JP5880238B2 - LAMINATE MEMBER, MANUFACTURING METHOD THEREOF, AND LAMINATE - Google Patents

Description

The present invention relates to a laminate member having an adhesive film on a base material, and a laminate in which another base material is laminated on the adhesive film of the laminate member. Specifically, the present invention relates to a laminate member capable of producing a laminate having excellent adhesion by having a porous film made of an inorganic material as an adhesive film on a substrate, and a laminate using the laminate member. .
The laminate member and laminate of the present invention are particularly suitably used as packaging materials, battery materials, optical materials, electric / electronic materials, and automobile materials.

In general, a polyester film or a polyimide film is used as an insulating film of a flexible printed wiring board used in electronic equipment. To laminate a copper foil, which is a conductor, on an insulating film such as a polyimide film to form a flexible printed wiring board, a method of providing an adhesive layer made of acrylic resin on the insulating film and then laminating the copper foil Is adopted (Japanese Patent Laid-Open No. 2010-222423).
However, since a high melting point material is used for the adhesive of the adhesive layer, there is a problem that the laminating process becomes high temperature and high pressure, and the flexible printed wiring board obtained after processing is warped.

In order to increase the adhesion strength between a film made of polyimide or epoxy resin, which is known as a resin that is difficult to bond with copper foil, and the copper foil, a roughening particle is used to increase the surface roughness of the copper foil. It has been proposed to perform the conversion processing (Japanese Patent Laid-Open No. 2010-13738).
In this method, by increasing the adhesion amount of roughened particles on the surface of the copper foil, the surface roughness of the copper foil surface can be increased and the adhesion to the resin film can be increased. It is not preferable to attach the crystallization particles, which is inappropriate for miniaturization of the wiring pattern.

On the other hand, for packaging materials such as foods, non-foods, and pharmaceuticals, a gas barrier that prevents gas such as oxygen and water vapor from permeating the packaging material in order to suppress the alteration of the contents and maintain their functions and characteristics. Sex is required. For this reason, conventionally, a packaging material made of a laminate film obtained by laminating a metal foil such as an aluminum foil, which is less affected by temperature and humidity, as a gas barrier layer on a base film has been generally used (Japanese Patent Laid-Open No. 2008-6663). No., JP-A-2008-184664).
However, since such a laminate film does not have sufficient adhesion between a metal foil such as aluminum and a base film, which is normally required for its use, the metal foil and the base film are peeled off during heat treatment. There was a problem that sometimes.

Conventionally, a solar cell module used for solar power generation is usually a glass substrate, an ethylene-vinyl acetate copolymer (EVA) sheet as a sealing material film, a silicon power generation element as a photoelectric conversion element, and a sealing material. An EVA sheet as a film and a back cover layer as a protective layer are laminated in this order (Japanese Patent Laid-Open No. 2002-170971).
However, the EVA sheet and the glass substrate have a problem in adhesion. In order to further enhance the adhesive force between the EVA sheet and the glass substrate, a silane coupling agent is blended or impregnated as an adhesion improver in the EVA sheet, but sufficient adhesion is not obtained.

JP 2010-222423 A JP 2010-13738 A JP 2008-6737 A JP 2008-184664 A JP 2002-170971 A

  An object of the present invention is to solve the above-mentioned conventional problems and provide a laminate member capable of realizing a laminate excellent in interlayer adhesion and adhesion, and a laminate using the laminate member. To do.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention improve interlayer adhesion by forming a specific porous film made of an inorganic material as an adhesive film on a substrate. I found.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] A laminate member having an adhesive film on a substrate, wherein the adhesive film is made of an inorganic material and has a modest pore size of 0.5 to 10 nm and a porosity of 15% or more. A laminate member characterized by being a porous film.

[2] The laminate member according to [1], wherein the inorganic material is silica.

[3] [1] or a method of manufacturing a laminated member according to [2] The method features and to Lula laminate-member comprises a step of forming a film of該接wear layer at 200 ° C. or less .

[4] A laminate in which another substrate is laminated on the adhesive film of the laminate member according to [1] or [ 2] .

[5] A laminate in which an adhesive layer and another base material are sequentially laminated on the adhesive film of the laminate member according to [1] or [ 2] .

According to the present invention, a porous film having a specific mode of pore diameter and porosity made of an inorganic material is formed on a substrate as an adhesive film. Adhesion can be improved.
When another base material is layered on this porous film and heated and pressurized, a part of the melted base material enters into the pores of the porous film and hardens, thereby exhibiting an anchor effect and adhesion. improves.
In addition, when another base material having an adhesive layer made of an adhesive or a pressure-sensitive adhesive is applied to the porous film and pressed, a part of the adhesive or the pressure-sensitive adhesive enters the pores of the porous film, resulting in an anchor effect. To improve adhesion.

It is typical sectional drawing which shows embodiment of the lamination member and laminated body of this invention.

Hereinafter, embodiments of a laminate member and a laminate according to the present invention will be described in detail with reference to the drawings.
Fig.1 (a) is typical sectional drawing which shows embodiment of the laminate member of this invention, FIG.1 (b), (c), (d) shows embodiment of the laminated body of this invention. It is typical sectional drawing.

  In the present invention, the term “adhesion” includes not only a state of being firmly bonded to such an extent that it cannot be peeled off after bonding, but also so-called “adhesion” that can be peeled off after bonding. .

[Laminate]
As shown in FIG. 1 (a), the laminate member 1 of the present invention is made of an inorganic material as an adhesive film on a substrate 2, and has a mode pore diameter of 0.5 to 10 nm and a porosity of 15%. The above porous film 3 is formed.

  Note that the laminate member of the present invention is not limited to one in which the porous film 3 is formed only on one surface of the base material 2 as shown in FIG. A material film 3 may be formed. In that case, the porous films formed on both surfaces of the substrate may be the same, or the constituent materials, the mode pore diameter, the porosity, the film thickness, etc. may be different.

