according to the present embodiment, the molar ratio of the metal atom M derived from the metal alkoxide to the total number of silicon atoms derived from the silane oligomer and the silane monomer (the first silane monomer and the second silane monomer) (M / Si) may be, for example, 0.00001 or more, preferably 0.0001 or more. This tends to result in better curability. The molar ratio (M / Si) may be, for example, 0.5 or less, preferably 0.2 or less. This tends to improve transparency.

The composition according to this embodiment may further contain a curing catalyst. The curing catalyst is not particularly limited as long as it promotes the polymerization reaction of the silane oligomer and the silane monomer.

Examples of the curing catalyst include acid catalysts containing hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid and the like, metal catalysts containing tin, titanium, aluminum, zinc, iron, cobalt, manganese and the like, aliphatic amines, ammonium hydroxide and water. Examples thereof include a base catalyst containing tetraethylammonium oxide, sodium carbonate, sodium hydroxide and the like.

The content of the curing catalyst may be, for example, 0.02 parts by mass or more, preferably 0.05 parts by mass or more, and may be 20 parts by mass or less, and 10 parts by mass with respect to 100 parts by mass of the silane oligomer. The following is preferable.

The composition according to this embodiment may further contain components other than the above. Examples of other components include resins having a hydroxyl group in the molecular structure, metal oxide particles, metal oxide fibers, and the like. Examples of the resin having a hydroxyl group in the molecular structure include polyvinyl alcohol and the like. Further, examples of the metal oxide particles include silica particles and alumina particles, and these particles are preferably nano-sized (for example, the particle size is 1 nm or more and less than 1000 nm) (that is, nanosilica particles, nanoalumina). Particles are preferred). Examples of the metal oxide fiber include alumina fiber, and the fiber diameter of these metal oxide fibers is preferably nano-sized (for example, the fiber diameter is 1 nm or more and less than 1000 nm) (that is, alumina nanofiber is preferable). .).

The content of the above other components is not particularly limited as long as the above effects can be obtained, and may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less with respect to 100 parts by mass of the silane oligomer. Is. Further, the content of the other components may be, for example, 10 parts by mass or more, or 20 parts by mass or more, based on 100 parts by mass of the silane oligomer.

Examples of the method for producing the composition according to the present embodiment include the following methods.

<Production method 1 of composition>
The present production method comprises a modification step of reacting a silane oligomer with a metal alkoxide to modify at least a part of the silane oligomer with the metal alkoxide. In this modification step, the metal alkoxide reacts with the silane oligomer to form a metal atom-oxygen atom-silicon atom bond.

The above reaction may be carried out in a liquid medium. Examples of the liquid medium include the same as above. The amount of the liquid medium is not particularly limited, and may be, for example, an amount such that the concentration of the silane oligomer in the reaction solution is 50 to 99% by mass (preferably 80 to 95% by mass).

The reaction conditions for the above reaction are not particularly limited. For example, the reaction temperature of the above reaction may be 60 to 100 ° C. or 70 to 90 ° C. The reaction time of the above reaction may be, for example, 0.5 to 5.0 hours, or 1.0 to 3.0 hours.

The present production method may further include a step of adding a silane oligomer to the reaction solution after the modification step. As a result, a composition containing a silane oligomer modified with a metal alkoxide and an unmodified silane oligomer can be obtained.

The present production method may further include a step of adding a first silane monomer (and a second silane monomer, if necessary) to the reaction solution after the modification step. That is, in this production method, the first step of preparing a silane oligomer at least partially modified with a metal alkoxide and the modified silane oligomer and the first silane monomer are mixed to prepare a composition for forming a barrier material. It may be a method including the second step of obtaining, and the first step may be the modification step. As a result, a composition containing the first silane monomer is obtained.

The present production method may further include a step of adding other components to the reaction solution after the modification step. The present production method may further include a step of adding a liquid medium to the reaction solution after the modification step, or a step of replacing the liquid medium in the reaction solution after the modification step with another liquid medium. By these steps, various aspects of the above composition can be prepared from the reaction solution after the modification step.

