Compositions for forming barrier materials, barrier materials and methods for manufacturing the same, and products and methods for manufacturing the same

Abstract

The present invention provides a composition for forming a barrier material comprising a silane oligomer, wherein at least a portion of the silane oligomer is modified with a metal alkoxide.

Description

Technical Field

[0001] The invention relates to a barrier material forming composition, a barrier material and a manufacturing method thereof, and a product and a manufacturing method thereof. Prior Art

[0002] Conventionally, in order to prevent moisture from entering into gaps formed in electronic components, studies have been conducted on how to seal electronic components with a barrier film or the like. For example, Patent Document 1 describes a barrier film laminate formed by laminating barrier films including an inorganic oxide layer. [Prior art literature] [Patent Document]

[0003] Patent Document 1: Japanese Patent Application Publication No. 2011-093195 Summary of the invention

[0004] [Problems to be solved by the invention] However, the barrier film laminate described in Patent Document 1 is in a film form, and therefore its applicable objects are limited.

[0005] In addition, there is also a method of sealing the gap by filling the gaps between the components of the electronic parts with solder or the like. However, in this method, if a small amount of water intrudes into the gaps and expands due to heating, there is a risk that the electronic parts will be damaged, and there are limitations on use in high temperature environments.

[0006] Therefore, the object of the present invention is to provide a barrier material that can be applied to objects of various shapes, has excellent moisture resistance, and can fully suppress damage caused by expansion of water that penetrates into the interior even when exposed to a high temperature environment. In addition, the object of the present invention is to provide a barrier material forming composition for forming the barrier material. Furthermore, the object of the present invention is to provide a method for manufacturing the barrier material, a product including the barrier material, and a method for manufacturing the product. [Methods to solve the problem]

[0007] The present invention provides a barrier material forming composition comprising a silane oligomer, wherein at least a portion of the silane oligomer is modified by a metal alkoxide.

[0008] This composition can be easily formed into a barrier material with excellent moisture resistance on an object by applying it to the object and heating it. In addition, the barrier material formed has flexibility and moisture-repelling properties, and even if the moisture that has penetrated into the object expands by heating, it can fully suppress the destruction of the object.

[0009] In one aspect, the ratio of the total number of silicon atoms bonded to three oxygen atoms and the total number of silicon atoms bonded to four oxygen atoms to the total number of silicon atoms in the silane oligomer may be 50% or more.

[0010] In one aspect, the silane oligomer can have a silicon atom bonded to three oxygen atoms.

[0011] One aspect of the composition may further contain a silane monomer.

[0012] In one aspect, the silane monomer may contain a silicon atom bonded to 3 or 4 oxygen atoms.

[0013] In one aspect, the silane monomer may be a silane monomer selected from the group consisting of alkyltrialkoxysilane, aryltrialkoxysilane and tetraalkoxysilane.

[0014] In one aspect, the content of the silane monomer may be 100 parts by mass or less relative to 100 parts by mass of the silane oligomer.

[0015] In one aspect, the metal alkoxide may be aluminum alkoxide.

[0016] In addition, the present invention provides a method for producing a barrier material forming composition, which comprises: a first step of preparing a silane oligomer at least partly modified by a metal alkoxide; and a second step of mixing the silane oligomer with a silane monomer to obtain the barrier material forming composition.

[0017] In one aspect, the first step may include the following steps: reacting a silane oligomer with a metal alkoxide, and modifying at least a portion of the silane oligomer with the metal alkoxide.

[0018] In one aspect, the first step may include the following steps: reacting a silane monomer with a metal alkoxide to form a silane oligomer at least partially modified by the metal alkoxide.

[0019] In addition, the present invention provides a method for manufacturing a barrier material, which includes the following steps: heating the barrier material forming composition to form the barrier material.

[0020] In addition, the present invention provides a method for manufacturing a product having a component subjected to moisture-proof treatment. The manufacturing method may include: a first step of applying the barrier material forming composition on the component; and a second step of heating the applied composition to form the barrier material on the component.

[0021] In addition, the present invention provides a method for manufacturing a product, wherein the product has a first member and a second member joined to the first member, and the joint between the first member and the second member is subjected to moisture-proof treatment. The manufacturing method may include: a first step of arranging the barrier material forming composition between the first member and the second member; and a second step of heating the composition to form a barrier material, and joining the first member and the second member via the barrier material.

[0022] In addition, the present invention provides a method for manufacturing a product including a moisture-proof member. The manufacturing method provides the following manufacturing method, which includes: a first step of heating the barrier material forming composition to produce a moisture-proof member having a barrier material; and a second step of assembling a plurality of members including the moisture-proof member.

[0023] In addition, the present invention provides a barrier material comprising a polysiloxane compound doped with metal atoms, wherein the ratio of the total number of silicon atoms bonded to three oxygen atoms and the total number of silicon atoms bonded to four oxygen atoms to the total number of silicon atoms in the polysiloxane compound is 50% or more.

[0024] In one aspect, the polysiloxane compound may contain a silicon atom bonded to three oxygen atoms.

[0025] In one aspect of the barrier material, more than 90% of oxygen atoms in the polysiloxane compound may be bonded to silicon atoms.

[0026] The barrier material of one aspect may have a water vapor transmission rate (40° C., 95% RH) per 25 μm thickness of 1 g / m 2·day or more.

[0027] The light transmittance of the barrier material in one aspect with respect to light of 550 nm per 1 mm thickness may be 95% or more.

[0028] In addition, the present invention provides a product comprising: a component; and the barrier material formed on the component.

[0029] In addition, the present invention provides a product comprising: a first component, a second component, and the barrier material disposed between the first component and the second component, wherein the first component and the second component are joined via the barrier material.