<Base material>
Although there is no restriction | limiting in particular as the material of the base material of the laminate member of this invention, Generally, glass, resin, metal used in field | areas, such as a packaging material, a battery material, an optical material, an electrical / electronic material, and an automotive material , Ceramics, carbon materials, semiconductors, or composite materials containing two or more of these. In the present invention, a resin material having a low melting point is applied to the base material by using an inorganic material such as silica that can be formed at a relatively low temperature, as described later, as the porous film formed on the base material. It is also possible.

  As the resin material of the base material, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene, polysulfone, polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polycarbonate , Triacetyl cellulose, polyvinyl chloride, acrylic resin, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester Copolymers and their metal cross-linked products, silicone resins and the like can be mentioned. The resin material of the base material may be a composite resin containing two or more of these resins.

  Examples of the metal include various metals such as copper (Cu), aluminum (Al), and silver (Ag), various steels including stainless steel, and various alloys.

  Also, as glass, various shot glasses such as silicon dioxide, BK7, SF11, LaSFN9, BaK1, F2, etc., fluorinated glass, phosphorous glass, boron-phosphorous glass, borosilicate glass, synthetic fused silica glass, optical crown glass, Low expansion borosilicate glass, sapphire, soda glass, alkali-free glass, calcium fluoride and the like can be mentioned.

  Examples of the ceramic include boron nitride, silicon carbide, silicon nitride, aluminum nitride, alumina, silica alumina, ferrite, zirconia, hydroxyapatite, zinc oxide, and tin-doped indium oxide.

  Examples of the carbon material include carbon fiber, graphite, graphene, carbon nanotubes, fullerenes, diamond and the like.

  Examples of the semiconductor include silicon, germanium, gallium arsenide, gallium nitride, indium phosphide, and germanium silicide.

  Examples of composite materials containing two or more of these include fiber reinforced plastics and plastics containing ceramic particles.

  Any substrate made of these glass, resin, metal, ceramic, carbon material, semiconductor, or a composite material containing two or more of these, the surface of the substrate (in the present invention, the “surface of the substrate” The surface on which the porous film is formed)) is subjected to surface treatment such as primer coating, corona treatment, plasma treatment, heat treatment, solvent treatment, and roughening treatment before the porous film is formed. In some cases, it is possible to improve the adhesion with the porous film and thus the adhesion with other substrates.

  There is no restriction | limiting in particular in the form of a base material, All can be applied in arbitrary shapes, such as a film, a board, a crush piece, a spherical shape, a protrusion shape, a column shape, a dome shape, a rectangular parallelepiped including a cube. In addition to a periodic or irregular pattern, an aperiodic pattern such as a circuit diagram may be formed on the surface of the substrate. The substrate surface may be a flat surface, a curved surface, or a step. Note that the surface of the substrate does not necessarily have to be entirely covered with a porous film, and the effects of the present invention can be obtained even when the porous film is partially formed.

  The thickness of the base material varies depending on the form of the base material, the use of the laminate member and the laminate, and the material of the base material. Usually, it is about 30 to 3000 μm if it is a resin film, and if it is glass paper or metal foil. In the case of a glass substrate or a metal substrate, the thickness is about 0.3 to 25 mm.

<Porous membrane>
In the present invention, the mode pore diameter of the porous film formed on the substrate is 0.5 to 10 nm, preferably 2 to 5 nm.

  If the mode pore size is too small, a part of the base material melted at the time of forming the laminate, or the adhesive or the pressure sensitive adhesive does not sufficiently enter the pores of the porous film, and a sufficient anchor effect cannot be obtained. If the mode pore size is too large, the molten base material, adhesive, or pressure sensitive adhesive hole that is effective for the anchor effect when part of the molten base material or adhesive or pressure sensitive adhesive enters the pores of the porous membrane. Since the contact area between these intruders and the hole wall is small with respect to the amount of penetration, the anchor effect is small and the adhesion is not improved.

The mode pore diameter of the porous membrane in the present invention can be determined by measuring a BET nitrogen adsorption isotherm using a sample of the porous membrane. The BET nitrogen adsorption isotherm can be measured by, for example, AS-1 manufactured by Cantachrome.
The sample of the porous film may be obtained by peeling the porous film from the laminate member of the present invention before forming the laminate of the present invention, or a porous material such as a raw material liquid for forming a porous silica film described later. The film-forming coating solution may be applied to a substrate such as Teflon or silicone resin under the same conditions as those for forming the porous film and dried.

The porosity of the porous membrane according to the present invention is 15% to 70 %, preferably 20 to 50 %.
The small porosity of the porous membrane means that there are few pores to obtain the anchor effect, and the amount of the molten base material, adhesive, or adhesive entering the pores of the porous membrane is small. A sufficient anchor effect cannot be obtained, and the adhesion is not improved. When the porosity is too large, the mechanical strength of the porous membrane is insufficient, the porous membrane is easily broken, and the adhesion is not improved.

In addition, the porosity of a porous film is the ratio of the volume which the air layer in a porous film occupies, and can be measured with the following method.
That is, for a sample in which a porous film is formed on a substrate, the refractive index n of the porous film is measured by a spectroscopic ellipsometer, the refractive index of the inorganic material constituting the porous film is n ₁ , and the refractive index of air is When n ₀ and the porosity of the porous membrane are X (%), the following equation (i) is established. Therefore, the porosity X of the porous membrane can be obtained from the following equation (ii).
_{n 1 × (100-X)} + n 0 × X = n × 100 (i)
X = (100n ₁ -100n) / (n ₁ -n ₀ ) (ii)
For example, when the inorganic material constituting the porous film is silica, the refractive index of silica n ₁ = 1.47 and the refractive index of air n ₀ = 1.00,
1.47 × (100−X) + 1.00 × X = n
And
X = (147-100n) /0.47
Is required.

