JP2007031669A - Liquid adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid adhesive in which thickness of the adhesive can be thickened and handling ability and workability can be improved. <P>SOLUTION: The liquid adhesive comprises an uncured liquid adhesive (A) and an uncured liquid adhesive (B) and the uncured liquid adhesive (A) is applied to either one counter surface periphery of a pair of transparent plates 2 and 2A constituting a dye-sensitization type solar cell 1 and the uncured liquid adhesive (B) is applied to the other counter surface periphery and each solvent is evaporated and then, transparent plates are attached to each other. As a result, a pair of transparent plates 2 and 2A are cured and strongly bonded. Since the liquid adhesive composed of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) which are not two-component definite-form adhesive which is definite when uncured and are not cured until transparent plates are attached to each other is used, the thickness of the adhesive can be thinned. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid adhesive made of silicone rubber or the like having long-term storage stability and high adhesive strength.

  Adhesives are used in a wide range of fields such as space, aviation, vehicles, ships, electricity, electronics, civil engineering, etc. Especially silicone adhesives have excellent heat resistance, cold resistance, weather resistance, electrical insulation, etc. Therefore, it is also suitably used for applications that cannot be used with ordinary types. However, conventional silicone adhesives are liquid or pasty, and they stick out when they adhere, contaminating parts that are not needed, finishing dirty, sticking hands and fingers with contact, etc. There is a problem.

  A silicone rubber fixed uncured adhesive has been proposed as an adhesive for solving such problems. As this silicone rubber fixed uncured adhesive, a one-component silicone addition-type fixed adhesive is known (see Patent Documents 1, 2, and 3). There is often a risk of lack of sex.

  In addition, as a method of curing an addition curable silicone uncured molded product, as an example of creating a molded product with a composition excluding a part of the cured component, and then curing by contacting or transferring the excluded component to the sheet A technique is known in which an uncured sheet is cured by applying hydrogen siloxane to an uncured sheet or impregnating a cured sheet with hydrogen polysiloxane and bringing the cured sheet into contact with the uncured sheet (patent) Reference 4). Moreover, the technique which hardens | cures by apply | coating the platinum compound which is a hydrosilylation catalyst to an uncured molded object is also known (refer patent document 5).

However, in the past, there were many problems when used as an adhesive, such as insufficient storage stability, application of liquid to an uncured molded body, or integration with a cured molded body. . As an adhesive that solves such a problem, a two-component fixed adhesive has been proposed (see Patent Document 6).
Japanese Patent Laid-Open No. 01-197587 Japanese Patent Laid-Open No. 06-108608 JP-A-10-017828 JP 59-059725 A JP-A-11-050038 Japanese Patent Laid-Open No. 2005-60549

  However, since the conventional two-component fixed adhesive is fixed even when uncured, even if a carrier film is used, a thickness of 100 μm or more is required from the viewpoint of handling. However, in recent years, it is often required to reduce the adhesion thickness in the field of electrical and electronic fields. For example, in a dye-sensitized solar cell or the like, the adhesion thickness is often 50 μm or less. Further, the conventional two-component fixed adhesive has a big problem that handling becomes difficult and the workability is remarkably lowered when the bonding shape is complicated.

  The present invention has been made in view of the above, and an object of the present invention is to provide a liquid adhesive that can reduce the thickness of the adhesive and improve handling properties and workability.

In the present invention, in order to solve the above-mentioned problem, the uncured liquid adhesive (A) and the uncured liquid adhesive (B) are included,
Uncured liquid adhesive (A)
1) Organopolysiloxane having at least two alkenyl groups and having a viscosity at 25 ° C. of 100,000 mPa · s or more 100 parts by weight 2) An amount sufficient to cure the hydrosilylation catalyst (A) and (B) 4) Filler 1 to 2,000 parts by weight 5) Adhesion imparting agent 0 to 10 parts by weight 6) Solvent 10 to 2,000 parts by weight
Uncured liquid adhesive (B)
1) An organopolysiloxane having at least two alkenyl groups and a viscosity at 25 ° C. of 100,000 mPa · s or more 100 parts by weight 3) It has at least two hydrosilyl groups and a viscosity of 10 to 1,000 mPa · s. s or more organohydrogenpolysiloxanes (A) and (B)
The amount of silicon-bonded hydrogen atoms is
4) Filler 1 to 2,000 parts by weight 5) Adhesive agent 0 to 10 parts by weight 6) Solvent 10 to 2,000 parts by weight Consisting of a composition,
The total amount of 5) is 0.1 to 20 parts by weight with respect to 200 parts by weight of the total amount of 1).

In addition, an uncured liquid adhesive (A) is applied to one of a pair of opposing substrates, and an uncured liquid adhesive (B) is applied to the other, and after the solvent is volatilized, they are bonded and cured and bonded. It is preferable.
Moreover, when the plasticity of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilizing the solvent is measured with a Williams plasticity meter, the plasticity may be in the range of 30 to 500, respectively. preferable.
Moreover, it is preferable that the thickness of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilizing the solvent is 1 mm or less, respectively.

Further, when the tackiness on the surfaces of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of the solvent was measured by a test method based on JISZ 0237, the ball numbers were 4 to 4 respectively. The range can be 21.
Moreover, a spacer can be filled in at least one of the uncured liquid adhesive (A) and the uncured liquid adhesive (B).