[0030] Furthermore, the present invention provides a product which is an assembly of a plurality of components including a moisture-proof component having the barrier material. [Effects of the Invention]

[0031] According to the present invention, there is provided a barrier material that can be applied to objects of various shapes, has excellent moisture resistance, and can fully suppress damage caused by expansion of water that penetrates into the interior even when exposed to a high temperature environment. In addition, the present invention can provide a barrier material-forming composition for forming the barrier material. Furthermore, the present invention can provide a method for manufacturing the barrier material, a product including the barrier material, and a method for manufacturing the product. Implementation

[0032] Hereinafter, a preferred embodiment of the present invention will be described. In this specification, the numerical range represented by "~" indicates a range including the numerical values recorded before and after "~" as the minimum and maximum values, respectively. The so-called "A or B" may include either A or B, or both. Unless otherwise specified, the materials exemplified in this embodiment may be used alone or in combination of two or more.

[0033] <Barrier Material Forming Composition> The barrier material forming composition of this embodiment includes a silane oligomer, and at least a part of the silane oligomer is modified with a metal alkoxide.

[0034] This composition can be easily formed into a barrier material with excellent moisture resistance on an object by applying it to the object and heating it. In addition, the barrier material formed has flexibility and moisture-repelling properties. Even if the moisture that has penetrated into the object expands by heating, the barrier material acts as a buffer material or the expanded water vapor escapes to the outside through the barrier material, thereby sufficiently suppressing the destruction of the object.

[0035] In addition, the barrier material has excellent moisture resistance and moderate moisture-removing properties. Therefore, when moisture enters the interior of an object sealed with the barrier material, the moisture inside can be significantly reduced by drying.

[0036] The barrier material forming composition of the present embodiment may be in a liquid state or a paste state, for example. From the viewpoint of being easy to apply to an object, the barrier material forming composition is preferably a liquid composition.

[0037] Silane oligomer is a polymer of silane monomers and has a structure in which a plurality of silicon atoms are linked via oxygen atoms. In this specification, silane oligomer refers to a polymer having a molecular weight of 100,000 or less.

[0038] In the present specification, the metal alkoxide-modified silane oligomer refers to a compound formed by the reaction of a silane oligomer and a metal alkoxide, and may also refer to a compound having a structure in which a silicon atom derived from a silane oligomer and a metal atom derived from a metal alkoxide are bonded via an oxygen atom.

[0039] The silane oligomer modified with a metal alkoxide (hereinafter referred to as "modified silane oligomer" as appropriate) may be a reaction product of a silane oligomer and a metal alkoxide, or a reaction product of a silane monomer and a metal alkoxide. In the latter case, the silane oligomer may be formed by reacting a silane monomer with a metal alkoxide and then reacting with another silane monomer to form a silane oligomer structure, or may be formed by reacting a silane oligomer formed by a reaction between silane monomers and a metal alkoxide.

[0040] Furthermore, regarding the composition of this embodiment, it is not necessary for all of the silane oligomers contained in the composition to be modified with the metal alkoxide. It is sufficient that at least a part of the silane oligomers is modified with the metal alkoxide.

[0041] The silicon atoms contained in the silane oligomer can be divided into silicon atoms bonded to one oxygen atom (M unit), silicon atoms bonded to two oxygen atoms (D unit), silicon atoms bonded to three oxygen atoms (T unit), and silicon atoms bonded to four oxygen atoms (Q unit). Examples of the M unit, D unit, T unit, and Q unit include the following formula (M), formula (D), formula (T), and formula (Q), respectively.

[0042] [Chemistry 1]

[0043] In the above formula, R represents an atom (hydrogen atom, etc.) or an atomic group (alkyl group, etc.) other than an oxygen atom bonded to a silicon atom. Information related to the content of these units can be obtained by Si-NMR (Si-Nuclear Magnetic Resonance Spectra).

[0044] 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, and may be 100%. According to such a silane oligomer, a barrier material with better moisture resistance can be obtained.

[0045] In a preferred embodiment, the silane oligomer preferably contains T units. The content of T units in the silane oligomer relative to the total number of silicon atoms 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, or 90% or more, and may also be 100%. Such silane oligomers tend to have further improved softness and dehumidification properties.

[0046] In another preferred embodiment, the content of Q units in the silane oligomer is, for example, 50% or more, preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and may be 100% relative to the total number of silicon atoms. Such silane oligomers tend to have further improved moisture resistance and transparency.

[0047] The silane oligomer preferably has an alkyl group or an aryl group as R in the formula (M), formula (D), formula (T) and formula (Q).

[0048] The alkyl group is preferably an alkyl group having no more than 6 carbon atoms, and more preferably an alkyl group having no more than 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, and butyl groups, among which methyl, ethoxy, and propyl groups are preferred, and methyl groups are more preferred.

[0049] Examples of the aryl group include phenyl and substituted phenyl. Examples of the substituent of the substituted phenyl include alkyl, vinyl, mercapto, amino, nitro, and cyano. The aryl group is preferably phenyl.

[0050] 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. In addition, the weight average molecular weight of the silane oligomer may be, for example, 30,000 or more, preferably 10,000 or less, and more preferably 6,000 or less. If the weight average molecular weight of the silane oligomer is large, the flexibility and dehumidification properties tend to be further improved, and if the weight average molecular weight of the silane oligomer is small, the moisture resistance and transparency tend to be further improved. Furthermore, in this specification, the weight average molecular weight of the silane oligomer represents the value of the weight average molecular weight expressed in terms of polystyrene measured by gel permeation chromatography (GPC).

[0051] The metal alkoxide can be represented by, for example, M(OR 1) n, where M represents an n-valent metal atom, R 1 represents an alkyl group, and n represents an integer greater than or equal to 1.

[0052] n is preferably 2-5, more preferably 3-4.

[0053] As M, aluminum, titanium, zirconium, niobium, etc. can be listed, among which aluminum, titanium, zirconium, and aluminum are preferred. That is, as metal alkoxides, aluminum alkoxides, titanium alkoxides, zirconium alkoxides, and niobium alkoxides can be listed, among which aluminum alkoxides, titanium alkoxides, and zirconium alkoxides are preferred, and aluminum alkoxides are more preferred.