  There is no particular limitation on the inorganic material that is a constituent material of the porous membrane, but it has excellent heat resistance, no problem of deterioration over time, can form a transparent porous membrane, and is compared at 200 ° C. or lower. Silica is preferable because it can be formed at a low temperature.

The reason why heat resistance and transparency are required for the porous membrane is as follows.
That is, the base material is melt-processed in the laminating step when the base material of the invention is manufactured by laminating another base material or another base material via the adhesive layer to the laminate member of the invention, or In order to prevent the porous film from changing in the heating process such as partial heat treatment such as heat sealing, heat treatment such as heat treatment, etc. Is desired to have excellent heat resistance.
Moreover, when applied to transparent materials such as optical and food container applications, the porous film is required to have excellent transparency.

  Moreover, if it can form into a film at 200 degrees C or less, for example, about 20-120 degreeC, a low melting point resin material can be applied as a base material, The application range is expanded greatly.

A porous film made of silica suitable for the present invention (hereinafter sometimes referred to as “the porous silica film of the present invention”) is preferably composed mainly of a silica (SiO ₂ ) composition. The porous silica film has a SiOx composition (provided that a silicon atom-carbon atom bond exists in a part of the silica composition by, for example, copolymerizing organic silanes in silica synthesis by a sol-gel method). , X is a positive number greater than 0 and less than 2.

  The production method of the porous silica membrane of the present invention is not particularly limited as long as it satisfies the above-mentioned mode pore diameter and porosity, but the porous silica membrane of the present invention can be produced efficiently and with high productivity. Examples of methods that can be membraned are detailed below.

(Method for forming porous silica film)
The porous silica film of the present invention is formed by the following steps.
(A) Step of preparing a raw material liquid for forming a porous silica film (b) Step of forming a porous silica film from the raw material liquid (c) Step of drying the porous silica film Hereinafter, each step will be described.

(A) a step of preparing a raw material liquid for forming a porous silica film;
The raw material liquid for forming the porous silica film is a hydrous organic solution mainly containing alkoxysilanes and containing a raw material compound capable of increasing the molecular weight by a hydrolysis reaction and a dehydration condensation reaction.

  The water-containing organic solution that is the raw material liquid for forming the porous silica film of the present invention contains alkoxysilanes, an organic solvent, water, and a catalyst that is added as necessary.

  Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetraisopropoxysilane, tetra (n-butoxy) silane, and the like, trimethoxysilane, triethoxysilane, and methyl. Trialkoxysilanes such as trimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, bis (Trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,4-bis (tri Toxylsilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,3,5-tris (trimethoxysilyl) benzene and the like, in which two or more trialkoxysilyl groups are bonded, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, An alkyl group substituted on a silicon atom, such as 3-carboxypropyltrimethoxysilane, has a reactive functional group, and may be a partial hydrolyzate or oligomer.

  Among these, tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, tetramethoxysilane, or tetraethoxysilane oligomer is particularly preferable. In particular, tetramethoxysilane oligomers are most preferably used because of their reactivity and controllability of gelation.

  Furthermore, monoalkoxysilanes having 2 to 3 hydrogen, alkyl groups, or aryl groups on silicon atoms can be mixed with the alkoxysilanes. By mixing monoalkoxysilanes, the resulting porous silica membrane can be hydrophobized to improve water resistance. Examples of monoalkoxysilanes include triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, and the like. The mixing amount of monoalkoxysilanes is desirably 70 mol% or less of the total alkoxysilanes. If the mixing amount exceeds 70 mol%, ideal gelation may not occur.

  (3,3,3-trifluoropropyl) trimethoxysilane, (3,3,3-trifluoropropyl) triethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, triethoxy-1H, When an alkoxysilane having a fluorinated alkyl group or a fluorinated aryl group such as 1H, 2H, 2H-tridecafluorooctylsilane is used in combination, excellent water resistance, moisture resistance, contamination resistance, and the like may be obtained.

The shape of the oligomer in the raw material liquid is not particularly limited, and examples thereof include linear, cross-linked, cage-type molecules (silsesquioxane, etc.) and the like.
In addition, when applying the above-described raw material liquid, it is necessary that a certain degree of high molecular weight (that is, a state in which condensation has progressed to some extent) has already been achieved. It is preferable that high molecular weight is achieved so that there is no insoluble matter and the raw material liquid maintains fluidity. The reason for this is that if a visible insoluble material exists in the raw material solution before coating, the film structure becomes non-uniform, cracks may occur from the insoluble material, and mechanical strength may be reduced. Because there is.

  As the organic solvent, those having the ability to mix alkoxysilanes constituting the raw material liquid, water and other organic compounds are preferably used. Examples of usable organic solvents include monohydric alcohols having 1 to 4 carbon atoms, dihydric alcohols having 1 to 4 carbon atoms, and alcohols such as polyhydric alcohols such as glycerin and pentaerythritol. These organic solvents may be used alone or as a mixture.

  In order to make the porous silica film of the present invention have an appropriate stable structure, an organic solvent having the ability to mix water and other organic compounds is preferable, among which methanol, ethanol, n-propanol, isopropyl alcohol, and butanol are more preferable. Further, methanol, ethanol and isopropyl alcohol are most preferable.

  A catalyst is mix | blended as needed. Examples of the catalyst include substances that promote the hydrolysis and dehydration condensation reactions of the alkoxysilanes described above. Specific examples include acids such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and maleic acid; amines such as ammonia, hydrazine, butylamine, dibutylamine and triethylamine; bases such as pyridine; acetylacetone complex of aluminum, etc. Lewis acids; and the like.

  Examples of the metal species of the metal chelate compound used as the catalyst include titanium, aluminum, zirconium, tin, and antimony. Specific examples of the metal chelate compound include the following.