Further, the uncured liquid adhesive (A) was applied to one of a pair of adherends facing each other with a gap of 50 μm or less, and the uncured liquid adhesive (B) was applied to the other to evaporate the solvent. It can be pasted and cured and bonded.
Furthermore, an uncured liquid adhesive (A) is provided on one peripheral edge of a pair of transparent plates of a dye-sensitized solar cell facing each other with a gap of 50 μm or less, and an uncured liquid adhesive is provided on the other peripheral edge. It is also possible to screen-print (B), volatilize each solvent, and bond them together to cure and bond them.

  Examples of means for applying the uncured liquid adhesive (A) or the uncured liquid adhesive (B) to the adherend in the claims include a screen printing method and the use of a brush. The solvent is preferably one that is soluble in silicone, but is not particularly limited. Further, a plurality of ball-shaped spacers or the like are interposed between the pair of adherends, and a gap can be formed between the pair of adherends by the plurality of spacers. Examples of the adherend include a glass plate, a substrate, a sheet, a film, and the like that face each other, and there is no particular question regarding the presence or absence of a plurality of substrates, flexibility, and permeability. Furthermore, the liquid adhesive can be used at least in the fields of space, aviation, vehicles, ships, liquid crystals, precision instruments, communications, electricity, electronics, civil engineering, heat dissipation, and the like.

  ADVANTAGE OF THE INVENTION According to this invention, while the thickness of an adhesive agent can be made thin, there exists an effect that handling property and workability | operativity can be improved. Moreover, since it does not harden | cure until it bonds together, the outstanding long-term storage property can be obtained.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the liquid adhesive in the present embodiment includes an uncured liquid adhesive (A) and an uncured liquid adhesive (B ), For example, an uncured liquid adhesive (A) is formed on one of the peripheral surfaces of the pair of transparent plates 2 and 2A constituting the dye-sensitized solar cell 1 for a building, and the peripheral surface of the other surface The uncured liquid adhesive (B) is thinly applied to the endless frame shape with a brush or the like, and the dried uncured liquid adhesive (A) and the uncured liquid adhesive (B) after solvent volatilization By being attached, it functions to firmly cure and bond the pair of transparent plates 2 and 2A.

  The uncured liquid adhesive (A) includes 1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups and a viscosity at 25 ° C. of 100,000 mPa · s or more, 2) a hydrosilylation catalyst (A ) And (B) in an amount sufficient to cure, 4) 1 to 2,000 parts by weight of filler, 5) 0 to 10 parts by weight of adhesion promoter, 6) 10 to 2,000 parts by weight of solvent. It consists of a composition to contain.

  The uncured liquid adhesive (B) is 1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups and a viscosity at 25 ° C. of 100,000 mPa · s or more, and 3) at least two hydrosilyls. The amount of silicon-bonded hydrogen atoms in the molar ratio of the organohydrogenpolysiloxane having a group and a viscosity of 10 to 1,000 mPa · s or more to the total of alkenyl groups derived from the components (A) and (B) Composition containing 0.01 to 20.0, 4) 1 to 2,000 parts by weight of filler, 5) 0 to 10 parts by weight of adhesion promoter, 6) 10 to 2,000 parts by weight of solvent. The total amount of the adhesion imparting agent of 5) is 0.1 to 20 parts by weight with respect to 200 parts by weight of the total amount of the organopolysiloxane of 1).

  1) Organopolysiloxane is the main component of the liquid adhesive and is contained in each of the uncured liquid adhesive (A) and the uncured liquid adhesive (B). This organopolysiloxane has an average of two or more alkenyl groups in one molecule, and examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and the like. Of these, vinyl groups are preferred.

  Examples of the organic group bonded to the silicon atom other than the alkenyl group in the organopolysiloxane include an alkenyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group An aryl halide group such as 3-chloropropyl group and 3,3,3-trifluoropropyl group. Among them, a methyl group is preferable.

  Examples of the molecular structure of the organopolysiloxane include linear, partially branched linear, branched, network, and dendritic structures. The viscosity of the organopolysiloxane at 25 ° C. is 100,000 mPa · s or more, preferably 10,000,000 mPa · s or more.

Examples of such organopolysiloxanes include polydimethylsiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain, dimethylsiloxane / methylvinylsiloxane copolymer blocked with dimethylvinylsiloxy group at both ends of the molecular chain, and trimethylvinylsiloxy group blocked at both ends of the molecular chain. Dimethylsiloxane / methylvinylsiloxane copolymer, a siloxane unit represented by the formula: (CH ₃ ) ₃ SiO _1/2 and a siloxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Formula: _{Polyorganosiloxanes} composed of siloxane units represented by SiO _4/2 , some or all of the methyl groups of these polyorganosiloxanes are alkyl groups such as ethyl groups and propyl groups, and aryls such as phenyl groups and tolyl groups Group and / or halogenation of 3,3,3-trifluoropropyl group, etc. Polyorganosiloxanes substituted with alkyl groups, polyorganosiloxanes in which some or all of the vinyl groups of these polyorganosiloxanes are substituted with alkenyl groups such as allyl groups and propenyl groups, and two or more of these polyorganosiloxanes Mixtures are exemplified.

  2) A platinum-based catalyst is preferably used as the hydrosilylation catalyst. Specific examples of the platinum-based catalyst include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum and diketone complexes, chloroplatinic acid and olefin complexes, chloroplatinic acid and alkenylsiloxane complexes. And those in which these are supported on a carrier such as alumina, silica, or carbon black. Among these, a complex of chloroplatinic acid and alkenylsiloxane is preferable because of its high catalytic activity as a hydrosilylation reaction catalyst, and in particular, chloroplatinic acid and divinyltetramethyldisiloxane as disclosed in Japanese Patent Publication No. 42-22924. The complex is optimal.