<Production method 2 of composition>
The production method comprises a modification step of reacting a silane monomer with a metal alkoxide to form a silane oligomer that is at least partially modified with the metal alkoxide. In the modification step, a silane oligomer is formed by polymerization of the silane monomer, and the formed silane oligomer may be modified with a metal alkoxide. Further, in the modification step, after the silane monomer is modified with a metal alkoxide, a silane oligomer moiety may be formed by the reaction of the modified silane monomer with another silane monomer.

The above reaction may be carried out in a liquid medium. Examples of the liquid medium include the same as above. The amount of the liquid medium is not particularly limited, and may be, for example, an amount such that the concentration of the silane monomer in the reaction solution is 50 to 99% by mass (preferably 80 to 95% by mass).

<Barrier material>
The barrier material according to this embodiment contains a polysiloxane compound doped with a metal atom. This barrier material may be a cured product of the above-mentioned composition for forming a barrier material. Further, this barrier material may be formed by heating the above-mentioned composition for forming a barrier material. By the heating, the silane oligomer and the silane monomer in the composition are polymerized to form a polysiloxane compound. At this time, since the silane oligomer is modified with the metal alkoxide, the metal atom derived from the metal alkoxide is doped in the formed polysiloxane compound.

The polysiloxane compound has a siloxane skeleton. Further, in the polysiloxane compound, the metal atom is bonded to the silicon atom constituting the polysiloxane skeleton via the oxygen atom.

The silicon atom contained in the polysiloxane compound is a silicon atom bonded to one oxygen atom (M unit), a silicon atom bonded to two oxygen atoms (D unit), and a silicon atom bonded to three oxygen atoms. It can be distinguished into (T unit) and a silicon atom (Q unit) bonded to four oxygen atoms. Examples of the M unit, the D unit, the T unit, and the Q unit include the above formulas (M), (D), (T), and (Q), respectively.

In the polysiloxane compound, the ratio of the total number of T units and Q units to the total number of silicon atoms is preferably 50% or more, more preferably 70% or more, still more preferably 90% or more. , 100%. According to such a polysiloxane compound, the moisture resistance of the barrier material is further improved.

In a preferred embodiment, the polysiloxane compound preferably contains T units. The content of T units in the polysiloxane compound may be, for example, 10% or more, 20% or more, 30% or more, 40% or more or 50% or more, and 70% or more, based on the total number of silicon atoms. Is more preferable, 80% or more is more preferable, 90% or more is further preferable, and 100% may be used. Such polysiloxane compounds tend to further improve flexibility.

In another preferred embodiment, the content of Q units in the polysiloxane compound may be, for example, 50% or more, preferably 70% or more, and preferably 80% or more, based on the total number of silicon atoms. More preferably, it is more preferably 90% or more, and it may be 100%. According to such a polysiloxane compound, the moisture resistance and transparency tend to be further improved.

In the polysiloxane compound, the molar ratio (M / Si) of the metal atom M to the total number of silicon atoms (Si) may be, for example, 0.0001 or more, preferably 0.001 or more. This tends to result in better curability. The molar ratio (M / Si) may be, for example, 0.5 or less, preferably 0.2 or less. This tends to make the transparency even better.

It is preferable that most of the oxygen atoms of the polysiloxane compound are bonded to at least one silicon atom. When the polysiloxane compound contains a small amount of alcoholic hydroxyl groups (C—OH), ether bonds (COC), etc., the moisture resistance tends to be further improved. For example, of the oxygen atoms in the polysiloxane compound, for example, 90% or more is preferably bonded to a silicon atom, 95% or more is preferably bonded to a silicon atom, and 99% or more is bonded to a silicon atom. It is more preferable that they are bonded.

The barrier material has a low water vapor permeability and is excellent in moisture resistance. Water vapor permeability of the barrier material per thickness 25μm (40 ℃, RH 95% ) , for example 4000g ^/ m 2 · day may be less, is preferably not more than ^{3500g / m 2 · day, 3000g} / m It is more preferably ^2. day or less.

