JP2005306938A - Sealant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealant which little breaks an adhesion interface, even when stressed or deformed before perfectly adhered and cured, can be expected to improve a sealing property by the synergistic effect of adhesion with a compression repulsive stress, has excellent workability, exhibits good thickness accuracy or good adhesiveness following uneven surfaces, can easily be finished, is little scattered with static electricity, and has excellent adhesive strength, creep resistance and adhesive strength at high temperature. <P>SOLUTION: This sealant comprises a flexible, long, narrow, and approximately linear elastic body 1 and a cylindrical un-cured adhesive layer 2 for covering the peripheral surface of the elastic body 1. The un-cured adhesive layer 2 is inserted into joints between PC panels used as adherends, and then adhered and cured to seal the joints. Since the elastic body 1 exhibits functions for supporting and reinforcing the adhesive layer 2, the sealant can effectively prevent the breakage of an adhesion interface and the development of adhesion failure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sealing material that is used for sealing joints and fixtures of buildings and prevents leakage of fluid and entry of dust from the outside.

Conventionally, as a sealing material, although not shown, a liquid sealing material that cures and adheres to an adherend and exhibits a sealing property, a shaped elastic body that exhibits a sealing property due to the compressive repulsion stress of an elastic body, and a one-pack type shaped adhesive Agents (see Patent Documents 1 and 2) and semi-cured (B-stage) adhesives have been proposed (see Patent Documents 3 and 4). Many proposals have also been made regarding a type in which a pressure-sensitive adhesive (adhesive) is applied to a crosslinked rubber sheet (see Patent Documents 5 and 6).
JP-A-1-197587 JP-A-6-108608 JP 2000-191987 JP 2000-281995 A JP-A-6-163762 Japanese Patent Application Laid-Open No. 2000-138489

  Conventional sealing materials are of the type described above. For example, in one-pack type fixed adhesives, the adhesive interface breaks down if deformation or stress acts on the bonding site before the sealing material is completely cured and bonded. There is a problem in that poor adhesion occurs. In addition, it is difficult to use in a portion having a tight tolerance such as thickness.

  Further, the B-stage adhesive also has a problem that if the deformation or stress is applied to the adhesion site before the sealing material is completely cured and adhered, the adhesion interface is destroyed and adhesion failure occurs. In addition, it is difficult to follow an uneven adherend, and there is a high possibility that a part that does not partially adhere is generated.

  In addition, the conventional liquid sealing material may cause the above-described poor adhesion, the adhesive may be scattered due to static electricity, and there is also a risk of surrounding contamination due to scattering or protrusion. In addition, composites of pressure-sensitive adhesives and cross-linked cured products may be simply applied, but interfacial peeling is likely to occur due to shear stress, inferior creep resistance, adhesive strength decreases at high temperatures, etc. There are various problems.

  The present invention has been made in view of the above, and even when stress or deformation is applied before completely cured and bonded, the adhesive interface is less likely to be destroyed, and the sealing performance is improved by the synergistic effect of adhesion and compression repulsion stress. Expected, excellent workability, good adhesion following thickness accuracy or unevenness, easy finishing, little scattering by static electricity, adhesive strength, creep resistance, high temperature adhesive strength The purpose is to provide an excellent sealing material.

In the present invention, in order to solve the above-mentioned problem, it is bonded and sealed to an adherend,
An elastic body and an uncured adhesive layer covering at least a part of the surface of the elastic body are included, and the uncured adhesive layer is adhesively cured to the adherend and sealed. .
The elastic body can be silicone rubber. The elastic body can be a silicone foam. Further, the uncured adhesive layer may be silicone (rubber) and its Williams plasticity may be set in the range of 30 to 500.

  Here, the adherends in the claims include at least a concrete structure, various building panels, a roof, an outer wall, a periphery of the opening, an interior, a pipe, a kitchen sink composed of a sink, a bathroom, a bathroom vanity, and the like. included. The elastic body can be formed into an oval cross-section, a triangle, a trapezoid, a polygonal string, a band, or the like.

  The uncured adhesive layer is formed in a shape that covers all or part of the surface of the elastic body, specifically, various cylindrical shapes, plate shapes, substantially C-shaped cross sections, substantially U-shaped cross sections, and substantially V-shaped cross sections. It does not matter whether there is a plurality or not. The uncured adhesive layer can be of a type that cures by a hydrosilylation reaction, a type that cures by a condensation reaction, or a type that cures by a radical reaction, and any of these may be used.