  The amount of hydrosilylation catalyst is sufficient to cure the uncured liquid adhesive (A) and the uncured liquid adhesive (B), specifically, the uncured liquid adhesive (A) and the uncured liquid adhesive. 1 to 1000 parts by weight, preferably 1 to 100 parts by weight, as platinum metal atoms, per 1,000,000 parts by weight of the total amount of organopolysiloxane contained in the agent (B).

  3) The organohydrogenpolysiloxane acts as a curing agent for the liquid adhesive, has at least two hydrosilyl groups, and has a bonding group bonded to a silicon atom. Examples of the bonding group bonded to the silicon atom include an alkenyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an aryl group such as a phenyl group, a tolyl group, and a xylyl group; a 3-chloropropyl group And halogenated alkyl groups such as 3,3,3-trifluoropropyl group, among which the methyl group is most suitable.

  Examples of the molecular structure of the organohydrogenpolysiloxane include linear, partially branched linear, branched, network, and dendritic structures. The viscosity of the organohydrogenpolysiloxane at 25 ° C. is not particularly limited, but is 1 to 1,000,000 mPa · s or more, preferably 10 to 1,000 mPa · s or more.

Examples of such organohydrogenpolysiloxane include polydimethylsiloxane blocked with dimethylvinylsiloxy group blocked at both ends of the molecular chain, trimethylsiloxy group-blocked polymethylhydrogensiloxane blocked at both ends of the molecular chain, trimethylsiloxy blocked dimethylsiloxane / methylhydrol. Genosiloxane copolymer, cyclic polymethylhydrogensiloxane, polyorganosiloxane comprising a siloxane unit represented by the formula: (CH ₃ ) ₂ SiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 Part or all of the methyl group of the organosiloxane was substituted with an alkyl group such as an ethyl group or a propyl group; an aryl group such as a phenyl group or a tolyl group; or a halogenated alkyl group such as a 3,3,3-trifluoropropyl group. Polyorganosiloxane, Beauty mixtures of two or more of these polyorganosiloxanes are exemplified. In these, since the mechanical property of the obtained hardened | cured material, especially elongation improves, it is preferable that it is a mixture of the polyorganosiloxane which has a silicon atom bond hydrogen atom only at both ends of a molecular chain.

  The content of the organohydrogenpolysiloxane contained in the uncured liquid adhesive (B) is based on the alkenyl group in the organopolysiloxane contained in the uncured liquid adhesive (A) and the uncured liquid adhesive (B). The amount by which the molar ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane is from 0.01 to 20, preferably from 0.1 to 10, more preferably from 0.1 to 5. When the content of the organohydrogenpolysiloxane is at least the lower limit of the above range, good curability can be imparted to the obtained liquid adhesive. Moreover, the mechanical characteristic of the adhesive hardened | cured material obtained can be improved by setting it as the upper limit of the said range.

  When a mixture of a polyorganosiloxane having a silicon atom-bonded hydrogen atom only at the molecular chain end and a polyorganosiloxane having a silicon atom bond in the molecular chain side chain is used as the organohydrogenpolysiloxane, both of the former molecular chains are used. The content of the polyorganosiloxane having a silicon atom-bonded hydrogen atom only at the terminal is 1) an amount in which the molar ratio of the silicon atom-bonded hydrogen atom in this component to the alkenyl group in the organopolysiloxane is 0.01 to 10, The amount is preferably 0.1 to 10, more preferably 0.1 to 5.

  The content of the polyorganosiloxane having a silicon atom bond in the latter molecular chain side chain is as follows: 1) The molar ratio of the silicon atom bonded hydrogen atom in this component to the alkenyl group in the organopolysiloxane is 0.5 to 20. The amount is optimal.

  4) The filler is added to improve the shape retention and mechanical strength of the composition constituting the liquid adhesive or to impart functions such as conductivity, thermal conductivity, and flame retardancy. As the filler, a compound usually used for blending silicone rubber is used. Examples of fillers that improve shape retention and mechanical strength include fumed silica, precipitated silica, calcined silica, pulverized quartz, and organosilicon compounds such as organoalkoxysilane, organohalosilane, and organosilazane. Silica-based fillers such as powder surface-treated with Calcium carbonate and the like are used.

As calcium carbonate, any of heavy, light or colloidal calcium carbonate can be used. Among these, silica powder having a BET specific surface area of 50 m ² / g or more is optimal in order to sufficiently improve the mechanical strength of the obtained adhesive cured product.

  Examples of fillers added to impart functions such as conductivity, thermal conductivity, and flame retardancy include fumed titanium oxide, carbon black, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, zinc oxide, and hydroxide. Aluminum, boron nitride, aluminum nitride, magnesium oxide, metal powder, a filler whose surface is treated with the above organosilicon compound, or the like is used.

  In the uncured liquid adhesive (A) and the uncured liquid adhesive (B), the filler is used in an amount of 1 to 2000 parts by weight per 100 parts by weight of the organopolysiloxane. When only a silica-based filler or a calcium carbonate-based filler is used as the filler, in the uncured liquid adhesive (A) and the uncured liquid adhesive (B), 100 parts by weight of the organopolysiloxane respectively. On the other hand, 1 to 1000 parts by weight, preferably 1 to 400 parts by weight is used.