[0054] As R1, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 2 to 4 carbon atoms is more preferred. Specific examples of the alkyl group of R1 include methyl, ethyl, propyl, and butyl groups, among which ethyl, propyl, and butyl groups are preferred, and propyl and butyl groups are more preferred.

[0055] The composition of the present embodiment may include a modified silane oligomer obtained by modifying a silane oligomer with 0.1 to 50 parts by mass of a metal alkoxide relative to 100 parts by mass of the silane oligomer. The amount of the metal alkoxide is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less relative to 100 parts by mass of the silane oligomer. If the amount of the metal alkoxide is large, the curability tends to be better, and by reducing the amount of the metal alkoxide, the transparency tends to be further improved.

[0056] The composition of this embodiment may further include a silane monomer. By blending the silane monomer, for example, the content of the T unit and the Q unit in the barrier material can be adjusted, and the barrier material can be given effects such as transparency and flexibility according to the application. In addition, by blending the silane monomer, there is a tendency that a barrier material with better moisture resistance can be obtained.

[0057] The content of the silane monomer is not particularly limited, and can be, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and more preferably 30 parts by mass or more, relative to 100 parts by mass of the silane oligomer. Thereby, the above effect is more significantly exerted. In addition, the content of the silane monomer can be, for example, 100 parts by mass or less, can be 60 parts by mass or less, preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. By setting it to such a range, there is a tendency for the curability to become better. Furthermore, in this specification, "100 parts by mass of the silane oligomer" refers to the mass of the metal alkoxide that does not include the modified silane oligomer, and the total amount of the silane oligomer part of the modified silane oligomer and the unmodified silane oligomer is set to 100 parts by mass.

[0058] As the silane monomer, a trifunctional monomer containing a silicon atom bonded to three oxygen atoms and a tetrafunctional monomer containing a silicon atom bonded to four oxygen atoms can be preferably used.

[0059] Examples of the trifunctional monomer include alkyltrialkoxysilanes and aryltrialkoxysilanes. Alkyltrialkoxysilanes are silane compounds in which one alkyl group and three alkoxy groups are bonded to the silicon atom. In addition, aryltrialkoxysilanes are silane compounds in which one aryl group and three alkoxy groups are bonded to the silicon atom.

[0060] The alkyl group of the alkyltrialkoxysilane is preferably an alkyl group having 6 or less carbon atoms, and more preferably an alkyl group having 4 or less carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, and butyl groups, among which methyl, ethyl, and propyl groups are preferred, and methyl groups are more preferred. In addition, the alkoxy group of the alkyltrialkoxysilane is preferably an alkoxy group having 6 or less carbon atoms, and more preferably an alkoxy group having 4 or less carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy groups, among which methoxy, ethoxy, and propoxy groups are preferred, and methoxy and ethoxy groups are more preferred.

[0061] Examples of the aryl group of the aryltrialkoxysilane include phenyl and substituted phenyl. Examples of the substituent of the substituted phenyl include alkyl, vinyl, mercapto, amino, nitro, cyano, and the like. The aryl group is preferably a phenyl. In addition, the alkoxy group of the aryltrialkoxysilane is preferably an alkoxy group having 6 or less carbon atoms, and more preferably an alkoxy group having 4 or less carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and the like, among which methoxy, ethoxy, propoxy, and more preferably methoxy and ethoxy are preferred.

[0062] Specific examples of the trifunctional monomer include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

[0063] Examples of the tetrafunctional monomer include tetraalkoxysilane, etc. Tetraalkoxysilane is a silane compound having four alkoxy groups bonded to a silicon atom.

[0064] The alkoxy group of the tetraalkoxysilane is preferably an alkoxy group having a carbon number of 6 or less, and more preferably an alkoxy group having a carbon number of 4 or less. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, etc. Among them, methoxy, ethoxy, propoxy, and more preferably methoxy and ethoxy.

[0065] Specific examples of the tetrafunctional monomer include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.

[0066] The composition of this embodiment may further include a liquid medium. Examples of the liquid medium include water and an organic solvent.

[0067] Examples of the organic solvent include alcohols, ethers, ketones, esters, hydrocarbons, etc. In addition to these, acetonitrile, acetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can also be used.

[0068] In a preferred embodiment, the composition may include water and alcohol as a liquid medium. By using such a liquid medium, a barrier material with excellent transparency can be easily obtained.

[0069] As alcohols, those that can be vaporized by heating when the barrier material is formed are preferred. As alcohols, for example, alcohols having 6 or less carbon atoms are preferred, and alcohols having 1 to 4 carbon atoms are more preferred.

[0070] As alcohols, for example, alcohols corresponding to the alkoxy groups of the metal alkoxide can also be used. That is, for example, when the metal alkoxide has a tert-butyloxy group, tert-butyl alcohol can be used as the alcohol. Thereby, there is a tendency that the transparency is further improved.

[0071] The content of the liquid medium is not particularly limited, and can be set to a content that provides a viscosity that is optimal for coating the composition. The viscosity of the composition is not particularly limited and can 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.

[0072] The viscosity of the composition at 25° C. may be, for example, 1 mPa·s to 6000 mPa·s, preferably 5 mPa·s to 3000 mPa·s. With such a composition, it is easier to apply to an object and form a barrier material on the object.

[0073] In the composition of this embodiment, the molar ratio (M / Si) of the metal atoms M derived from the metal alkoxide relative to the total number of silicon atoms derived from the silane oligomer and the silane monomer may be, for example, 0.0001 or more, preferably 0.001 or more. This tends to improve the curability. In addition, the molar ratio (M / Si) may be, for example, 0.5 or less, preferably 0.2 or less. This tends to further improve the transparency.