The water vapor permeability of the barrier material per 25μm thick (40 ℃, RH 95%), for example may be at 500g ^/ m 2 · day or more, preferably 1000g ^/ m 2 · day or more. Such a barrier material has a dehumidifying property, and even when used in a high temperature environment, it can sufficiently suppress destruction due to expansion of water that has entered the inside.

The water vapor transmittance of the barrier material is based on JIS K7129 and indicates a value measured by the humidity sensor method (Lyssy method).

The barrier material may have transparency. Such a barrier material can be suitably used as a coating material for covering an image sensor in an application that requires transparency, for example, an image sensor package. In addition, having transparency here means that the visible light transmittance (light transmittance of 550 nm) per 1 mm of thickness is 95% or more.

The barrier material has a visible light transmittance (light transmittance of 550 nm) per 1 mm of thickness preferably 95% or more, more preferably 97% or more, still more preferably 99% or more. .. The visible light transmittance of the barrier material is measured by a spectrophotometer.

The shape of the barrier material is not particularly limited. The barrier material may be formed into a film, for example, and such a barrier material can be used as a moisture-proof barrier film. Further, the barrier material may be formed so as to fill the gaps between the members, and in this case, the intrusion of moisture from the gaps can be prevented. Further, the barrier material may be formed so as to cover the member, and in this case, contact with the moisture of the member can be prevented.

<Manufacturing method of barrier material>
The method for producing a barrier material according to the present embodiment includes a heating step of heating the above-mentioned composition to form a barrier material. In this production method, the silane oligomer and the first silane monomer in the composition are polymerized by heating to form a polysiloxane compound. At this time, since at least a part of the silane oligomer is modified with a metal alkoxide in the above composition, a metal atom derived from the metal alkoxide is doped in the polysiloxane compound. Further, in the present embodiment, since the first silane monomer has a reactive functional group, a crosslinked structure other than the siloxane bond is formed by the reaction between the reactive functional groups, the reaction between the reactive functional group and the silanol group, and the like. It is believed that this will provide excellent moisture resistance and flexibility. Further, in the present embodiment, since the first silane monomer has a reactive functional group, it is considered that the reactive functional group is bonded to the functional group existing on the surface of the object, thereby providing better moisture resistance and moisture resistance. Flexibility is expected to be achieved.

In the heating step, the liquid medium in the composition may be removed by heating. That is, the heating step may be a step of forming a barrier material containing a polysiloxane compound by heating and drying the composition.

The heating temperature in the heating step is not particularly limited as long as the silane oligomer can be polymerized. When the composition contains a liquid medium, the heating temperature is preferably a temperature at which the liquid medium volatilizes. The heating temperature may be, for example, 70 ° C. or higher, preferably 100 ° C. or higher. The heating temperature may be, for example, 200 ° C. or lower, preferably 180 ° C. or lower.

The present production method may further include a coating step of coating the composition. At this time, the heating step can be said to be a step of heating the applied composition.

The method of applying the composition is not particularly limited, and may be appropriately changed depending on the shape of the object to be applied, the thickness of the barrier material, and the like.

In this production method, the composition may be applied to an object to which moisture resistance is to be imparted, and a barrier material may be formed on the object. Further, in the present manufacturing method, a barrier material having a predetermined shape may be manufactured and then the manufactured barrier material may be applied onto the object.

<Use of barrier material>
The use of the barrier material according to the present embodiment is not particularly limited, and it can be suitably applied to various uses requiring moisture resistance. For example, the barrier material can be suitably used as a moisture-proof barrier material for electronic parts.

The barrier material according to this embodiment has excellent moisture resistance even in a high temperature environment (for example, 100 ° C. or higher). Therefore, the barrier material according to the present embodiment is suitably used for, for example, a moisture-proof barrier material for electronic parts used in a high-temperature environment, a moisture-proof barrier material for electronic parts that undergo a high-temperature process at the time of mounting, and the like. Can be done. Specifically, for example, it can be suitably used as a moisture-proof barrier material for power semiconductors, a moisture-proof barrier material for image sensors, a moisture-proof barrier material for displays, and the like.