  This is because when the amount is less than 1 part by weight, the shape of the adhesive is not sufficiently maintained, and improvement in mechanical strength after curing cannot be expected. Conversely, when the amount exceeds 1000 parts by weight, the adhesive becomes hard, and when the uncured liquid adhesive (A) and the uncured liquid adhesive (B) are pasted, the unevenness on each surface is pressed. This is because the shape cannot be changed due to the unevenness, and bubbles remain on the sticking surface, resulting in a decrease in adhesive strength.

  In the case of adding a filler for imparting functions such as conductivity, thermal conductivity and flame retardancy, in the uncured liquid adhesive (A) and the uncured liquid adhesive (B), It is preferable to use 10 to 2000 parts by weight with respect to 100 parts by weight. If 10 parts by weight or more is used, shape retention can be imparted without using a silica filler or a calcium carbonate filler.

  When the amount is less than 10 parts by weight, the intended function is not sufficiently imparted. Conversely, when the amount exceeds 2000 parts by weight, the adhesive becomes hard, and the uncured liquid adhesive (A) is uncured. This is because when the liquid adhesive (B) is stuck, bubbles remain on the sticking surface and the adhesive strength is lowered.

  Of course, a silica-based filler or a calcium carbonate-based filler may be used in combination with a filler for imparting functions such as conductivity, thermal conductivity, and flame retardancy. In this case, in the uncured liquid adhesive (A) and the uncured liquid adhesive (B) as the whole filler, each is used in the range of 1 to 2000 parts by weight with respect to 100 parts by weight of the organopolysiloxane. Without using the filler or calcium carbonate filler as much as possible, it is preferable to reduce the amount appropriately in consideration of the hardness of the adhesive.

  In addition, since fillers for imparting functions such as conductivity, thermal conductivity, and flame retardancy also exhibit a certain degree of mechanical strength improvement effect and shape retention effect, when used in combination, silica-based fillers and carbonic acid It is not necessary to limit the use of calcium-based fillers other than 1 part by weight.

  5) The adhesion-imparting agent imparts adhesiveness and functions as an adhesive. This adhesion-imparting agent includes methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- Silane coupling agents such as (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilyl) propane, bis (trimethoxysilyl) hexane, and partial hydrolysates thereof; epoxy group, acid anhydride An organic compound having a physical group, an α-cyanoacryl group, and a siloxane compound containing these groups, or an organic compound or siloxane compound having both of these groups and an alkoxysilyl group or a hydrosilyl group; tetraethyl titanate, tetrapro Titanium compounds such as rutitanate, tetrabutyl titanate, tetra (2-ethylhexyl) titanate, titanium ethyl acetonate, titanium acetyl acetonate; ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropyl Aluminum compounds such as aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate); zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate, etc. A zirconium compound may be contained.

  The content of these adhesion-imparting agents is an arbitrary amount that may not be contained in each of the uncured liquid adhesive (A) and the uncured liquid adhesive (B), and 1) 100 parts by weight of the organopolysiloxane. The amount is 0 to 10 parts by weight with respect to 1) The amount of the polyorganosiloxane is 0.1 to 20 parts by weight with respect to the total amount of 200 parts by weight of the organopolysiloxane, and the uncured liquid adhesive (A) and uncured liquid In each of the adhesives (B), it is necessary that 1) 0.01 to 10 parts by weight with respect to 100 parts by weight of the organopolysiloxane.

  Silicone compositions include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol to adjust curability Acetylene-based compounds such as 3-methyl-1-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, etc .; 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, silanol group-blocked methylvinylsiloxane, both molecular chains Organosiloxane compounds having 5% by mass or more of vinyl groups in one molecule such as terminal silanol-blocked methylvinylsiloxane / dimethylsiloxane copolymer; Riazor acids, phosphines, mercaptans, may contain a curing inhibitor such as hydrazines. Although content of these hardening inhibitors is not limited, it is suitable that it is 0.001-5 weight part with respect to 100 weight part of 1) organopolysiloxane.

  6) The solvent is not particularly limited, and an organic solvent that dissolves the organic polymer may be used. Examples of the organic solvent for dissolving the organic polymer include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, ligroin, kerosene, and mineral spirits, and alicyclic rings such as cyclohexane and decahydronaphthalene. Hydrocarbon, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol, hexyl alcohol, and other alcohol systems, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, diethyl carbonate, dipropyl carbonate, ethylene carbonate, propylene Examples include carbonate solvents such as carbonate, and ester solvents such as ethyl acetate, n-propyl acetate, and isobutyl acetate, and malon esters, succinates, adipates, and phthalates. .

  About the compounding quantity of a solvent, 10-2000 weight part is good with respect to 100 weight part of 1) organopolysiloxane. This is because, when the amount of the solvent is less than 10 parts by weight, the viscosity of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) becomes high and coating becomes impossible. Based. On the contrary, when the amount exceeds 2000 parts by weight, the viscosity of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) becomes low, and the solvent volatilization time takes a long time. This is based on the reason that causes a decrease in workability.

  The preparation method of this composition is not particularly limited, and if necessary, arbitrary components are mixed using a kneading apparatus such as a two-roll roll, a kneader mixer, or a loss mixer to prepare the present composition. However, it is preferable to add the remaining components to a base compound prepared by heating and mixing 1) an organopolysiloxane and 4) a filler. When the remaining components are added, they may be added when preparing the base compound.