  According to the present invention, since the elastic body of the sealing material exhibits the function of supporting and reinforcing the adhesive layer, even if deformation, stress, etc. act on the adherend before the sealing material is cured and bonded, Breakage can be suppressed and the occurrence of adhesion failure can be prevented through this. In addition, since the elastic body compresses or bends in the thickness direction, etc., it can be used for parts with tight tolerances such as thickness, etc., and can be flexibly adapted to adherends with unevenness etc. It becomes.

  According to the present invention, even when stress or deformation is applied before completely curing and bonding, the bonding interface is less likely to be destroyed, and the improvement in sealing performance can be expected due to the synergistic effect of bonding and compression repulsion stress. There is. In addition, it has excellent workability, and good adhesion can be obtained by following thickness accuracy or unevenness, finishing is easy and there is little scattering due to static electricity, and it is excellent in adhesive strength, creep resistance, and adhesive strength at high temperature. Sealing material can be provided.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIGS. 1 to 5, the composite sealing material in the present embodiment exhibits a support function and a reinforcing function as a support. A substantially linear elastic body 1 and a cylindrical uncured adhesive layer 2 covering a peripheral surface which is the surface of the elastic body 1 are provided, and the uncured adhesive layer 2 is a plurality of adherends. The joints 11 are inserted into the joints 11 between the PC panels 10 and cured by adhesion, and the joints 11 are sealed.

  As shown in FIGS. 1 to 4, the elastic body 1 that is a rubber cross-linked body is formed into an elongated cylindrical or prismatic shape having flexibility. Any material can be selected as the elastic body 1 as long as it is a cured rubber elastic body excellent in elasticity and heat resistance.

However, since the adhesive layer 2 positioned as a sealing material on the front side is mainly made of silicone, it is necessary to avoid the use of a material that interferes with the hardening of the adhesive layer 2 or the development of adhesiveness. From this point, as the material of the elastic body 1, silicone rubber or fluororubber is optimal.
Note that the elastic body 1 is more preferably a silicone rubber foam because the stress when the sealing material is compressed to a predetermined thickness can be reduced and the generation of stress when deformation is applied can be reduced.

  The thickness of the elastic body 1 is in the range of 10 to 10,000 μm. When the thickness is less than 10 μm, the thickness accuracy is governed by the adhesive layer 2, and the reinforcing property as a support is lost even during work, and the superiority with respect to the uncured sheet becomes difficult to recognize. This is because the necessity of stacking is diminished. On the other hand, when the thickness exceeds 10,000 μm, the use as a sealing material is limited, and when heat curing is taken into consideration, heat conduction is deteriorated, and adverse effects such as time-consuming curing occur.

  In the case where the elastic body 1 is made of silicone rubber, the silicone rubber cross-linked body may be a commercially available cured product by radical reaction, an addition reaction cured product by a platinum-based catalyst, a cured product by condensation reaction, a cross-linked by ultraviolet ray or electron beam curing. Silicone rubber cross-linked bodies by any cross-linking method such as body can be used. However, in practice, a cured product by addition reaction or a cured product by radical reaction is preferable from an economical and physical viewpoint.

  When the elastic body 1 is made of fluoro rubber, the fluoro rubber cross-linked body includes a radical reaction cross-linked body, a polyol reaction cross-linked body, and an amine reaction cross-linked body, both of which can be used. From the viewpoint of strength at the time of being integrated with each other, a crosslinked product by radical reaction is preferable. Furthermore, since triisocyanurate as a crosslinking aid is effective for integration with silicone rubber, a crosslinked product using 2 parts by mass or more of triallyl isocyanurate with respect to 100 parts by mass of the fluororubber component is more preferable. . In this case, a method in which a thin silicone rubber layer is integrally formed with fluororubber in advance and an uncured adhesive layer 2 is laminated on the silicone layer is more advantageous for improving the adhesive strength at the interface.

  As shown in FIGS. 1 to 5, the uncured adhesive layer 2 is made of a silicone adhesive or the like, and is extruded by inserting the elastic body 1 or applied to the elastic body 1 to be flexible. It is formed and integrated into an elongated cylindrical shape or rectangular tube shape. In addition, it is formed into a long and narrow cylindrical or rectangular tube having flexibility, and is fitted and integrated with the elastic body 1. The adhesive layer 2 made of a silicone adhesive is required to keep its shape without departing from the elastic body 1. For this reason, when the plasticity of the silicone adhesive is measured with a Williams plasticity meter, it is preferably in the range of 30 to 500.