[0074] The composition of this embodiment may further contain a hardening catalyst. The hardening catalyst is not particularly limited as long as it promotes the polymerization reaction of the silane oligomer and the silane monomer.

[0075] Examples of the hardening catalyst include acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and phosphoric acid; metal catalysts such as tin, titanium, aluminum, zinc, iron, cobalt, and manganese; and alkaline catalysts such as aliphatic amines, ammonium hydroxide, tetraethylammonium hydroxide, sodium carbonate, and sodium hydroxide.

[0076] The content of the hardening catalyst may be, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and may be 20 parts by mass or less, preferably 10 parts by mass or less, relative to 100 parts by mass of the silane oligomer.

[0077] The composition of this embodiment may further contain other components other than those described above. As other components, for example, resins having hydroxyl groups in the molecular structure, metal oxide particles, metal oxide fibers, etc. can be cited. As resins having hydroxyl groups in the molecular structure, for example, polyvinyl alcohol, etc. can be cited. In addition, as metal oxide particles, for example, silica particles, alumina particles, etc. can be cited, and these particles are preferably nano-sized (for example, the particle diameter is greater than 1 nm and less than 1000 nm) (that is, preferably nano-silica particles, nano-alumina particles). As metal oxide fibers, for example, alumina fibers can be cited, and the fiber diameters of these metal oxide fibers are preferably nano-sized (for example, the fiber diameter is greater than 1 nm and less than 1000 nm) (that is, preferably alumina nanofibers).

[0078] The content of the other components is not particularly limited as long as it is within the range for obtaining the above effects, and for example, it can be 50 parts by mass or less, preferably 40 parts by mass or less, relative to 100 parts by mass of the silane oligomer. In addition, the content of the other components can be, for example, 10 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of the silane oligomer.

[0079] As a method for producing the composition of this embodiment, the following method can be mentioned.

[0080] <Method 1 for producing composition> The manufacturing method includes the following modification step: reacting a silane oligomer with a metal alkoxide, and modifying at least a portion of the silane oligomer with the metal alkoxide. In the modification step, the metal alkoxide reacts with the silane oligomer to form a metal atom-oxygen atom-silicon atom bond.

[0081] The reaction can be carried out in a liquid medium. As the liquid medium, the same as described above can be exemplified. The amount of the liquid medium is not particularly limited, and for example, it can be an amount such that the concentration of the silane oligomer in the reaction solution becomes 50% to 99% by mass (preferably 80% to 95% by mass).

[0082] The reaction conditions of the reaction are not particularly limited. For example, the reaction temperature of the reaction may be 60°C to 100°C, or 70°C to 90°C. In addition, the reaction time of the reaction may be, for example, 0.5 hours to 5.0 hours, or 1.0 hours to 3.0 hours.

[0083] The manufacturing method may further include the step of adding silane oligomer to the reaction solution after the modification step. Thus, a composition containing silane oligomer modified with metal alkoxide and unmodified silane oligomer can be obtained.

[0084] The manufacturing method may further include a step of adding a silane monomer to the reaction solution after the modification step. That is, the manufacturing method may be a method comprising: a first step of preparing a silane oligomer at least partly modified with a metal alkoxide; and a second step of mixing the modified silane oligomer with the silane monomer to obtain a barrier material forming composition, and the first step may be the modification step. In this way, a composition containing a silane monomer can be obtained.

[0085] In addition, the present production method may further include the step of adding other components to the reaction solution after the modification step. In addition, the present production method may further include the step of adding a liquid medium to the reaction solution after the modification step, or the step of replacing the liquid medium in the reaction solution after the modification step with another liquid medium. Through these steps, various aspects of the composition can be prepared from the reaction solution after the modification step.

[0086] <Method 2 for producing composition> The manufacturing method includes the following modification step: reacting a silane monomer with a metal alkoxide to form a silane oligomer at least partially modified by the metal alkoxide. In the modification step, the silane oligomer is formed by polymerizing the silane monomer, and the formed silane oligomer can be modified by the metal alkoxide. In addition, in the modification step, after the silane monomer is modified by the metal alkoxide, the silane oligomer part can also be formed by reacting the modified silane monomer with other silane monomers.

[0087] The reaction can be carried out in a liquid medium. As the liquid medium, the same as described above can be exemplified. The amount of the liquid medium is not particularly limited, and for example, it can be an amount such that the concentration of the silane monomer in the reaction solution becomes 50% to 99% by mass (preferably 80% to 95% by mass).

[0088] The reaction conditions of the reaction are not particularly limited. For example, the reaction temperature of the reaction may be 60°C to 100°C, or 70°C to 90°C. In addition, the reaction time of the reaction may be, for example, 0.5 hours to 5.0 hours, or 1.0 hours to 3.0 hours.

[0089] The manufacturing method may further include the step of adding silane oligomer to the reaction solution after the modification step. Thus, a composition containing silane oligomer modified with metal alkoxide and unmodified silane oligomer can be obtained.

[0090] The manufacturing method may further include a step of adding a silane monomer to the reaction solution after the modification step. That is, the manufacturing method may be a method comprising: a first step of preparing a silane oligomer at least partly modified with a metal alkoxide; and a second step of mixing the modified silane oligomer with the silane monomer to obtain a barrier material forming composition, and the first step may be the modification step. In this way, a composition containing a silane monomer can be obtained.

[0091] In addition, the present production method may further include the step of adding other components to the reaction solution after the modification step. In addition, the present production method may further include the step of adding a liquid medium to the reaction solution after the modification step, or the step of replacing the liquid medium in the reaction solution after the modification step with another liquid medium. Through these steps, various aspects of the composition can be prepared from the reaction solution after the modification step.

[0092] <Barrier Material> The barrier material of this embodiment includes a polysiloxane compound doped with metal atoms. The barrier material may be formed by heating the barrier material forming composition. By heating, the silane oligomer and the silane monomer in the composition are polymerized to form a polysiloxane compound. At this time, the silane oligomer is modified with a metal alkoxide, and therefore, the formed polysiloxane compound is doped with metal atoms derived from the metal alkoxide.