  Further, when there is a possibility that this additive component is altered by heating and mixing, it may be added when 2) the hydrosilylation catalyst and 3) the organohydrogenpolysiloxane are added. When preparing the base compound, an organosilicon compound may be added and 5) the surface of the adhesion-imparting agent may be treated in-situ.

  The plasticity of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of each solvent is in the range of 30 to 500, preferably 100 to 500, respectively, as measured with a Williams plasticity meter. Scope. This is based on the reason that when the plasticity is less than 30, the shape retention of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after solvent volatilization is hindered. Conversely, when the plasticity exceeds 500, it is difficult to remove bubbles remaining at the interface when the uncured liquid adhesive (A) and the uncured liquid adhesive (B) are bonded together, This is based on the reason that the contact area is reduced by the remaining bubbles and the adhesive force is reduced.

  Moreover, the thickness of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after each solvent volatilization is 1 mm or less, respectively, and the total is 2 mm or less. This is because when it exceeds 2 mm, uncured portions may be formed at a portion exceeding 2 mm from the bonding surface.

  Moreover, the tackiness on the surfaces of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of each solvent, in other words, the surface tack is a test method based on JISZ 0237 (ball rolling method). When measured, the ball number is in the range of 4-21. This is because when the ball number is less than 4, the adhesiveness to the transparent plates 2 and 2A cannot be sufficiently maintained. In addition, when the ball number exceeds 21, it is difficult to remove air during bonding.

  When adhering the uncured liquid adhesive (A) and the uncured liquid adhesive (B) to the transparent plates 2 and 2A of the dye-sensitized solar cell 1, a primer is applied to the transparent plates 2 and 2A. Adhesion can be improved. The primer is obtained by dissolving a surface treatment agent in a solvent or a dispersion medium, and this surface treatment agent is preferably a silane coupling agent. As this silane coupling agent, epoxy group-containing silanes or partial hydrolysis condensates thereof, (meth) acrylic group-containing silanes or partial hydrolysis condensates thereof, vinyl group-containing silanes or partial hydrolysis condensates thereof, One or more substances selected from the group consisting of cyclic siloxane, chain siloxane, and cyanuric ring-containing organosilicon compound may be used.

  Examples of epoxy group-containing silanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 2- (3,4-epoxy Examples include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl (methyl) diethoxysilane.

  Examples of the (meth) acrylic group-containing silane include 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-methacryloyloxypropyl (methyl) diethoxysilane. Examples of vinyl group-containing silanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and the like.

  Examples of the cyclic siloxane include 3-glycidoxypropyl group-containing methylhydrogen cyclic tetrasiloxane, 3-methacryloxypropyl group-containing methylhydrogen cyclic tetrasiloxane, 3-glycidoxypropyl group-containing methylmethoxy cyclic siloxane, 3- Examples include methylhydrogen cyclic siloxane having a glycidoxypropyl group and 2- (trimethoxysilyl) ethyl group, and 2-[(3-trimethoxysilyl) propyloxycarbonyl] propyl group-containing methylhydrogen cyclic tetrasiloxane. The

  Examples of the chain siloxane include 3-glycidoxypropyl group-containing methylmethoxysiloxane, 3-glycidoxy group and methylhydrogensiloxane having a vinyl group, and 3-glycidoxy group and 2- (trimethoxysilyl) ethyl group. Etc. are exemplified. Examples of the cyanuric ring-containing organosilicon compound include tris (3-trimethoxysilylpropyl) isocyanurate.

  The silane coupling agent is preferably added in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the solvent or dispersion medium. This is because if the blending amount is less than 1 part by weight, there is a possibility that the adhesion may be hindered. Conversely, if it exceeds 50 parts by weight, the workability will be reduced. These primers may be applied to the transparent plates 2 and 2A of the dye-sensitized solar cell 1 using a brush or the like, but may be applied by a coating machine such as a spray coater or a roll coater, or in the primer solution. The transparent plates 2 and 2A may be dipped.

  The dye-sensitized solar cell 1 has a pair of transparent plates 2 and 2A facing each other with a narrow space of 10 to 50 μm or less, and an electron transfer device enclosed in a gap between the pair of transparent plates 2 and 2A. The electrolyte solution 5 is configured. The pair of transparent plates 2 and 2A is made of, for example, a conductive glass plate, and has heat resistance against heat of about 500 ° C. The one transparent plate 2 functions as an anode, and the other transparent plate 2A Functions as a cathode. A transparent conductive film 3 as an electrode is laminated and formed on the opposing surfaces of the pair of transparent plates 2 and 2A.

  On the opposite surface of the transparent plate 2A, a porous film 4 of semiconductor is laminated and formed by applying and heating titanium oxide particles, and a sensitizing dye that efficiently absorbs sunlight is chemisorbed on the porous film 4. The porous film 4 on which the sensitizing dye is laminated absorbs light by the electrolyte solution 5 and emits electrons, and the electrons move quickly to the electrode. It will be transmitted.

As the sensitizing dye, for example, a metal complex or an organic dye is used. In addition, as the electrolyte solution 5, for example, redox electrolytes such as I / I ₃ , Br / Br ₃ , and xylene / hydroquinone are used as electrochemically inert solvents such as acetonitrile, propylene carbonate, and ethylene carbonate (and these). A colorable solution dissolved in a mixed solvent) is used.