The preferred form of the use of the barrier material will be described in detail below, but the use of the barrier material is not limited to the following.

<Application example 1>
The application according to one form relates to a product having a moisture-proof treated member. Such products include a member and a barrier material formed on the member. The barrier material may be formed on one member or may be formed on a plurality of members. The barrier material may be formed, for example, to cover one or more members, or may be formed to cover the joint between the two members.

Such a product includes a first step of applying the barrier material forming composition on the member and a second step of heating the applied composition to form the barrier material on the member. Manufactured by the manufacturing method.

Specific examples of such applications include the following electronic components.

(Electronic component A-1)
The electronic components according to one form include a substrate, a cover glass, an image sensor arranged between the substrate and the cover glass, a support member for supporting the cover glass and the image sensor on the substrate, and a cover glass and a support member. The barrier material provided on the joint portion of the above is provided.

For such electronic components, for example, a coating step of applying a barrier material forming composition to a joint portion between a support member and a cover glass and a coating step of heating the applied composition to form a barrier material on the joint portion. It can be manufactured by a manufacturing method including a barrier material forming step.

(Electronic component A-2)
The electronic component according to one form includes a substrate, an image sensor arranged on the substrate, and the barrier material provided on the image sensor.

The barrier material can be excellent in moisture resistance and transparency. Therefore, the barrier material can also be suitably used as a sealing material for sealing the image sensor. Since such an electronic component can form an image sensor package without using a cover glass, it can be expected that the component size can be reduced and the handleability can be improved.

In this application, the visible light transmittance (550 nm) of the barrier material per 1 mm of thickness is preferably 95% or more, more preferably 97% or more, and further preferably 99% or more.

Such electronic components include, for example, a coating step of applying a barrier material forming composition on an image sensor and a barrier material forming step of heating the applied composition to form a barrier material on the image sensor. , Can be manufactured by a manufacturing method comprising.

<Application example 2>
The application according to one embodiment relates to a product having a first member and a second member joined to the first member, and the joint portion between the first member and the second member is moisture-proofed. Such a product comprises a first member, a second member, and a barrier material provided between the first member and the second member, and the first member and the second member. Is joined via a barrier material.

In such a product, the first step of arranging the composition for forming a barrier material between the first member and the second member and the first step of heating the composition to form the barrier material are performed. It can be manufactured by a manufacturing method including a second step of joining a member and a second member via a barrier material.

(Electronic component B-1)
The electronic components according to one form include a substrate, a cover glass, an image sensor arranged between the substrate and the cover glass, a support member for supporting the cover glass and the image sensor on the substrate, and a cover glass and a support member. It is provided with a barrier material for joining.

For such electronic components, for example, a step of arranging a composition for forming a barrier material between a support member and a cover glass and a step of heating the composition to form a barrier material, and the support member and the cover glass are formed. It can be manufactured by a manufacturing method including a step of joining via a barrier material.

<Application example 3>
The application according to one form relates to a product provided with a moisture-proof member. Such a product includes a moisture-proof member made of a barrier material, and may be, for example, an assembly of a plurality of members including the moisture-proof member.

Such a product includes a first step of heating the composition for forming a barrier material to produce a moisture-proof member made of the barrier material, and a second step of assembling a plurality of members including the moisture-proof member. It can be manufactured by a manufacturing method.

(Electronic component C-1)
The electronic component according to one form includes a substrate, at least one component selected from the group consisting of a MEMS sensor, a wireless module, and a camera module, and a moisture-proof member having a barrier material.

The above barrier material has excellent moisture resistance. Therefore, the electronic component has excellent moisture resistance, and deterioration of sensing characteristics due to moisture absorption is sufficiently prevented.