  When the thickness of the adhesive layer 2 is less than 5 μm, the superiority of the follow-up of the unevenness is lost compared to the B-stage adhesive, and conversely, when it exceeds 10,000 μm, it is difficult to maintain the thickness accuracy. Therefore, it is necessary to keep in mind. The silicone adhesive layer 2 can also use a silicone rubber adhesive by any crosslinking method such as radical reaction, addition reaction with a platinum-based catalyst, condensation reaction, ultraviolet light, electron beam curing, and the like. However, actually, from the economical and physical viewpoints, a cured product by addition reaction or a cured adhesion by condensation reaction is preferable.

I. Addition-curing type silicone adhesive layer This adhesive layer generally has the following basic composition.
(1) Polyorganosiloxane:
Polyorganosiloxane is a main component of an addition-curable silicone adhesive layer composition, and has an average of two or more alkenyl groups in one molecule. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable.

  Examples of organic groups bonded to silicon atoms other than alkenyl groups in this component include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups and other alkyl groups; phenyl groups, tolyl groups, xylyl groups, etc. Aryl groups; halogenated alkyl groups such as 3-chloropropyl group, 3,3,3-trifluoropropyl group and the like are mentioned, and methyl group is preferable. Examples of the molecular structure of this component include a straight chain, a partially branched straight chain, a branched chain, a network, and a dendrite. The viscosity of this component at 25 ° C. is 100,000 mPa · s or more, preferably 10,000,000 mPa · s or more.

As the polyorganosiloxane of this component, molecular chain both ends dimethylvinylsiloxy group-blocked polydimethylsiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethyl Siloxane-methylvinylsiloxane copolymer, siloxane unit represented by the formula: (CH ₃ ) ₃ SiO _1/2 and siloxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 : _{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; aryl groups such as phenyl groups and tolyl groups; Poly substituted with a halogenated alkyl group such as 3,3,3-trifluoropropyl group Lugano siloxane, allyl some or all of the vinyl groups of these polyorganosiloxanes, polyorganosiloxanes substituted with alkenyl groups such as propenyl group, and mixtures of two or more of these polyorganosiloxanes can be mentioned.

(2) Hydrogenated polyorganosiloxane:
The hydrogenated polyorganosiloxane acts as a curing agent for the present composition, and has an average of two or more silicon-bonded hydrogen atoms in one molecule. Examples of the organic group bonded to the silicon atom in this component include an alkyl 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; -Halogenated alkyl groups such as chloropropyl group, 3,3,3-trifluoropropyl group and the like are exemplified, and methyl group is preferable. Examples of the molecular structure of this component include linear, partially branched, branched, network, and dendritic. The viscosity of this component at 25 ° C. is not particularly limited, but is preferably in the range of 1 to 1,000,000 mPa · s, more preferably in the range of 1 to 10,000 mPa · s.

The polyorganosiloxane of this component includes molecular chain both ends dimethylhydrogensiloxy-blocked polydimethylsiloxane, molecular chain both ends trimethylsiloxy group-blocked polymethylhydrogensiloxane, molecular chain both ends trimethylsiloxy-blocked dimethylsiloxane and methylhydrogen. Siloxane copolymer, cyclic polymethylhydrogensiloxane, polyorganosiloxane comprising a siloxane unit represented by the formula: (CH ₃ ) ₂ HSiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 , and these polyorgano Polysiloxanes in which some or all of the methyl groups of siloxane are substituted with alkyl groups such as ethyl groups and propyl groups; aryl groups such as phenyl groups and tolyl groups; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups. Organosiloxanes and their A mixture of two or more types of reorganosiloxane is exemplified, and the resulting cured product has improved mechanical properties, particularly elongation, so that polyorganosiloxane and molecular chain having silicon-bonded hydrogen atoms only at both ends of the molecular chain. A mixture of polyorganosiloxane having a silicon atom bond in the side chain is preferred.