  According to the above, a liquid adhesive composed of an uncured liquid adhesive (A) and an uncured liquid adhesive (B) which is not a fixed two-component fixed adhesive such as a sheet even when uncured, and does not cure until sticking Since the agent is used, the adhesion thickness can be extremely reduced. Therefore, it can be used suitably also for the dye-sensitized solar cell 1 etc. which require the adhesion thickness of 50 micrometers or less. Further, it is possible to effectively solve the problem that handling becomes difficult and workability is deteriorated.

  In addition, by adjusting the amount of liquid adhesive used, it is possible to reduce the sticking out of the adhesive when the pair of transparent plates 2 and 2A are attached, thereby preventing and preventing contamination other than the adhesive portion. In addition, since it does not cure until sticking, it is possible to obtain excellent long-term storage stability. Furthermore, the bonding shape can be freely changed, and there is very little risk of air intrusion.

  Furthermore, if the uncured liquid adhesive (A) and the uncured liquid adhesive (B) are screen-printed with a small printing pressure, they can be easily printed on rough surfaces and curved surfaces, Adjustment of the thickness of the adhesive layer is facilitated, and the adhesive can be applied with high accuracy.

  Next, FIG. 2 shows a second embodiment of the present invention. In this case, an uncured liquid adhesive (A) and an uncured liquid adhesive (B) are provided. The uncured liquid adhesive (A) is formed on one peripheral edge of the pair of substrates 11 and 11A, and the uncured liquid adhesive (B) is formed on the other peripheral edge of the other substrate by a brush or the like. A thin uncoated liquid adhesive (A) and an uncured liquid adhesive (B) that are applied to the substrate and evaporated after solvent volatilization are pasted together to firmly cure and bond the pair of substrates 11 and 11A. Function.

  The pair of substrates 11 and 11A face each other through a narrow gap, and the narrow gap is maintained by a plurality of spacers 12 having a particle shape, and the gap is filled with the liquid crystal composition 13. One substrate 11 has a wiring electrode 14 and an alignment film 15 stacked on each other on the surface that is the opposite surface, and a polarizing plate 16 is stacked on the back surface. Further, the other substrate 11A has a plurality of wiring electrodes 14 arranged in parallel on the surface which is the opposite surface, and a polarizing plate 16 is laminated on the back surface. The other parts are the same as those in the above embodiment, and the description thereof is omitted.

  In this embodiment, the same effect as that of the above embodiment can be expected, and the uncured liquid adhesive (A) and the uncured liquid adhesive (B) are required for adhering with the spacer 12 having a simple configuration. It is obvious that the distance between the pair of substrates 11 and 11A can be maintained over a long period of time since the above-described collapse is prevented.

Examples of the liquid adhesive according to the present invention will be described below together with comparative examples. The viscosity is a value at 25 ° C., and the surface tack is a numerical value based on JIS Z 0237.
Example 1

First, 100 parts by weight of polymethylvinylsiloxane blocked with a dimethylvinylsiloxy group-blocked polymethylvinylsiloxane having a methylvinyl group in a raw rubber-like side chain having a viscosity of 1,000,000 mPa · s or more, and a BET specific surface area of 200 m ² / g. A base compound is prepared by uniformly mixing 10 parts by weight of fumed silica, 1.5 parts by weight of hexamethyldisilazane as a surface treating agent for silica, and 1 part by weight of water, followed by heating and mixing at 170 ° C. for 2 hours under reduced pressure. did.

  Next, 100 parts by weight of the prepared base compound was mixed with 1,3-divinyltetramethyldisiloxane complex of platinum (30 parts by weight of platinum metal in the catalyst with respect to 1 million parts by weight of polydimethylsiloxane in the base compound). The composition A) was prepared by mixing 1.0 part by weight of vinyl triethoxysilane and 100 parts by weight of toluene.

  Next, 100 parts by weight of the base compound is mixed with a polydimethylsiloxane blocked with a dimethylhydrogensiloxy group at both ends of a molecular chain having a viscosity of 10 mPa · s (a silicon atom in this component relative to a vinyl group in the polydimethylsiloxane contained in the base compound). (Mole ratio of bonded hydrogen atoms is 0.2), and the molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane having an average of 3 silicon-bonded hydrogen atoms in one molecule and a viscosity of 6 mPa · s A copolymer (amount such that the molar ratio of silicon atom hydrogen atoms in this component to vinyl groups in the polydimethylsiloxane contained in the base compound is 2.8) and 1.0 part by weight of vinyltriethoxysilane; Composition B) was prepared by mixing 100 parts by weight of toluene.

  Subsequently, it measured according to the plasticity test prescribed | regulated to Williams plasticity: JIS K6249: 1997 "Test method of uncured and cured silicone rubber". Specifically, toluene as the solvent of the above compositions A) and B) was heated to completely evaporate, and 2 g each was used as a spherical test piece.

  When the test piece is manufactured in this way, the test piece is sandwiched between cellophane papers, set in a parallel plate plasticity meter with a dial gauge (manufactured by Ueshima Seisakusho; Williams Plastometer), and a load of 49 N is applied and left for 3 minutes. When the dial gauge scale was read to 1 / 100th of a millimeter, the thickness of the test piece was recorded, and the value was multiplied by 100 to obtain the plasticity. The results shown in Table 1 were obtained.

  Next, the composition A) and B) were coated on an 125 μm thick PET film with an applicator so that the thickness after drying was 1.0 mm, and dried at 100 ° C. for 30 minutes to remove toluene as a solvent. All samples were volatilized to prepare a sample piece of 15 × 400 × 1.0 mm. Once the sample pieces were prepared, the surface tack was measured using the sample pieces of compositions A) and B), and the results shown in Table 1 were obtained.