Such electronic components are manufactured by, for example, a manufacturing method including a step of producing a moisture-proof member having a barrier material by heating a composition for forming a barrier material, and a step of assembling a plurality of members including the moisture-proof member. can do. Here, the barrier material may be formed independently of the substrate and the component, and may be integrally formed with the component by heating the barrier material forming composition applied on the component.

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example A-1)
[Composition for Forming Barrier Material A-1]
7. Aluminum sec-butoxide (manufactured by Matsumoto Fine Chemical Industries, Ltd., product name: AL-3001, hereinafter abbreviated as "AL-3001") by 3.8 parts by mass, tert-butyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 7. After mixing 6 parts by mass, 0.3 parts by mass of water, 0.3 parts by mass of acetic acid, and 64.9 parts by mass of silane oligomer (manufactured by Momentive Performance Materials, product name: XC31-B2733), 70 parts by mass. The reaction was carried out at ° C. for 1 hour. Next, 23.4 parts by mass of tetraethoxysilane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "TEOS") was mixed, and then reacted at 25 ° C. for 2 hours. Next, 1 part by mass of N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-603, hereinafter abbreviated as "KBE-603") was mixed. A composition for forming a barrier material A-1 was obtained.

[Evaluation film A-1 with barrier material]
The barrier material forming composition A-1 was applied to both sides of a 0.125 mm thick polyimide film (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H) so that the thickness after drying was 15 μm. It was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film A-1 with a barrier material was obtained.

[Evaluation method]
The hygroscopicity (%) and adhesion of the evaluation film A-1 with a barrier material were evaluated by the following methods.
<Evaluation of hygroscopicity (1)>
The evaluation film with a barrier material was dried at 130 ° C. for 1 hour using a safety oven (manufactured by ESPEC CORPORATION, product name: SPHH-202) to obtain a measurement sample. The mass of the obtained measurement sample was measured, and the initial mass m1 was determined. Next, a sample after the constant temperature and humidity treatment was performed by treating for 40 hours in an atmosphere of 85 ° C./85% RH using a constant temperature and humidity chamber (manufactured by Kato Co., Ltd., product name: SE-44CI-A). Got The mass of the measurement sample after the constant temperature and humidity treatment was measured, and the mass m2 after the constant temperature and humidity treatment was determined. From the initial mass m1 and mass m2 after constant temperature and humidity treatment, according to the following formula to determine the moisture ratio Q _{A (%).}
_{Q A = 100 × (m1-} m2) / m2
<Adhesion>
The evaluation film with a barrier material was visually observed to confirm the presence or absence of peeling of the barrier material. The case where there was no peeling was evaluated as A, and the case where there was peeling was evaluated as B.

(Example A-2)
Composition A for forming a barrier material in the same manner as in Example A-1 except that 64.9 parts by mass of a silane oligomer (manufactured by Momentive Performance Materials, product name: TSR165) was used instead of TSR165. I got -2.

Next, the composition A-for forming a barrier material so that the thickness after drying is 10 μm for both sides of a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H). 2 was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film A-2 with a barrier material was obtained. The hygroscopicity and adhesion of the obtained evaluation film A-2 with a barrier material were evaluated in the same manner as in Example A-1.

(Example A-3)
Instead of TSR165, 64.9 parts by mass of silane oligomer (manufactured by Momentive Performance Materials, product name: TSR165) was used, and instead of KBE-603, 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. , Product name: KBE-903) A barrier material forming composition A-3 was obtained in the same manner as in Example A-1 except that 1 part by mass was used.

Next, the composition A-for forming a barrier material so that the thickness after drying is 10 μm for both sides of a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H). 3 was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film A-3 with a barrier material was obtained. The hygroscopicity and adhesion of the obtained evaluation film A-3 with a barrier material were evaluated in the same manner as in Example A-1.

(Example A-4)
64.9 parts by mass of silane oligomer (manufactured by Momentive Performance Materials, product name: TSR165) was used instead of TSR165, and phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM) was used instead of TEOS. -103, hereinafter abbreviated as "PTMS") A composition for forming a barrier material A-4 was obtained in the same manner as in Example A-1 except that 23.4 parts by mass was used.