  Examples of aluminum complexes include diethoxymono (acetylacetonate) aluminum, di-n-propoxy (acetylacetonato) aluminum, diisopropoxy (acetylacetonato) aluminum, di-n-butoxy (acetylacetonato) aluminum, di-sec. -Butoxy (acetylacetonato) aluminum, di-tert-butoxy (acetylacetonato) aluminum, ethoxybis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, diethoxy (ethylacetoacetate) aluminum, ethoxybis (ethylacetoacetate) And aluminum chelate compounds such as aluminum and tris (ethylacetoacetate) aluminum.

  Examples of the titanium complex include triethoxy (acetylacetonato) titanium, tri-n-propoxy (acetylacetonato) titanium, triisopropoxy (acetylacetonato) titanium, tri-n-butoxy (acetylacetonato) titanium, tri-sec. -Butoxy (acetylacetonato) titanium, tri-tert-butoxy (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, ethoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy (ethylacetate) Acetate) titanium, diethoxybis (ethyl acetoacetate) titanium, ethoxytris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, (acetylacetonate) ) Tris (ethyl acetoacetate) may be cited titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonate) and (ethylacetoacetate) titanium.

  In addition to these catalysts, weak alkaline compounds such as basic catalysts such as ammonia may be used. In this case, it is preferable to appropriately adjust the silica concentration, the organic solvent species, and the like. Moreover, when preparing a water-containing organic solution, it is preferable not to increase the catalyst concentration in a solution rapidly. As a specific example, there is a method of mixing alkoxysilanes and a part of an organic solvent, then mixing water, and finally mixing the remaining organic solvent and base.

  In order to make the local hydrolysis reaction and dehydration condensation reaction to be performed later optimally, the silica network structure needs to be formed homogeneously. The addition amount of the catalyst is preferably adjusted according to the reaction rate of the raw material. The hydrolysis reaction and the dehydration condensation reaction may proceed simultaneously. In that case, the pH is preferably adjusted to 3 to 7, more preferably adjusted to 4 to 6. Alternatively, the hydrolysis reaction may proceed preferentially under acidic conditions, and the dehydration condensation reaction may proceed preferentially under alkaline conditions. The hydrolysis reaction is preferably adjusted to pH 8 or lower, more preferably adjusted to pH 5 or lower. The dehydration condensation reaction is preferably adjusted to have a pH of 6 or more, and more preferably adjusted to have a pH of 9 or more.

The raw material liquid for forming the porous silica film of the present invention is formed by blending the above-mentioned raw materials.
The blending ratio of the alkoxysilanes is preferably 1 to 60% by weight and more preferably 5 to 40% by weight with respect to the whole raw material liquid. When the blending ratio of alkoxysilanes exceeds 60% by weight, it is difficult to maintain the stability of the raw material liquid, and the porous silica film may be broken during film formation. On the other hand, when the compounding ratio of alkoxysilanes is less than 1% by weight, the hydrolysis reaction and dehydration condensation reaction may be extremely slow, or the film formability may be deteriorated (film unevenness).

  Water is necessary for the hydrolysis of alkoxysilanes, and is important from the viewpoint of the stability of the coating solution and the film forming property of the porous silica film. Therefore, when the amount of water required for hydrolysis is defined by a molar ratio with respect to the amount of alkoxy groups, it is 0.1 to 1.6 mol times the amount of 1 mol of alkoxy groups in the alkoxysilane, particularly 0.3 to 1 .2 mole times, particularly 0.5 to 1.0 mole times is preferred. The amount of water in the coating solution is not limited to this, and in order to adjust the stability of the coating solution and the film forming property, it is added in an upper limit of 50 mol times, preferably 40 mol times after the hydrolysis reaction. Also good.

  Water may be added at any time after the alkoxysilanes are dissolved in an organic solvent. Desirably, the alkoxysilanes, catalyst and other additives are sufficiently dispersed in the solvent, and then water is added. The hydrolysis reaction is caused by adding water, but the water can be added as an aqueous alcohol solution or as water vapor without being particularly limited. In addition, if water is added rapidly, depending on the type of alkoxysilane, the hydrolysis reaction and the dehydration condensation reaction occur too quickly, and precipitation may occur. Therefore, in order to prevent such precipitation, take sufficient time to add water, make the alcohol solvent coexist in a state where water is added uniformly, and add water at a low temperature. It is preferable to use means such as suppressing the reaction alone or in combination.

  As the water to be used, it is preferable to use water subjected to any one of treatments such as ion exchange, distillation, and filtration, or a combination of two or more. For example, when the porous silica film of the present invention is used in an application field that particularly dislikes minute impurities such as battery materials, optical materials, and electric / electronic materials, a porous silica film with higher purity is required. It is desirable to use ion-exchanged water and use ultrapure water that has passed through a filter having a pore size of 0.01 to 2 μm, for example.

The atmospheric temperature in the preparation of the raw material liquid and the mixing order are arbitrary, but in order to obtain a uniform structure formation in the raw material liquid, water is preferably mixed last. In addition, in order to suppress extreme hydrolysis and dehydration condensation reaction of alkoxysilanes in the raw material liquid, the raw material liquid is usually prepared at a temperature range of 0 to 60 ° C., particularly 15 to 40 ° C., particularly 15 to 30 ° C. It is preferable to carry out under wet conditions.
At the time of liquid preparation, the stirring operation of the raw material liquid is arbitrary, but it is more preferable to stir every mixing.

  Further, after the raw material solution is prepared, the solution is preferably aged in order to promote hydrolysis and dehydration condensation reaction of alkoxysilanes. During this ripening period, it is preferable that the hydrolyzed condensate of the alkoxysilanes to be produced is in a state of being more uniformly dispersed in the raw material liquid, so that the liquid is preferably stirred.