  In this composition, the content of this component is such that the molar ratio of silicon atom-bonded hydrogen atoms in this component to alkenyl groups in (1) component is in the range of 0.01 to 20, preferably 0.0. The amount is in the range of 1 to 10, and particularly preferably the amount is in the range of 0.1 to 5. This is because when the content of this component is less than the lower limit of the above range, the resulting adhesive layer 2 tends not to be sufficiently cured. Conversely, when the upper limit of the above range is exceeded, the mechanical properties of the resulting adhesive layer 2 tend to be reduced.

  When using a mixture of polyorganosiloxane having silicon atom-bonded hydrogen atoms only at both ends of the molecular chain and polyorganosiloxane having silicon atom bonds in the side chain of the molecular chain, the former polyorganosiloxane content Is an amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to alkenyl groups in component (1) is in the range of 0.01 to 10, preferably in the range of 0.1 to 10, More preferably, the amount is in the range of 0.1 to 5.

  The content of the latter polyorganosiloxane is such that the molar ratio of silicon atom-bonded hydrogen atoms in this component to alkenyl groups in component (1) is in the range of 0.5 to 20, more preferably 0.5. An amount that falls within the range of 10 to 10, more preferably an amount that falls within the range of 0.5 to 5 is preferable.

(3) Curing catalyst:
Platinum catalysts for hydrosilylation include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of platinum and diketone, complexes of chloroplatinic acid and olefins, complexes of chloroplatinic acid and alkenylsiloxane. 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, the chloroplatinic acid and divinyltetramethyldisiloxane complex disclosed in JP-B-42-22924 is preferred. preferable. The addition amount of this component is 1-1000 mass parts as a platinum metal atom with respect to 1 million mass parts of (1) component, Preferably it is 1-100 mass parts.

(4) Filler:
A filler is added in order to improve the mechanical strength of this composition, and is a compound normally used for mix | blending a silicone rubber. Examples of the component include fumed silica, precipitated silica, calcined silica, pulverized quartz, and powder obtained by surface-treating these silica powders with organosilicon compounds such as organoalkoxysilane, organohalosilane, and organosilazane. In particular, in order to sufficiently improve the mechanical strength of the obtained cured adhesive, it is preferable to use silica powder having a BET specific surface area of 50 m ² / g or more as this component.

  In this composition, although content is arbitrary, in order to improve the mechanical strength of the silicone rubber hardened | cured material obtained, it is in the range of 1-1000 mass parts with respect to 100 mass parts of (1) component. Preferably, it is preferable to be within the range of 1 to 400 parts by mass. Further, in the present composition, as other optional components, for example, fumed titanium oxide, carbon black, carbon nanotube, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, calcium carbonate, zinc oxide, aluminum hydroxide, Inorganic fillers such as silver, gold and nickel, inorganic and organic fillers plated with gold or silver; a filler obtained by treating the surface of these fillers with the above organosilicon compound may be contained.

(5) Adhesion imparting component:
The adhesion-imparting component is for imparting and improving adhesion in order for this addition-curable silicone adhesive to function as an adhesive. This includes methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilyl) propane, silane coupling agents such as bis (trimethoxysilyl) hexane, and partial hydrolysates thereof; epoxy group, acid anhydride group, Organic compounds having an α-cyanoacryl group and siloxane compounds containing these groups, or organic compounds or siloxane compounds having both of these groups and alkoxysilyl groups; tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, Titanium compounds such as la (2-ethylhexyl) titanate, titanium ethyl acetonate, titanium acetyl acetonate; ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl) Acetonates), aluminum compounds such as aluminum monoacetylacetonate bis (ethyl acetoacetate); zirconium compounds such as zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate good. The content of these adhesion-imparting agents is not particularly limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of component (1).

  Furthermore, this composition contains 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyne-3 for adjusting curability. -Acetylene compounds such as ol; Enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-in; 1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, silanol group-blocked methylvinylsiloxane, molecular chain Silanol group-blocked methyl vinyl siloxane / dimethyl siloxane copolymer and other organosiloxane compounds having 5% by weight or more of vinyl groups in one molecule; triazoles such as benzotriazole; Sufin acids, mercaptans, preferably contains a curing inhibitor such as hydrazines. Although content of these hardening inhibitors is not specifically limited, It is preferable to exist in the range of 0.001-5 mass parts with respect to 100 mass parts of (1) component.

  The present composition is not particularly limited, and can be prepared by mixing other optional components as necessary. However, the (1) component and the (3) component are heated and mixed in advance. The remaining components should be added to the prepared base compound.