Next, the barrier material forming composition A- 4 was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film A-4 with a barrier material was obtained. The hygroscopicity and adhesion of the obtained evaluation film A-4 with a barrier material were evaluated in the same manner as in Example A-1.

(Comparative Example X-1)
A barrier material forming composition X-1 was obtained in the same manner as in Example A-1 except that KBE-603 was not added.

Next, the barrier material forming composition X-so that the thickness after drying is 15 μm for both sides of a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H). 1 was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film X-1 with a barrier material was obtained. The hygroscopicity and adhesion of the obtained evaluation film X-1 with a barrier material were evaluated in the same manner as in Example A-1.

(Reference example 1)
For a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H), the moisture absorption rate of Example A-1 was evaluated without forming a barrier material. The results are shown in Table 1.

(Example B-1)
Example A-4 except that 1 part by mass of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-1003, hereinafter abbreviated as "KBM-1003") was used instead of KBE-603. The barrier material forming composition B-1 was obtained in the same manner as in the above.

Next, the barrier material forming composition B- was applied to both sides of a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name: Kapton (registered trademark) 500H) so that the thickness after drying was 20 μm. 1 was applied and dried at 150 ° C. for 4 hours. As a result, a barrier material was formed on the base material, and an evaluation film B-1 with a barrier material was obtained. The hygroscopicity of the obtained evaluation film B-1 with a barrier material was measured by the following method. Further, the adhesion of the obtained evaluation film B-1 with a barrier material was evaluated in the same manner as in Example A-1.

<Evaluation of hygroscopicity (2)>
The evaluation film with a barrier material was dried at 130 ° C. for 1 hour using a safety oven (manufactured by ESPEC CORPORATION, product name: SPHH-202) to obtain a measurement sample. The mass of the obtained measurement sample was measured, and the initial mass m3 was determined. Next, a sample after the constant temperature and humidity treatment was performed by treating for 190 hours in an atmosphere of 85 ° C./85% RH using a constant temperature and humidity chamber (manufactured by Kato Co., Ltd., product name: SE-44CI-A). Got The mass of the measurement sample after the constant temperature and humidity treatment was measured, and the mass m4 after the constant temperature and humidity treatment was determined. From initial mass m3 and constant temperature and humidity treatment after the mass m4, by the following equation to determine the moisture ratio Q _{B (%).}
_{Q B = 100 × (m3-} m4) / m4

(Example B-2)
Except that 1 part by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-403, hereinafter abbreviated as "KBM-403") was used instead of KBM-1003. A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in Example B-1.

(Example B-3)
Implemented except that 1 part by mass of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-503, hereinafter abbreviated as "KBM-503") was used instead of KBM-1003. A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in Example B-1.

(Example B-4)
Implemented except that 1 part by mass of 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-5103, hereinafter abbreviated as "KBM-5103") was used instead of KBM-1003. A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in Example B-1.

(Example B-5)
Except for the use of 1 part by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-573, hereinafter abbreviated as "KBM-573") instead of KBM-1003. Made and evaluated a composition for forming a barrier material and an evaluation film with a barrier material in the same manner as in Example B-1.

(Example B-6)
Examples except that 1 part by mass of 3-isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-9007N, hereinafter abbreviated as "KBE-9007N") was used instead of KBM-1003. A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in B-1.

(Example B-7)
Except for the use of 1 part by mass of tris- (trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-9569, hereinafter abbreviated as "KBM-9655") instead of KBM-1003. , A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in Example B-1.

(Example B-8)
Examples except that 1 part by mass of 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-803, hereinafter abbreviated as "KBM-803") was used instead of KBM-1003. A composition for forming a barrier material and an evaluation film with a barrier material were prepared and evaluated in the same manner as in B-1.

(Reference example 2)
The hygroscopicity of Example B-1 was evaluated for a polyimide film having a thickness of 0.125 mm (manufactured by Toray DuPont Co., Ltd., product name Kapton (registered trademark) 500H) without forming a barrier material. The results are shown in Table 2.