  The temperature during the aging period is arbitrary, and in general, it may be heated at room temperature or continuously or intermittently. Among these, heat aging is preferable in order to form a uniform three-dimensional network structure by the hydrolysis condensate of alkoxysilanes. The specific temperature is not particularly limited as long as it is equal to or lower than the boiling point of the organic solvent to be used, and heat aging can be performed at a temperature equal to or higher than the boiling point of the organic solvent used under pressure. The heat aging time is appropriately adjusted depending on the temperature to be applied, but is preferably 15 hours or less, and more preferably 5 hours or less.

(B) Step of forming a porous silica film from a raw material liquid The porous silica film is formed by applying the raw material liquid prepared above onto the substrate of the laminate member of the present invention described above.
The raw material liquid may be used as it is, and depending on the coating method, it may be diluted with the organic solvent used for preparing the raw material liquid, water, or a mixed solvent of organic solvent and water used for preparing the raw material liquid. Good. In the case of dilution, the raw material liquid is usually diluted 5 times or less, more preferably 4 times or less, and most preferably 2 times or less.

  As a means for applying the raw material liquid, a casting method in which the raw material liquid is extended onto the substrate using a bar coater, an applicator or a doctor blade, a dip method in which the substrate is immersed in the raw material liquid, and a spin coating method are used. Well-known methods can be mentioned. In order to continuously form a homogeneous film, the casting method is particularly preferable.

  When the raw material liquid is applied by the casting method, the casting speed is 0.1 to 1000 m / min, preferably 0.5 to 700 m / min, and more preferably 1 to 500 m / min. The rotation speed in the place where the raw material liquid is applied and formed by the spin coating method is 10 to 100,000 rotations / minute, preferably 50 to 50,000 rotations / minute, and more preferably 100 to 10,000 rotations / minute.

  In the dip coating method, the substrate may be dipped in the raw material liquid and pulled up at an arbitrary speed. The pulling speed at this time is preferably 0.01 to 100 mm / sec, more preferably 0.05 to 80 mm / sec, and particularly preferably 0.1 to 50 mm / sec. Although there is no restriction | limiting in the speed | rate which immerses a base material in a raw material liquid, It is preferable to immerse a base material in a raw material liquid at a speed | rate comparable as a raising speed | rate. The substrate may be immersed for an appropriate period of time until it is immersed in the raw material liquid and pulled up, and this duration is usually 1 second to 48 hours, preferably 3 seconds to 24 hours, more preferably 5 seconds to 12 hours.

  The atmosphere during coating may be air or an inert gas such as nitrogen or argon, and the temperature is usually 0 to 60 ° C., preferably 10 to 50 ° C., more preferably 20 to 40 ° C. The humidity is usually 5 to 90%, preferably 10 to 80%, more preferably 15 to 70%. There is a difference in the drying speed between the dip coating method and the spin coating method, and a slight difference may occur in the stable structure of the film immediately after coating. This can be adjusted by changing the atmosphere during application. In addition, it can be dealt with by surface treatment of the substrate.

(C) a step of drying the porous silica membrane;
The drying step is performed for the purpose of removing volatile components remaining in the porous silica membrane and / or for the purpose of proceeding the hydrolysis condensation reaction of alkoxysilanes. The drying temperature is 0 to 200 ° C., preferably 5 to 190 ° C., more preferably 10 to 180 ° C., and the drying time is 10 seconds to 50 hours, preferably 20 seconds to 30 hours, more preferably 30 seconds to 15 hours.

  The drying method can be performed by a known method such as blow drying or drying under reduced pressure, and may be combined. After the blast drying, vacuum drying for the purpose of sufficiently removing volatile components can be added.

  By treating the obtained porous silica film with a silylating agent, it is possible to make the surface more functional. By treating with a silylating agent, hydrophobicity is imparted to the porous silica film and the pores can be prevented from being contaminated by impurities such as alkaline water. A laminate having excellent adhesion can be obtained by increasing the affinity between the laminate to be represented by the laminate and the porous silica film.

  Examples of the silylating agent include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethylethoxysilane, methyldiethoxysilane, dimethylvinylmethoxysilane, and dimethyl. Alkoxysilanes such as vinylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, methyldichlorosilane, dimethylchlorosilane, dimethylvinylchlorosilane, Methyl vinyl dichlorosilane, methyl chloro disilane, triphenyl chloro silane, methyl diphenyl chloro Chlorosilanes such as silane, diphenyldichlorosilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, N-trimethylsilylacetamide, dimethyltrimethylsilylamine, diethyltriethylsilylamine, trimethylsilylimidazole and other silazanes, (3, 3,3-trifluoropropyl) trimethoxysilane, (3,3,3-trifluoropropyl) triethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, triethoxy-1H, 1H, 2H, 2H -Alkoxysilanes having a fluorinated alkyl group or a fluorinated aryl group such as tridecafluorooctylsilane.

  Silylation is performed by applying a silylating agent to the porous silica film, immersing the porous silica film in the silylating agent, or exposing the porous silica film to the vapor of the silylating agent. Can do. Alternatively, a solution obtained by adding water to the silylating agent and hydrolyzing the silylating agent in the absence of a catalyst or in the presence of a catalyst to increase the reactivity may be used in the same manner as described above. When using a catalyst, bases such as sodium hydroxide, ammonia, hydrazine, and amines may be used in addition to acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid. At this time, an organic solvent such as alcohol may be used in combination.

In the present invention, there is no particular limitation on the film thickness of the porous film such as the porous silica film formed in this way, the use of the laminate member and the obtained laminate, the mode pore size and the void of the porous film. Although it is arbitrarily determined depending on the porosity, material, etc., if it is excessively thin, the above-mentioned anchor effect may not be sufficiently obtained. Conversely, if it is excessively thick, the mechanical strength of the membrane tends to decrease. Therefore, it is usually preferably 0.03 to 5 μm, particularly preferably about 0.05 to 3 μm.
The film thickness of the porous film can be analyzed by, for example, an SEM photograph or an ellipsometer, or measured by a stylus type step / surface roughness / fine shape measuring device or the like.