  In addition, when other optional components need to be added, they may be added when preparing the base compound, and when this is altered by heating and mixing, components (2) to (4) are added. It is good to add when doing. Moreover, when preparing this base compound, the said organosilicon compound may be added and the surface of (3) component may be processed in-situ. In preparing this adhesive, a known kneading apparatus such as a two-roll, a kneader mixer, or a loss mixer can be used.

II Condensation-curable silicone adhesive layer This adhesive layer generally has the following basic composition.
(1) 'polyorganosiloxane:
This polyorganosiloxane is a main component of a condensation-curable silicone adhesive and is a diorganopolysiloxane represented by the following general formula (1) or (2).

  In the formula, R represents a substituted or unsubstituted monovalent hydrocarbon group, X represents an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and n represents a viscosity of the diorganopolysiloxane at 25 ° C. of 1,000,000. 000cs or more.

  In the formula, Y is a hydrolyzable group, a is 2 or 3, and R, X, and n are the same as above. Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group or an octyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, a vinyl group, a propenyl group, a butenyl group, or a heptenyl. Group, hexenyl group, alkenyl group such as allyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group such as diphenyl group, aralkyl group such as benzyl group, phenylethyl group, or the carbon atom of these groups Identical or different non-selective groups selected from a chloromethyl group, a trifluoropropyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, etc. in which some or all of the bonded hydrogen atoms are substituted with halogen atoms, cyano groups, etc. Substitution or substitution is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms.

X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, the divalent hydrocarbon group _{- (CH 2) m - (} m is 1-8) is represented by. Among these, an oxygen atom and —CH ₂ CH ₂ — are preferable. N is a number that makes the viscosity of the diorganopolysiloxane at 25 ° C. 100 to 1,000,000 cs, preferably 500 to 500,000 cs.

  Y is a hydrolyzable group, specifically, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, a ketoxime group such as a dimethylketoxime group or a methylethylketoxime group, an acyloxy group such as an acetoxy group, Examples thereof include an alkenyloxy group such as a propenyloxy group and an isobutenyloxy group. Such a diorganopolysiloxane can be produced by a known method such as obtaining a cyclic siloxane or a linear oligomer which is a monomer of various organopolysiloxanes by an equilibrium reaction with an acid or base catalyst.

Further, when a branched structure is introduced into the diorganopolysiloxane, the silane or siloxane containing SiO _3/2 units and / or SiO _4/2 units is not gelled during the equilibration polymerization. It is usual to add. Further, it is preferable that the low molecular weight siloxane is removed from the diorganopolysiloxane by stripping or washing. When such an organosiloxane is used, the initial contamination can be reduced.

(2) 'Crosslinking agent:
As this crosslinking agent, a silane having two or more, preferably three or more hydrolyzable groups in one molecule, or a partial hydrolysis condensate thereof is used. In this case, hydrolyzable groups include alkoxy groups such as methoxy, ethoxy and butoxy groups, ketoximes such as dimethyl ketoxime and methylethyl ketoxime, acyloxy such as acetoxy, isopropenyloxy and isobutyl. Examples thereof include alkenyloxy groups such as a tenenyloxy group, amino groups such as an N-butylamino group and N, N-diethylamino group, and amide groups such as an N-methylacetamide group. Among these, an alkoxy group, a ketoxime group, an acyloxy group, and an alkenyloxy group are preferable.

  The compounding amount of the crosslinking agent is 1 to 50 parts, preferably 2 to 30 parts, more preferably 5 to 20 parts, with respect to 100 parts (parts by mass, the same applies hereinafter) of the diorganopolysiloxane.

(3) 'Curing catalyst:
Curing can be accelerated by using a curing catalyst in the composition of the adhesive layer made of silicone rubber according to the present invention. Examples of the curing catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin dioctoate, tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetate). Na) Titanic acid esters or titanium chelate compounds such as titanium and titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethyl Organometallic compounds such as hexoate, manganese-2-ethylhexoate, cobalt naphthenate, alkoxyaluminum compounds, 3-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrime Aminoalkyl group-substituted alkoxysilanes such as toxisilane, amine compounds such as hexylamine and dodecylamine phosphate and salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, alkali metals such as potassium acetate, sodium acetate and lithium oxalate. Lower fatty acid salt, dialkylhydroxylamine such as dimethylhydroxylamine, diethylhydroxylamine, tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, etc. Examples thereof include silane or siloxane containing guanidyl group. These are not limited to one type, and may be used as a mixture of two or more types. The optimum amount of these curing catalysts is 0 to 20 parts, preferably 0.001 to 10 parts, and more preferably 0.01 to 5 parts with respect to 100 parts of the diorganopolysiloxane.