  Moreover, when the sample pieces of the compositions A) and B) were superposed in order from the end, no bubbles were mixed between A) and B). Furthermore, when the said adhesion | attachment sample piece was left to stand at room temperature and the hardening state was investigated, the result as shown in Table 2 was obtained.

実施例２

Example 2

  First, two pieces of 100 × 25 × 8 mm float glass were prepared, and the composition A) and B) of Example 1 were uniformly applied to the portion from the end of the float glass to 25 mm with a brush at 100 ° C. 15 The solvent toluene was volatilized using a drier for a minute. The thicknesses of the compositions A) and B) after drying were both 20 μm.

Then, according to JIS K 6850 tensile shear bond strength test method, the dried composition A) on the float glass and the dried composition B) on the other float glass are superposed and 1 at room temperature. Left for days. After standing for 1 day in this way, this was fixed to a tensile tester and pulled at a speed of 10 mm / min. As a result, an overlap shear strength of 1.8 N / mm ² was obtained, and the fracture state was composition A), or It was destruction of B).

Furthermore, the compositions A) and B) dried on the used float glass were left for 6 months in an atmosphere of 23 ° C. and 50% RH and 40 ° C. and 50% RH. After standing for 6 months in this way, both were stuck and allowed to stand at room temperature for 1 day, and the tensile shear bond strength similar to the above was measured. As a result, the composition A) and B) after passage of 23 ° C. and 50% RH for 6 months was 2.1 N / mm ² , and the composition A) and B) after 40 ° C. and 50% RH for 6 months passed was 1.9 N / mm 2. ^No decrease in adhesive strength was observed in either case.
Comparative Example 1

First, 100 parts by weight of polymethylvinylsiloxane blocked with a dimethylvinylsiloxy group-blocked polymethylvinylsiloxane having a methylvinyl group in a raw rubber-like side chain having a viscosity of 1,000,000 mPa · s or more, and a BET specific surface area of 200 m ² / g. A base compound is prepared by uniformly mixing 45 parts by weight of fumed silica, 6.5 parts by weight of hexamethyldisilazane as a silica surface treatment agent, and 1 part by weight of water, followed by heating and mixing at 170 ° C. for 2 hours under reduced pressure. did.

  Next, 100 parts by weight of the prepared base compound was mixed with 1,3-divinyltetramethyldisiloxane complex of platinum (30 parts by weight of platinum metal in the catalyst with respect to 1 million parts by weight of polydimethylsiloxane in the base compound). ), 1.0 part by weight of vinyltriethoxysilane and 200 parts by weight of toluene were mixed to prepare composition C).

  Next, 100 parts by weight of the base compound is mixed with a polydimethylsiloxane blocked with a dimethylhydrogensiloxy group at both ends of a molecular chain having a viscosity of 10 mPa · s (a silicon atom in this component relative to a vinyl group in the polydimethylsiloxane contained in the base compound). (Mole ratio of bonded hydrogen atoms is 0.2), and the molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane having an average of 3 silicon-bonded hydrogen atoms in one molecule and a viscosity of 6 mPa · s A composition obtained by mixing a copolymer (amount such that the molar ratio of silicon atom hydrogen atoms in this component to 2.8 in the polydimethylsiloxane contained in the base compound is 2.8) and toluene in 200 parts by weight of toluene. D) was prepared.

  Subsequently, it measured according to the plasticity test prescribed | regulated to Williams plasticity: JIS K6249: 1997 "Test method of uncured and cured silicone rubber". Specifically, toluene as the solvent of the above compositions C) and D) was heated to completely evaporate, and 2 g was used as a spherical test piece.

  When the test piece is manufactured, the test piece is sandwiched between cellophane papers and set in a parallel plate plasticity meter (Kamijima Seisakusho; Williams Plastometer) equipped with a dial gauge. A load of 49 N is applied and left for 3 minutes. When the scale of the dial gauge was read to 1/100 of a millimeter, the thickness of the test piece was recorded, and the value was multiplied by 100 to obtain the plasticity. The results shown in Table 3 were obtained.

  Next, the above compositions C) and D) were coated on a 125 μm-thick PET film with an applicator so that the thickness after drying was 1.0 mm, and dried at 100 ° C. for 30 minutes to remove all toluene as a solvent. Volatilization was performed to prepare a sample piece of 15 × 400 × 1.0 mm. Once the sample pieces were prepared, the surface tack was measured using the sample pieces of the above compositions C) and D). As a result, the results shown in Table 3 were obtained.

  Furthermore, when the sample pieces of the above compositions C) and D) were stacked in order from the end, a large number of bubbles were generated between C) and D), and the bubbles were pushed out. The sheet was pressed, but the sheet was so plastic that it was impossible to remove the bubbles. Furthermore, when the bonded sample piece was left at room temperature and its cured state was examined, the results shown in Table 4 were obtained.

比較例２

Comparative Example 2

First, 100 parts by weight of polymethylvinylsiloxane blocked with a dimethylvinylsiloxy group-blocked polymethylvinylsiloxane having a methylvinyl group in a raw rubber-like side chain having a viscosity of 1,000,000 mPa · s or more, and a BET specific surface area of 200 m ² / g. 7 parts by weight of fumed silica, 1.0 part by weight of hexamethyldisilazane as a surface treatment agent for silica, and 1 part by weight of water are uniformly mixed, and then heated and mixed at 170 ° C. for 2 hours under reduced pressure to prepare a base compound. did.