Claims

Containing a silane oligomer and a silane monomer having a reactive functional group,
A composition for forming a barrier material, wherein at least a part of the silane oligomer is modified with a metal alkoxide.
The barrier material according to claim 1, wherein the reactive functional group is selected from the group consisting of a vinyl group, an epoxy group, a glycidyl group, a (meth) acryloyl group, an amino group, an isocyanate group, an isocyanurate group and a mercapto group. Composition for formation.
The composition for forming a barrier material according to claim 1 or 2, wherein the reactive functional group is an amino group.
The composition for forming a barrier material according to any one of claims 1 to 3, wherein the silane oligomer contains a silicon atom bonded to three oxygen atoms.
Claims 1 to 4 in which the ratio of the total number of silicon atoms bonded to 3 oxygen atoms and the total number of silicon atoms bonded to 4 oxygen atoms to the total number of silicon atoms in the silane oligomer is 50% or more. The composition for forming a barrier material according to any one of the above.
The composition for forming a barrier material according to any one of claims 1 to 5, wherein the content of the silane monomer is 0.01 to 5 parts by mass with respect to 100 parts by mass of the silane oligomer.
The composition for forming a barrier material according to any one of claims 1 to 6, further comprising a second silane monomer selected from the group consisting of alkyltrialkoxysilanes, aryltrialkoxysilanes and tetraalkoxysilanes.
The composition for forming a barrier material according to claim 7, wherein the content of the second silane monomer is 5 to 40 parts by mass with respect to 100 parts by mass of the silane oligomer.
The composition for forming a barrier material according to any one of claims 1 to 8, wherein the metal alkoxide is an aluminum alkoxide.
The first step of preparing a silane oligomer that is at least partially modified with metal alkoxide,
The second step of mixing the silane oligomer with the silane monomer having a reactive functional group to obtain a composition for forming a barrier material, and
A method for producing a composition for forming a barrier material.
The production method according to claim 10, wherein the first step includes a step of reacting a silane oligomer with a metal alkoxide and modifying at least a part of the silane oligomer with a metal alkoxide.
The production method according to claim 10, wherein the first step includes a step of reacting a silane monomer with a metal alkoxide to form a silane oligomer at least partially modified with the metal alkoxide.
A method for producing a barrier material, comprising a step of heating the composition for forming a barrier material according to any one of claims 1 to 9 to form the barrier material.
A method for manufacturing a product having a moisture-proof treated member.
The first step of applying the barrier material forming composition according to any one of claims 1 to 9 onto the member, and
A second step of heating the applied composition for forming a barrier material to form a barrier material on the member, and
A manufacturing method.
A method for manufacturing a product having a first member and a second member joined to the first member, and a joint portion between the first member and the second member being moisture-proofed. ,
The first step of arranging the barrier material forming composition according to any one of claims 1 to 9 between the first member and the second member,
A second step of heating the barrier material forming composition to form a barrier material and joining the first member and the second member via the barrier material.
A manufacturing method.
A method of manufacturing a product equipped with a moisture-proof member.
The first step of heating the barrier material forming composition according to any one of claims 1 to 9 to prepare a moisture-proof member having a barrier material, and
A second step of assembling a plurality of members including the moisture-proof member, and
A manufacturing method.
A barrier material which is a cured product of the composition for forming a barrier material according to any one of claims 1 to 9.
Water vapor transmission rate per thickness 25μm (40 ℃, 95% RH ) is not more than 4000g / m 2 · day, barrier material of claim 17.
The barrier material according to claim 17 or 18, wherein the transmittance for light at 550 nm per 1 mm of thickness is 90% or more.
Members and
The barrier material according to any one of claims 17 to 19 formed on the member.
The product.
The barrier material according to any one of claims 17 to 19 provided between the first member, the second member, and the first member and the second member is provided.
A product in which the first member and the second member are joined via the barrier material.
A product which is an assembly of a plurality of members including a moisture-proof member having the barrier material according to any one of claims 17 to 19.