[0093] The polysiloxane compound has a siloxane skeleton. In the polysiloxane compound, metal atoms are bonded to silicon atoms constituting the polysiloxane skeleton via oxygen atoms.

[0094] The silicon atoms contained in the polysiloxane compound can be divided into silicon atoms bonded to one oxygen atom (M unit), silicon atoms bonded to two oxygen atoms (D unit), silicon atoms bonded to three oxygen atoms (T unit), and silicon atoms bonded to four oxygen atoms (Q unit). Examples of the M unit, D unit, T unit, and Q unit include the above formula (M), formula (D), formula (T), and formula (Q), respectively.

[0095] 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, further preferably 90% or more, and may be 100%. According to such a polysiloxane compound, the moisture resistance of the barrier material is further improved.

[0096] In a preferred embodiment, the polysiloxane compound preferably contains T units. The content of T units in the polysiloxane compound relative to the total number of silicon atoms may be, for example, 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more, preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and may be 100%. According to such a polysiloxane compound, there is a tendency that the softness and moisture-removing property are further improved.

[0097] In another preferred embodiment, the content of the Q unit in the polysiloxane compound relative to the total number of silicon atoms may be, for example, 50% or more, preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and may be 100%. According to such a polysiloxane compound, there is a tendency that the moisture resistance and transparency are further improved.

[0098] In the polysiloxane compound, the molar ratio (M / Si) of the metal atoms M relative to the total number of silicon atoms (Si) may be, for example, 0.0001 or more, preferably 0.001 or more. This tends to improve the curability. In addition, the molar ratio (M / Si) may be, for example, 0.5 or less, preferably 0.2 or less. This tends to improve the transparency.

[0099] In the polysiloxane compound, most of the oxygen atoms are preferably bonded to at least one silicon atom. In the polysiloxane compound, alcoholic hydroxyl groups (C-OH) and ether bonds (COC) are few, and thus, the moisture resistance and moisture desorption properties tend to be further improved. For example, among the oxygen atoms in the polysiloxane compound, preferably, for example, 90% or more are bonded to silicon atoms, more preferably, 95% or more are bonded to silicon atoms, and even more preferably, 99% or more are bonded to silicon atoms.

[0100] The barrier material has a low water vapor permeability and excellent moisture resistance. The water vapor permeability (40°C, 95% RH) of the barrier material per 25 μm thickness may be, for example, 600 g / m 2·day or less, preferably 300 g / m 2·day or less, and further preferably 100 g / m 2·day or less.

[0101] In addition, the water vapor permeability (40°C, 95%RH) of the barrier material per 25 μm thickness can be, for example, 1 g / m 2·day or more, preferably 10 g / m 2·day or more. Such a barrier material has dehumidification properties, and even when used in a high temperature environment, it can fully suppress damage caused by the expansion of water that penetrates into the interior. Furthermore, the water vapor permeability of the barrier material represents the value measured by the Lyssy method in accordance with Japanese Industrial Standards (JIS) K7129.

[0102] The barrier material may also be transparent. Such a barrier material can be preferably used for applications requiring transparency, for example, it can be preferably used as a coating material on an image sensor in an image sensor package. Furthermore, transparency here means that the visible light transmittance (light transmittance of 550 nm) per 1 mm thickness is 95% or more.

[0103] The visible light transmittance (550 nm light transmittance) of the barrier material per 1 mm thickness is preferably 95% or more, more preferably 97% or more, and further preferably 99% or more. The visible light transmittance of the barrier material is measured by a spectrophotometer.

[0104] 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 may be used as a moisture-proof barrier film. In addition, the barrier material may be formed in a manner that fills the gaps between the components, in which case moisture can be prevented from entering the gaps. In addition, the barrier material may be formed in a manner that covers the components, in which case the components can be prevented from contacting with moisture.

[0105] <Method for producing barrier material> The method for manufacturing the barrier material of the present embodiment includes a heating step of heating the composition to form the barrier material. In the manufacturing method, the silane oligomer and the silane monomer in the composition are polymerized by heating to form a polysiloxane compound. At this time, in the composition, at least a part of the silane oligomer is modified by a metal alkoxide, so that the polysiloxane compound is doped with metal atoms derived from the metal alkoxide.

[0106] In the heating step, the liquid medium in the composition can be removed by heating. That is, the heating step can be a step of forming a barrier material containing a polysiloxane compound by heating and drying the composition.

[0107] The heating temperature in the heating step is not particularly limited, as long as it is a temperature at which the silane oligomer can be polymerized. In addition, when the composition includes 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 more, preferably 100° C. or more. In addition, the heating temperature may be, for example, 200° C. or less, preferably 170° C. or less.

[0108] The manufacturing method may further include a coating step of coating the composition. In this case, the heating step may refer to a step of heating the coated composition.

[0109] The method for applying the composition is not particularly limited and can be appropriately changed according to the shape of the object to be applied, the thickness of the barrier material, etc.

[0110] In the manufacturing method, the composition can be applied to an object to be given moisture resistance, and a barrier material can be formed on the object. In addition, in the manufacturing method, after manufacturing a barrier material of a predetermined shape, the manufactured barrier material can be applied to the object.

[0111] <Use of barrier materials> The use of the barrier material of this embodiment is not particularly limited, and can be preferably applied to various uses requiring moisture resistance. For example, the barrier material can be preferably used as a moisture-proof barrier material for electronic parts.

[0112] The barrier material of this embodiment can fully suppress the damage caused by the expansion of water intruding into the interior under high temperature environment (for example, above 100°C). As a barrier material, it can be preferably used in applications such as moisture barrier materials for electronic parts used in high temperature environments and moisture barrier materials for electronic parts that undergo high temperature steps during installation. Specifically, it can be preferably used as moisture barrier materials for power semiconductors, moisture barrier materials for image sensors, moisture barrier materials for displays, etc.