[Laminate]
As shown in FIGS. 1B and 1D, the laminate 4A of the present invention is a porous film that is an adhesive film of the laminate member 1 of the present invention in which the porous film 3 is formed on the substrate 2 described above. The other base material 5 is laminated on 3. Alternatively, as shown in FIG. 1 (c), the laminate 4B of the present invention is formed on the porous film 3 which is an adhesive film of the laminate member 1 of the present invention in which the porous film 3 is formed on the base material 2 described above. The adhesive layer 6 and the other base material 5 are sequentially laminated.
In these laminates 4A and 4B, since the adhesive layer is the porous film 3, the rate of distortion when the laminates 4A and 4B are stressed is small, and the base material 2 and the other base material 5 Improved adhesion.
In particular, in the laminates shown in FIGS. 1B and 1C, as described above, the adhesive or pressure-sensitive adhesive of the molten base material or the adhesive layer penetrates into the pores of the porous film 3 to obtain a good anchor effect. Thereby, high adhesion is obtained, which is preferable.

  In the laminate of the present invention, as shown in FIGS. 1B, 1C and 1D, the base material 5, the adhesive layer 6 and the base material 5 are laminated only on one surface of the laminate member 1. Not limited to this, as described above, a laminate member in which the porous film 3 is formed on both surfaces of the substrate 2 may be used, and these other substrates may be laminated on both surfaces of the laminate member. . In that case, the other base material and the adhesive layer laminated on both surfaces of the laminate member may be the same or different. Further, in any of FIGS. 1A to 1D, the base material 2 and the other base material 5 do not necessarily have a flat surface, and regular and irregular irregularities are formed on the surface to be laminated. Or a shape such as a curved surface or a staircase shape.

<Other base materials>
As the other base material of the laminate of the present invention, the same material, form and thickness as those exemplified as the base material of the above-mentioned laminate member of the present invention can be used. The same material as the base material of the laminate member may be used, or a different material may be used. Generally, it is often a multi-functional laminate made of different materials. The form and thickness of the other base material may be the same as or different from the form and thickness of the base material of the laminate member.

  In order to laminate and integrate the base material on the porous film of the laminate member without using the adhesive layer described later, the other base material is melted under heating and / or pressure conditions during the stacking described later. Thus, it is preferable to use a material that allows the melt to enter the pores of the porous membrane.

<Adhesive layer>
When the adhesive layer and the other base material are laminated in this order on the porous film of the laminate member of the present invention to form the laminate of the present invention, the adhesive for the adhesive layer is not particularly limited. For the adhesive layer, general adhesives such as epoxy, rubber, acrylic, silicone, and thermoplastic elastomer can be used, and various types such as solvent type, emulsion type, and hot melt type should be used. Can do. Various curing methods such as thermal curing and photocuring can be used.

For example, the epoxy adhesive is preferably a polyfunctional epoxy compound, for example, bisphenol A, novolac type phenol resin, biphenyl type, or the like is used.
The rubber adhesive is composed of natural rubber, isoprene rubber, styrene / butadiene rubber, butyl rubber, polyisobutylene, styrene / isoprene / styrene block copolymer rubber, styrene / butadiene / styrene block copolymer rubber, and the like.
The acrylic adhesive is composed of an alkyl ester having about 2 to 12 carbon atoms of acrylic acid or methacrylic acid as the main monomer, and has a functional group such as acrylic acid, hydroxyethyl methacrylate or glycidyl methacrylate. A polymer copolymerized with monomers.
Silicone adhesive is polydimethylsiloxane, which is the main polymer, and is composed of silicone rubber or silicone resin in which a part of methyl group is substituted with phenyl group or vinyl group, or modified silicones modified with acrylic acid derivatives, etc. Can also be included.
Hot melt adhesives include polyethylenes such as ethylene / vinyl acetate copolymers, dienes such as styrene / butadiene copolymers, acrylic ester copolymers, polyvinyl ethers, polyurethanes, and polyamides.

The above various adhesives can be blended with rosin-based, terpene-based, petroleum resin-based tackifier resins, tackifiers, additives, and curing agents.
In addition, a commercially available adhesive may be used.

  Further, the adhesive layer is not limited to the adhesive, and may be formed of an adhesive.

  Such an adhesive layer made of an adhesive or a pressure-sensitive adhesive is usually laminated in advance on another substrate, and bonded to the porous film of the laminate member of the present invention as a substrate with an adhesive layer.

In this case, the adhesive layer is the above-mentioned adhesive layer forming adhesive or adhesive composition or pressure-sensitive adhesive on another substrate, for example, direct gravure coat, reverse gravure coat, kiss coat, die coat, roll coat, dip coat. After coating by knife coating, spray coating, fountain coating, or other methods, it is formed by curing at a predetermined temperature for a predetermined time. Here, the coating thickness is preferably about 0.1 to 8 g / m ² as a dry adhesive or pressure-sensitive adhesive coating amount. If the coating amount is too small, the amount of the adhesive or pressure-sensitive adhesive is too small to sufficiently obtain the anchor effect described above. If the coating amount is too large, the protruding adhesive may contaminate the laminate.

<Lamination method>
In order to laminate and integrate the above-mentioned other base material, or the adhesive layer and the other base material on the porous film which is the adhesive film of the laminate member of the present invention, the laminate of the present invention is usually used. On the porous film of the laminate member of the invention, another substrate, or an adhesive layer and another substrate (preferably a substrate with an adhesive layer) are superposed and heated and / or pressurized.

  When heating at the time of this lamination process, the heating temperature is preferably 200 ° C. or lower, particularly preferably 180 ° C. or lower. When this heating temperature is too high, a low melting point resin material may not be used as a base material (a base material of a laminate member and another base material laminated on the laminate member).