(4) 'Filler:
In the composition of the adhesive layer made of silicone rubber according to the present invention, it is preferable to use one or more fillers for the purpose of reinforcement in addition to the above components. Examples of such fillers include fumed silica, precipitated silica, silica whose surface is hydrophobized with an organosilicon compound, quartz powder, carbon black, talc, zeolite, bentonite and other reinforcing agents, asbestos, Examples thereof include fiber fillers such as glass fiber, carbon fiber and organic fiber, and basic fillers such as calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide and celite. Of these fillers, silica, calcium carbonate, zeolite and the like are preferable, and particularly, fumed silica and calcium carbonate whose surfaces have been subjected to a hydrophobic treatment are optimal.

  The blending amount of the filler may be selected depending on the purpose and the kind of the filler, but is 1 to 500 parts, particularly 5 to 100 parts, with respect to 100 parts of the diorganopolysiloxane (1) ′ component of the base polymer. Is good.

(5) 'Adhesive component:
Adhesion promoters include amino group-containing organoalkoxysilanes such as γ-aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane, and epoxy groups containing γ-glycidoxypropyltrimethoxysilane. Examples thereof include a reaction mixture of a mercapto-containing organoalkoxysilane such as an organoalkoxysilane and γ-mercaptopropyltrimethoxysilane, an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane. The compounding quantity of this component is 0.1-5 mass parts normally with respect to 100 mass parts of (1) 'component.

III Organic Peroxide Curing Silicone Adhesive When the organopolysiloxane composition is a curable silicone rubber composition based on an organic peroxide, the organopolysiloxane used as the base polymer is preferably a gum type, A type having a viscosity at 25 ° C. of 100 to 1,000,000 cs and having at least two alkenyl groups such as vinyl groups in the molecular chain terminal and / or molecular chain is more preferable.

  An organic peroxide is used as the curing catalyst. Examples of the organic peroxide include alkyl organic peroxides such as dicumyl peroxide and di-t-butyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and orthomethylbenzoyl peroxide. Acyl organic peroxides such as paramethylbenzoyl peroxide are used as suitable compounds. The blending amount is preferably 0.1 to 10 parts by mass, particularly preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the base polymer organopolysiloxane.

IV. Radiation curable silicone adhesive When the organopolysiloxane composition is a radiation curable silicone rubber composition, the organopolysiloxane used as the base polymer includes vinyl groups in the molecular chain terminals and / or molecular chains, Those having two or more aliphatic unsaturated groups such as an allyl group, an alkenyloxy group, an acrylic group, and a methacryl group, a mercapto group, an epoxy group, and a hydrosilyl group are used. The viscosity at 25 ° C. is preferably 100 to 1,000,000 cs.

  As reaction initiators, known acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4- Methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone 3-chloroxanthol, 3,9-dichloroxanthol, 3-chloro-8-nonylxanthol, benzoin, benzoin methyl ether, benzoin butyl ether , Bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone Torr, and the like. The blending amount is optimally 0.1 to 20 parts by mass, particularly 0.5 to 10 parts by mass with respect to 100 parts by mass of the base polymer organopolysiloxane.

  The composition of the uncured adhesive layer can be obtained by mixing a predetermined amount of the above components with a kneader such as a kneader mixer or a biaxial continuous kneader. In the present embodiment, the adhesion of the adhesive layer 2 can be improved by applying a primer to the PC panel 10. Most of the primers are obtained by dispersing a surface treatment agent containing various substances in a solvent. In this primer, the surface treatment agent is preferably a silane coupling agent. The silane coupling agent is preferably blended in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the solvent.

  Here, the preferable blending amount of the silane coupling agent is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the dispersion medium. This is because harmful effects occur. On the contrary, if it exceeds this range, the workability is lowered.

  As silane coupling agents, 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, cyclic It is preferable to use one or more substances selected from the group consisting of siloxane, chain siloxane, and cyanuric ring-containing organosilicon compound.

  Examples of the epoxy group-containing silane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxy Examples include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl (methyl) triethoxysilane. Examples of the (meth) acryl group-containing silane include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyl (methyl) dimethoxysilane.