  When the base compound is prepared, 100 parts by weight of the base compound is mixed with 1,3-divinyltetramethyldisiloxane complex of platinum (30 parts by weight of platinum metal in the catalyst with respect to 1 million parts by weight of polydimethylsiloxane in the above base compound). A composition E) was prepared by mixing 1.0 part by weight of vinyl triethoxysilane and 200 parts by weight of toluene.

  Next, 100 parts by weight of the base compound is mixed with a polydimethylsiloxane blocked with a dimethylhydrogensiloxy group at both ends of a molecular chain having a viscosity of 10 mPa · s (a silicon atom in this component relative to a vinyl group in the polydimethylsiloxane contained in the base compound). (Mole ratio of bonded hydrogen atoms is 0.2), and the molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane having an average of 3 silicon-bonded hydrogen atoms in one molecule and a viscosity of 6 mPa · s A copolymer (amount such that the molar ratio of silicon atom hydrogen atoms in this component to vinyl groups in the polydimethylsiloxane contained in the base compound is 2.8) and 1.0 part by weight of vinyltriethoxysilane; Composition F) was prepared by mixing 200 parts by weight of toluene.

Subsequently, it measured according to the plasticity test prescribed | regulated to Williams plasticity: JIS K6249: 1997 "Test method of uncured and cured silicone rubber". Specifically, toluene as the solvent of the above compositions E) and F) was heated to completely evaporate, and 2 g was used as a spherical test piece.
Then, place the test piece in cellophane paper and place it in a parallel plate plasticity meter with a dial gauge (Kamijima Seisakusho; Williams Plastometer). Reading up to 1/100 of a millimeter, then recording the thickness of the test piece and multiplying that value by 100 to give the plasticity, the results shown in Table 5 were obtained.

  Next, the composition E) and F) were coated on a 125 μm-thick PET film with an applicator so that the thickness after drying was 1.0 mm, and dried at 100 ° C. for 30 minutes to remove all toluene as a solvent. Volatilization was performed to prepare a sample piece of 15 × 400 × 1.0 mm. And when the test piece was stuck, the said composition E) and F) protruded from the bonding edge part, and the circumference | surroundings were violently soiled.

比較例３

Comparative Example 3

First, the compositions A) and B) used in Example 1 were coated on a 125 μm-thick PET film with an applicator so that the thickness after drying was 1.2 mm, and dried at 100 ° C. for 30 minutes. All the toluene which is was volatilized, and the sample piece of 15x400x1.2mm was produced. Once the sample pieces were prepared in this way, the sample pieces of the compositions A) and B) were superposed in order from the end.
As a result, no mixing of bubbles was confirmed between A) and B). Moreover, when the bonded sample piece was allowed to stand at room temperature and its cured state was examined, the results shown in Table 6 were obtained.

It is a section explanatory view showing an embodiment of a liquid adhesive concerning the present invention. It is a section explanatory view showing a 2nd embodiment of the liquid adhesive concerning the present invention.

Explanation of symbols

1 Dye-sensitized solar cell 2 Transparent plate (adherend)
2A transparent plate (adherence)
5 Electrolyte Solution 10 LCD Panel 11 Substrate (Substrate)
11A substrate (adherence)
12 spacer 13 liquid crystal composition 14 wiring electrode 15 alignment film 16 polarizing plate

Claims (5)

A liquid adhesive comprising an uncured liquid adhesive (A) and an uncured liquid adhesive (B),
Uncured liquid adhesive (A)
1) Organopolysiloxane having at least two alkenyl groups and having a viscosity at 25 ° C. of 100,000 mPa · s or more 100 parts by weight 2) An amount sufficient to cure the hydrosilylation catalyst (A) and (B) 4) Filler 1 to 2,000 parts by weight 5) Adhesion imparting agent 0 to 10 parts by weight 6) Solvent 10 to 2,000 parts by weight
Uncured liquid adhesive (B)
1) An organopolysiloxane having at least two alkenyl groups and a viscosity at 25 ° C. of 100,000 mPa · s or more 100 parts by weight 3) It has at least two hydrosilyl groups and a viscosity of 10 to 1,000 mPa · s. s or more organohydrogenpolysiloxanes (A) and (B)
The amount of silicon-bonded hydrogen atoms is
4) Filler 1 to 2,000 parts by weight 5) Adhesive agent 0 to 10 parts by weight 6) Solvent 10 to 2,000 parts by weight Consisting of a composition,
A liquid adhesive, wherein the total amount of 5) is 0.1 to 20 parts by weight with respect to 200 parts by weight of the total amount of 1).   An uncured liquid adhesive (A) is applied to one of a pair of opposed substrates and an uncured liquid adhesive (B) is applied to the other, and after the solvent is volatilized, they are bonded and cured and adhered. The liquid adhesive according to claim 1.   The plasticity of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of the solvent is in the range of 30 to 500 when measured with a Williams plasticity meter. The liquid adhesive according to 2.   The liquid adhesive according to claim 1, 2, or 3, wherein the thickness of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of the solvent is 1 mm or less. When the tackiness on the surfaces of the uncured liquid adhesive (A) and the uncured liquid adhesive (B) after volatilization of the solvent is measured by a test method based on JISZ 0237, the ball numbers are 4 to 21, respectively. The liquid adhesive according to any one of claims 1 to 4, which is in a range.

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