In addition, the degree of pressurization in the case of pressurizing during the lamination process is preferably 500 kgf / cm ² or less, particularly 100 kgf / cm ² or less. If this pressure is too high, the substrate may be damaged.

[Usage]
Although there is no restriction | limiting in particular in the use of the laminate member and laminated body of this invention, It uses suitably for the following uses.
(1) When laminating a metal foil such as a copper foil as a conductor to an insulating film such as a polyester film or a polyimide film of a flexible printed wiring board.
In this case, a porous film such as the aforementioned porous silica film of the present invention is formed on a base film such as a polyimide film, and a metal foil such as a copper foil is heated and pressed against the porous film. Stack and integrate. Alternatively, a porous film such as the porous silica film of the present invention may be first formed on the side of a metal foil such as a copper foil, and then laminated and integrated.
(2) When a gas barrier layer is formed by laminating a metal foil such as an aluminum foil on a base film as a packaging material for food, non-food and pharmaceuticals.
In this case, a porous film such as the above-described porous silica film of the present invention is formed on the base film, and a metal foil such as an aluminum foil is heated and pressed on the porous film to be laminated and integrated. Alternatively, a porous film such as the porous silica film of the present invention may be first formed on the side of a metal foil such as an aluminum foil and then laminated and integrated.
(3) In a solar cell module, a glass substrate, an EVA sheet, a silicon power generation element, an EVA sheet, and a back cover are laminated and integrated.
In this case, a porous film such as the aforementioned porous silica film of the present invention is formed on the surface of the glass substrate, and an EVA sheet, a silicon power generation element, an EVA sheet and a back cover are laminated on the porous film, Integrate by heating and pressing.
Furthermore, a porous film such as the porous silica film of the present invention described above can also be formed on the EVA sheet laminated surface side of the back cover.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Example 1]
0.85 g of methyltrimethoxysilane, 0.15 g of dimethyldimethoxysilane, and 1.00 g of a tetramethoxysilane condensate (methyl silicate heptamer) were stirred at room temperature in 2.00 g of ethanol. To this solution, 0.30 g of 0.1 mol / L hydrochloric acid and 1.00 g of water were added and stirred at room temperature under acidity (pH 2) for hydrolysis. The mixture was aged by stirring in a constant temperature bath at 60 ° C. for 30 minutes. Further, with stirring at room temperature, 3.00 g of ethanol, 15.00 g of water, 4.00 g of 0.25 mol / L sodium hydroxide aqueous solution, and 7.00 g of ethanol were added in this order. Under basic condition (pH 11) It was dehydrated and condensed. Then, it aged by stirring for 60 minutes in a 60 degreeC thermostat, and obtained the raw material liquid for porous silica film formation.
In order to obtain the target film, this raw material solution was diluted 2 times with ethanol to obtain a silica coating solution.

  A silica coating solution is placed on a glass substrate, spin-coated at 1000 rpm for 30 seconds, dried at 120 ° C. for 20 minutes, and then a laminate member of the present invention in which a porous silica film having a thickness of 0.1 μm is formed on the glass substrate is obtained. It was.

Put 1 g of commercially available EVA resin (manufactured by Tokyo Ink) into a mold with a 5 cm square hole, sandwich it between a silicone sheet and a metal plate, press at 105 ° C. and 10 kg / cm ^{2 for} 90 seconds, about 1 mm A thick EVA film was obtained.
The obtained EVA film was stacked on the porous silica film of the laminate member, and this was put into a press heater whose upper and lower press surfaces were heated to 150 ° C., and heated and pressurized (3 kgf / cm ² , 150 ° C.). The laminate was obtained by holding for 10 minutes.

<Measurement of the most frequent pore diameter of the porous silica film>
10 g of the silica coating solution was placed in a Teflon petri dish, dried at room temperature for 24 hours, and then dried with a vacuum dryer. Using 100 mg of the solid content collected from the petri dish, the BET nitrogen adsorption isotherm was measured with AS-1 manufactured by Cantachrome, and the mode pore diameter was determined. As a result, the most frequent pore diameter was 5 nm.
In the most frequent pore diameter measurement, the most frequent pore diameter of the porous film in the laminate member (porous silica film / glass substrate) is not directly measured. However, in the temperature range from room temperature to 120 ° C., it is considered that the mode pore size of the silica film is not affected, so the mode pore size of the porous membrane of the laminate member is also considered to be 5 nm. This is because the surface area of silica (reduction of vacancies) generally occurs under heating conditions of 650 ° C. or higher, and it is considered that heating for about 1 hour at around 100 ° C. does not change.

<Measurement of porosity of porous silica membrane>
About the sample of said porous silica film / glass substrate, when the refractive index n of the porous film was measured with the spectroscopic ellipsometer and the porosity X was computed from the above-mentioned formula (i), (ii) (n ₀ = 1.00, n ₁ = 1.47), and the porosity of the porous silica film was 40%.

<Peel strength test>
With respect to the laminate of the above EVA film / porous silica film / glass substrate, the peel strength was measured under the following measurement conditions, which was 10N.

(Peel strength measurement conditions)
(1) A 7.5 cm long cut was made in the EVA film / porous silica membrane with a cutter to a width of 24 mm from above the EVA film of the sample (EVA film / porous silica membrane / glass substrate).
(2) Both ends of the sample were fixed with cellophane tape.
(3) A gavel type attachment and clip were attached to the measurement shaft side of the push-pull scale (manufactured by Imada Co., Ltd.), and the end of the EVA film was fixed with the clip.
(4) The push-pull scale was pulled up to 90 ° to peel off the EVA film.
(5) The maximum value of the scale at this time was taken as the peel strength

<Measurement of transparency of porous membrane>
About the sample of the porous silica film / glass substrate of the laminate member obtained above, YI value, haze, and total light transmittance were measured (JIS K 7105) using COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. However, the following results were obtained, and it was confirmed that the transparency was excellent.
YI: 1.12
Hayes: 0.07%
Total light transmittance: 95.79%

  From the above results, according to the laminate member of the present invention, it is possible to form a laminate having excellent interlayer adhesion, and it is excellent in transparency by forming a porous silica film as the porous film. It turns out that it can be set as a laminated body.