[0113] A preferred form of the use of the barrier material is described in detail below, but the use of the barrier material is not limited to the following.

[0114] <Application Example 1> One form of use is related to a product having a component that has been treated to prevent moisture. The product includes: a component; and a barrier material formed on the component. The barrier material can be formed on one component or on multiple components. The barrier material can be formed, for example, by covering one or more components or by covering a joint between two components.

[0115] This product is manufactured by the following manufacturing method, which includes: a first step of coating the barrier material forming composition on the component; and a second step of heating the coated composition to form the barrier material on the component.

[0116] Specific examples of such applications include the following electronic components.

[0117] (Electronic Components A-1) An electronic component of one form includes: a substrate; a cover glass; an image sensor disposed between the substrate and the cover glass; a support member that supports the cover glass and the image sensor on the substrate; and the blocking material disposed on the joint between the cover glass and the support member.

[0118] The barrier material has excellent moisture resistance, and even when used in a high temperature environment, it can fully suppress damage caused by expansion of moisture that has penetrated into the interior. Therefore, the electronic component has excellent moisture resistance, and even when moisture penetrates into the gap between the cover glass and the substrate, it can fully prevent the cover glass, the supporting member, etc. from being damaged by the expansion of the moisture.

[0119] Such an electronic component can be manufactured, for example, by the following manufacturing method, which includes: a coating step of coating a barrier material forming composition on a joint portion between a support member and a cover glass; and a barrier material forming step of heating the coated composition to form a barrier material on the joint portion.

[0120] (Electronic Components A-2) An electronic component of one form includes: a substrate; an image sensor disposed on the substrate; and the blocking material disposed on the image sensor.

[0121] The barrier material can be made to have excellent moisture resistance and transparency. Therefore, the barrier material can also be preferably used as a sealing material for sealing an image sensor. Such an electronic component can form an image sensor package without using a cover glass, so it is expected to reduce the size of the component and improve operability.

[0122] In the above application, the visible light transmittance (550 nm) of the barrier material per 1 mm thickness is preferably 95% or more, more preferably 97% or more, and further preferably 99% or more.

[0123] Such an electronic component can be manufactured, for example, by the following manufacturing method, which includes: a coating step of coating a barrier material forming composition on an image sensor; and a barrier material forming step of heating the coated composition to form a barrier material on the image sensor.

[0124] <Application Example 2> One form of use is related to a product having a first component and a second component joined to the first component, and the joint between the first component and the second component is subjected to moisture-proof treatment. The product includes: a first component, a second component, and a barrier material disposed between the first component and the second component, and the first component and the second component are joined via the barrier material.

[0125] This product can be manufactured by the following manufacturing method, which includes: a first step of configuring a barrier material forming composition between a first component and a second component; and a second step of heating the composition to form a barrier material, and bonding the first component and the second component via the barrier material.

[0126] Specific examples of such applications include the following electronic components.

[0127] (Electronic Components B-1) An electronic component of one form includes: a substrate; a cover glass; an image sensor disposed between the substrate and the cover glass; a support member that supports the cover glass and the image sensor on the substrate; and a barrier material that joins the cover glass and the support member.

[0128] The barrier material has excellent moisture resistance, and even when used in a high temperature environment, it can fully suppress damage caused by expansion of moisture that has penetrated into the interior. Therefore, the electronic component has excellent moisture resistance, and even when moisture penetrates into the gap between the cover glass and the substrate, it can fully prevent the cover glass, the supporting member, etc. from being damaged by the expansion of the moisture.

[0129] Such an electronic component can be manufactured, for example, by the following manufacturing method, which includes: a step of arranging a barrier material forming composition between a support member and a cover glass; and a step of heating the composition to form a barrier material, and bonding the support member and the cover glass via the barrier material.

[0130] <Application Example 3> One form of use is related to a product including a moisture-proof component. Such a product includes a moisture-proof component including a barrier material, for example, an assembly of multiple components including the moisture-proof component.

[0131] This product can be manufactured by the following manufacturing method, which includes: a first step of heating the barrier material forming composition to make a moisture-proof component containing the barrier material; and a second step of assembling multiple components containing the moisture-proof component.

[0132] Specific examples of such applications include the following electronic components.

[0133] (Electronic Components C-1) An electronic component of one form includes: a substrate; at least one component selected from the group consisting of a micro-electro mechanical system (MEMS) sensor, a wireless module and a camera module; and a moisture-proof component having a barrier material.

[0134] The barrier material has excellent moisture resistance and moisture desorption properties. Therefore, the electronic component has excellent moisture resistance and can fully prevent the degradation of sensing characteristics caused by moisture absorption.

[0135] Such an electronic component can be manufactured, for example, by the following manufacturing method, the manufacturing method comprising: a step of manufacturing a moisture-proof member having a barrier material by heating a barrier material forming composition; and a step of assembling a plurality of members including the moisture-proof member. Here, the barrier material can be formed independently of the substrate and the component, or can be formed integrally with the component by heating the barrier material forming composition applied to the component.

[0136] As mentioned above, the preferred embodiments of the present invention have been described, but the present invention is not limited to the above embodiments. [Example]

[0137] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.

[0138] (Example 1) [Barrier Material Forming Composition 1] 3.8 parts by mass of sec-aluminum butoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., product name: AL-3001, hereinafter referred to as "AL-3001"), 7.6 parts by mass of tert-butyl alcohol (Wako Pure Chemical Industries, Ltd.), 0.3 parts by mass of water, and 64.9 parts by mass of silane oligomer (manufactured by Momentive, product name: XR31-B1410) were mixed and reacted at 70° C. for 1 hour. Subsequently, 23.4 parts by mass of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-13, hereinafter referred to as "MTMS") were mixed to obtain a barrier material forming composition 1.

[0139] [Evaluation substrate 1 with barrier material] A single side of a 0.4 mm thick copper-clad laminate MCL-E-705G (manufactured by Hitachi Chemical Co., Ltd., product name) was masked and immersed in a copper etching solution to prepare a 40 mm square base substrate from which the copper foil on one side was removed. Subsequently, a barrier material forming composition 1 was applied to the surface of the base substrate from which the copper foil was removed so that the thickness after drying was 35 μm, and dried at 150° C. for 4 hours. In this way, a barrier material was formed on the substrate, thereby obtaining an evaluation substrate 1 with a barrier material.

[0140] (Example 2) [Barrier material forming composition 2] 3.8 parts by mass of AL-3001, 7.6 parts by mass of tertiary butyl alcohol, 0.3 parts by mass of water, and 64.9 parts by mass of silane oligomer (produced by Momentive, product name: XR31-B2733) were mixed and reacted at 70° C. for 1 hour. Then, 23.4 parts by mass of tetraethoxysilane (produced by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “TEOS”) was mixed to obtain a barrier material forming composition 2.

[0141] [Evaluation substrate 2 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 2, thereby obtaining an evaluation substrate 2 with a barrier material.

[0142] (Example 3) [Barrier material forming composition 3] A barrier material forming composition 3 was obtained in the same manner as in Example 2 except that 23.4 parts by mass of MTMS was mixed instead of TEOS.

[0143] [Evaluation substrate 3 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 3, thereby obtaining an evaluation substrate 3 with a barrier material.

[0144] (Example 4) [Barrier material forming composition 4] 3.8 parts by mass of AL-3001, 7.6 parts by mass of tertiary butyl alcohol, 0.3 parts by mass of water, and 64.9 parts by mass of silane oligomer (produced by Momentive, product name: TSR-165) were mixed and reacted at 70° C. for 1 hour. Subsequently, 23.4 parts by mass of TEOS was mixed to obtain a barrier material forming composition 4.

[0145] [Evaluation substrate 4 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 4, thereby obtaining an evaluation substrate 4 with a barrier material.

[0146] (Example 5) [Barrier material forming composition 5] A barrier material forming composition 5 was obtained in the same manner as in Example 1 except that 23.4 parts by mass of TEOS was mixed instead of MTMS, and 2.0 parts by mass of CR15 (product name, manufactured by Momentive Corporation) was mixed as a curing catalyst.

[0147] [Evaluation substrate 5 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 5, thereby obtaining an evaluation substrate 5 with a barrier material.

[0148] (Example 6) [Barrier Material Forming Composition 6] 2.0 parts by mass of a hardening catalyst (CR15) was further mixed with the barrier material forming composition 2 of Example 2 to obtain a barrier material forming composition 6.

[0149] [Evaluation substrate 6 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 6, thereby obtaining an evaluation substrate 6 with a barrier material.

[0150] (Example 7) [Barrier material forming composition 7] 2.0 parts by mass of a hardening catalyst (CR15) was further mixed with the barrier material forming composition 3 of Example 3 to obtain a barrier material forming composition 7.

[0151] [Evaluation substrate 7 with barrier material] A barrier material was formed on a substrate in the same manner as in Example 1 except that the barrier material-forming composition 1 was changed to the barrier material-forming composition 7, thereby obtaining an evaluation substrate 7 with a barrier material.

[0152] (Example 8) [Barrier material forming composition 8] A barrier material forming composition 8 was obtained in the same manner as in Example 2 except that 23.4 parts by mass of methyl silicate MS53A (product name, manufactured by Colcoat Co., Ltd.) was mixed instead of TEOS.

[0153] [Evaluation substrate 8 with barrier material] An evaluation substrate 8 with a barrier material was obtained in the same manner as in Example 1 except that the barrier material forming composition 1 was changed to the barrier material forming composition 8.

[0154] (Example 9) [Barrier material forming composition 9] 3.8 parts by mass of AL-3001, 7.6 parts by mass of tertiary butyl alcohol, 0.3 parts by mass of water, and 64.9 parts by mass of MTMS were mixed and reacted at 70° C. for 1 hour. Subsequently, 23.4 parts by mass of TEOS and 2.0 parts by mass of a curing catalyst (CR15) were mixed to obtain a barrier material forming composition 9.

[0155] [Evaluation substrate 9 with barrier material] An evaluation substrate 9 with a barrier material was obtained in the same manner as in Example 1 except that the barrier material forming composition 1 was changed to the barrier material forming composition 9.

[0156] (Comparative Example 1) [Comparative evaluation substrate 1] A copper-clad laminate MCL-E-705G having a thickness of 0.4 mm and a size of 40 mm square was used as an evaluation substrate of Comparative Example 1 (comparative evaluation substrate 1).

[0157] (Comparative Example 2) [Comparative evaluation substrate 2] The base substrate produced by the method described in Example 1 was used as an evaluation substrate of Comparative Example 2 (comparative evaluation substrate 2).

[0158] The evaluation substrates obtained in the examples and comparative examples were evaluated by measuring the water absorption rate at constant temperature and humidity and the moisture desorption rate at high temperature using the following method. The results are shown in Table 1.