[Comparative Example 1]
The EVA film used in Example 1 was directly stacked on the glass substrate used in Example 1, heated at 150 ° C. for 10 minutes, and pressed at 3 kg / cm ² to obtain an EVA film / glass substrate laminate.
A peel strength test was conducted on this EVA film / glass substrate laminate in the same manner as in Example 1, and the result was 2N.

[Example 2]
An adhesive tape having a width of 18 mm and a length of 8 cm on a porous silica film of a laminate member (glass substrate with a porous silica film) prepared in the same manner as in Example 1 (transparent adhesive tape “Transparent beautiful color” manufactured by Sumitomo 3M Limited) Was 5 cm, and a peel strength test was conducted under the following measurement conditions. The result was 8.4 N.
(Peel strength measurement conditions)
(1) A small cage attachment and clip were attached to the measurement shaft side of the push-pull scale (manufactured by Imada Co., Ltd.), and the end of the cellophane tape was fixed with the clip.
(2) The push-pull scale was pulled up in the direction perpendicular to the bonding surface, and the cellophane tape was peeled off.
(3) The maximum value of the scale at this time was defined as the peel strength.

[Comparative Example 2]
When 5 cm of an adhesive tape having a width of 18 mm and a length of 8 cm (transparent adhesive tape “Transparent beautiful color” manufactured by Sumitomo 3M Co., Ltd.) was applied to a glass substrate and a peel strength test was performed under the same measurement conditions as in Example 2, 1 It was 5N.

[Example 3]
Using a PET (polyethylene terephthalate) film subjected to easy adhesion processing instead of the glass substrate of Example 1, and changing the drying conditions after spin-coating the silica coating solution on the substrate at 80 ° C. for 20 minutes A laminate member was obtained in the same manner as in Example 1. When the same test as in Example 2 was performed using this, the peel strength was 8.3N.

[Comparative Example 3]
When a test similar to that of Comparative Example 2 was performed using a PET film subjected to easy adhesion processing instead of the glass substrate of Comparative Example 2, the peel strength was 3.6 N.

[Example 4]
When the same test as in Example 3 was performed using an aluminum plate instead of the PET film subjected to the easy adhesion process in Example 3, the peel strength was 9.2N.

[Comparative Example 4]
When a test similar to that of Comparative Example 2 was performed using an aluminum plate instead of the glass substrate of Comparative Example 2, the peel strength was 2.1 N.

[Example 5]
When the same test as in Example 3 was performed using a stainless steel plate instead of the PET film subjected to the easy adhesion process in Example 3, the peel strength was 8.2N.

[Comparative Example 5]
When the same test as Comparative Example 2 was performed using a stainless steel plate instead of the glass substrate of Comparative Example 2, the peel strength was 1.0 N.

[Example 6]
When the same test as in Example 3 was performed using a stainless steel plate whose surface was roughened with an abrasive of # 80 instead of the PET film subjected to the easy adhesion process in Example 3, the peel strength was 10.1N.

[Example 7]
When the same test as in Example 3 was performed using a polycarbonate resin plate instead of the PET film subjected to the easy adhesion process in Example 3, the peel strength was 3.3N.

[Comparative Example 6]
When a test similar to that of Comparative Example 2 was performed using a polycarbonate resin plate instead of the glass substrate of Comparative Example 2, the peel strength was 0.4 N.

  The results of Examples 2 to 8 and Comparative Examples 2 to 8 are summarized in Table 1.

[Example 8]
In the same manner as in Example 1, a porous silica film was formed on a glass substrate. This corresponds to a length of 5 cm of a tape (no adhesive layer) made of a silicone resin having a width of 18 mm and a thickness of 0.5 mm, the surface of which has been previously washed with ethanol at room temperature on the porous silica film of this glass substrate. The part was crimped at about 1 kg / cm ² . When the laminate was used and a peel strength test was performed in the same manner as in Example 2, the peel strength was 1.0 N.

[Comparative Example 7]
When a tape made of a silicone resin was pressure-bonded onto a glass substrate without a porous silica film in the same manner as in Example 8, and the peel strength test was performed using the laminate, the peel strength was 0.2N.

[Example 9]
When a porous silica film was formed on the surface of a PET film that had been subjected to easy adhesion processing in the same manner as in Example 3, and the peel strength test was performed in the same manner as in Example 8, the peel strength was 0.4 N.

[Comparative Example 8]
When a peel strength test similar to that of Example 8 was performed using a PET film that had been subjected to easy adhesion processing without a porous silica film, the peel strength was 0.2 N.

  Table 2 summarizes the results of Examples 8 to 9 and Comparative Examples 7 to 8.

DESCRIPTION OF SYMBOLS 1 Laminate member 2 Base material 3 Porous film | membrane 4A, 4B Laminated body 5 Other base materials 6 Adhesive layer

Claims (5)

  A laminate member having an adhesive film on a substrate, wherein the adhesive film is made of an inorganic material and is a porous film having a modest pore diameter of 0.5 to 10 nm and a porosity of 15% or more. There is a laminate member.   The laminate member according to claim 1, wherein the inorganic material is silica. A method of manufacturing a laminated member according to claim 1 or 2, the manufacturing method of the characteristics and to Lula laminate-member comprises a step of forming a film of該接wear layer at 200 ° C. or less. The laminated body which laminated | stacked another base material on the film | membrane for adhesion | attachment of the laminate member of Claim 1 or 2 . A laminate in which an adhesive layer and another substrate are sequentially laminated on the adhesive film of the laminate member according to claim 1 or 2 .

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