[0159] <(1) Determination of water absorption under constant temperature and humidity> The evaluation substrate was dried at 130°C for 1 hour using a safety oven (manufactured by Espec Co., Ltd., product name: SPHH-202) to obtain a measurement sample. The mass of the obtained measurement sample was measured to obtain the initial mass m1. Then, the obtained measurement sample was treated for 100 hours in an environment of 85°C / 85%RH using a constant temperature and humidity chamber (manufactured by Kato Co., Ltd., product name: SE-44CI-A) to obtain a sample after constant temperature and humidity treatment. The mass of the measurement sample after constant temperature and humidity treatment was measured to obtain the mass m2 after constant temperature and humidity treatment. Based on the initial mass m1 and the mass m2 after constant temperature and humidity treatment, the water absorption rate QA (%) was calculated by the following formula. QA=100×(m1-m2) / m2

[0160] <(2) Dehumidification rate at high temperature> The sample after the constant temperature and humidity treatment in (1) was dried at 130°C for 1 hour using a safety oven (manufactured by Espec Co., Ltd., product name: SPHH-202) to obtain a sample after high temperature treatment. The mass m3 of the sample after high temperature treatment was measured, and the moisture removal rate QD (%) was calculated based on m1, m2 and m3 using the following formula. QD=100×{1-(m3-m2) / (m1-m2)}

[0161] [Table 1] Water absorption Dehumidification rate Example 1 0.26 98.4 Example 2 0.21 98.6 Example 3 0.29 98.4 Example 4 0.24 98.2 Example 5 0.20 98.6 Example 6 0.20 98.8 Example 7 0.27 98.6 Example 8 0.19 98.8 Example 9 0.20 98.6 Comparative Example 1 0.09 66.6 Comparative Example 2 0.46 65.2

[0162] Comparison between Examples 1 to 9 and Comparative Example 2 shows that the barrier materials of Examples 1 to 9 sufficiently suppress the water absorption rate under constant temperature and humidity, and that the barrier materials of Examples 1 to 9 have excellent moisture resistance. In addition, comparison between Examples 1 to 9 and Comparative Example 1 shows that the barrier materials of Examples 1 to 9 have a superior dehumidification rate for escaping internal moisture to the outside, compared with the case of using a copper plate coating.

[0163] In addition, when the water absorption rate after the dehumidification rate is measured is compared, the comparative example 1 is about 0.03%, while the examples 1 to 9 are less than 0.005%. Therefore, it is confirmed that when the barrier materials of examples 1 to 9 are used, the internal moisture can be significantly reduced by drying.

[0164] Furthermore, the transmittance of the barrier materials formed in Examples 1 to 9 with respect to light of 550 nm per 1 mm thickness was measured, and the result was 95% or more in any of the Examples.

Claims

1. A composition for forming a barrier material comprising a silane oligomer containing silicon atoms bonded to three oxygen atoms, wherein at least a portion of the silane oligomer is modified with a metal alkoxide represented by M(OR1)n, wherein M represents an n-valent metal atom, which is aluminum, titanium, zirconium or niobium, R1 is an alkyl group having 1 to 6 carbon atoms, and n is 2 to 5.

2. The composition as claimed in claim 1, wherein 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 in the silane oligomer is 50% or more.

3. The composition as claimed in claim 1, further comprising a silane monomer.

4. The composition as claimed in claim 3, wherein the silane monomer contains silicon atoms bonded to 3 or 4 oxygen atoms.

5. The composition as claimed in claim 3, wherein the silane monomer is selected from the group consisting of alkyltrialkoxysilanes, aryltrialkoxysilanes, and tetraalkoxysilanes.

6. The composition as claimed in claim 3, wherein the content of the silane monomer is 100 parts by mass or less relative to 100 parts by mass of the silane oligomer.

7. The composition as claimed in claim 1, wherein the metal alkoxide is aluminum alkoxide.

8. A method for manufacturing a composition for forming a barrier material, comprising: The first step of preparing at least a portion of the silane oligomer modified with metal alkoxides represented by M(OR1)n; The second step involves mixing the silane oligomer with a silane monomer to obtain a composition for forming a barrier material, wherein the silane oligomer contains silicon atoms bonded to three oxygen atoms, and M represents an n-valent metal atom, which is aluminum, titanium, zirconium, or niobium, R1 is an alkyl group having 1 to 6 carbon atoms, and n is 2 to 5.

9. The manufacturing method as claimed in claim 8, wherein the first step comprises the steps of: reacting a silane oligomer containing silicon atoms bonded to three oxygen atoms with a metal alkoxide, and modifying at least a portion of the silane oligomer with the metal alkoxide.

10. The manufacturing method as claimed in claim 8, wherein the first step comprises the step of reacting a silane monomer with a metal alkoxide to form at least a portion of a silane oligomer modified with the metal alkoxide.

11. A method for manufacturing a barrier material, comprising the step of heating a composition as described in any one of claims 1 to 7 to form a barrier material.

12. A method for manufacturing a product treated with moisture-proof properties, the method comprising: The first step of applying the composition as described in any one of claims 1 to 7 onto the component; The second step involves heating the coated composition to form a barrier material on the component.

13. A method of manufacturing a moisture-proof product, the product having a first component and a second component joined to the first component, and the joint between the first component and the second component being moisture-proofed, the manufacturing method comprising: The first step of disposing of the component as described in any one of claims 1 to 7 between the first component and the second component; The second step involves heating the composition to form a barrier material and joining the first component and the second component via the barrier material.

14. A method for manufacturing a moisture-proof product, the method comprising: The first step of heating the composition as described in any one of claims 1 to 7 to produce a moisture-proof component having a barrier material; The second step involves assembling a plurality of components including the moisture-proof component.

15. A barrier material formed by heating a composition as claimed in any one of claims 1 to 7, the barrier material comprising a polysiloxane compound doped with metal atoms, and wherein the ratio of silicon atoms bonded to 3 oxygen atoms and silicon atoms bonded to 4 oxygen atoms to the total number of silicon atoms in the polysiloxane compound is 50% or more.

16. The barrier material as claimed in claim 15, wherein more than 90% of the oxygen atoms in the polysiloxane compound are bonded to silicon atoms.

17. The blocking material as claimed in claim 15, wherein the transmittance per 1 mm thickness is greater than 95% relative to light at 550 nm.

18. An electronic component comprising: member; And the blocking material as described in claim 15 formed on the component.

19. An electronic component comprising: A first component, a second component, and a barrier material as described in claim 15 disposed between the first component and the second component, wherein the first component and the second component are joined via the barrier material.

20. An electronic component comprising an assembly of a plurality of components having a moisture-proof component having a barrier material as described in claim 15.