  Examples of the vinyl group-containing silane 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, Methylhydrogen cyclic siloxane having 3-glycidoxypropyl group and 2- (trimethoxysilyl) ethyl group, methylhydrogen cyclic siloxane having 3-methacryloxypropyl group and 2- (trimethoxysilyl) ethyl group, 2 -[(3-trimethoxysilyl) propyloxycarbonyl] propyl group-containing methylhydrogen cyclic siloxane and the like. Examples of the chain siloxane include 3-glycidoxypropyl group-containing methylmethoxysiloxane, 3-glycidoxy group and methylhydrogensiloxane having a vinyl group, 3-glycidoxy group and 2- (trimethoxysilyl) ethyl group. Examples thereof include methylsiloxane.

  Examples of the cyanuric ring-containing organosilicon compound include tris (3-trimethoxysilylpropyl) isocyanurate. Since these primers are applied to the adherend using a brush or the like, the primer is applied by a coating machine such as a spray coater or a roll coater, or the adherend is dipped into the primer solution and applied. Etc. are possible.

  In the above, when the joint 11 between the PC (precast concrete) panels 10 is sealed, one side of the PC panel 10 shown in FIG. 5 is positioned at a predetermined position, the sealing surface of the PC panel 10 is arranged cleanly, The sealing material according to the invention is stuck and fixed. Then, when the other PC panel 10 is moved to a predetermined position, the sealing material is compressed and left for a predetermined time, and the joint 11 and the adhesive layer 2 constituting the sealing material are adhered and cured, so that the space between the PC panels 10 is The joint 11 can be sealed.

  According to the above configuration, since the elastic body 1 that is the core of the sealing material exhibits the support function and the reinforcing function of the outer adhesive layer 2, deformation and stress are applied to the joint 11 before the sealing material is completely cured and bonded. Even if it acts, it is possible to suppress and prevent the breakage of the adhesive interface, and to extremely effectively prevent the occurrence of adhesion failure. Further, since the elastic body 1 is compressed or bent in the radial direction, the thickness direction, and the width direction, the elastic body 1 can be easily used for a portion having a tight tolerance such as a thickness. Can be made to follow smoothly, and there is no possibility that a part that is not partially bonded will be generated.

  Further, since the processing of the adhesive layer 2 is easy, the adhesive layer 2 does not protrude, it becomes a dirty finish, and the adhesive is not scattered by static electricity. Further, interfacial delamination is less likely to occur due to shear stress, and the creep resistance can be improved, and the adhesive strength does not decrease even at high temperatures.

Next, FIG. 6 shows another embodiment of the present invention. In this case, the elastic body 1 is formed into a strip shape, and uncured adhesive layers 2 are laminated on the front and back surfaces, respectively. A sealing material covering only both surfaces of the body 1 is formed. Since other parts are the same as those in the above embodiment, the description thereof is omitted.
Also in this embodiment, it is obvious that the same effect as the above embodiment can be expected, and the pattern of the sealing material can be diversified.

Examples of the sealing material according to the present invention will be described below together with comparative examples.
Example Preparation of elastic body

  First, 100 mass of an organopolysiloxane comprising 99.535 mol% of dimethylsiloxy group units, 0.44 mol% of methylvinylsiloxy group units, 0.025 mol% of dimethylvinylsiloxy groups, and having an average degree of polymerization of about 8,000. 30 parts by mass of dry silica (product name: Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) and 2 parts by mass of dimethylpolysiloxane having a degree of polymerization of both terminal dimethylhydroxysilyl group blockings are uniformly mixed. The mixture was mixed while heating at 150 ° C. for 1 hour under a nitrogen aeration atmosphere, and cooled.

  When cooling is completed in this way, a mixing roll is used, and di-(-ortho-methylbenzoyl) peroxide (diluted to 50% by weight with dimethyl silicone oil) with respect to 100 parts by mass of the kneaded material in the cooled state 1 0.5 parts by mass and 2.0 parts of azobisbutyronitrile as a foaming material were uniformly kneaded to prepare a composition. Then, the silicone rubber composition was extruded and subjected to primary vulcanization at 300 ° C. for 1 minute and further at 200 ° C. for 4 hours to produce a silicone rubber foam molded article having a diameter of 2 mm and a specific gravity of 0.3.

Preparation of uncured adhesive layer Viscosity of 15,000,000 mPa · s, dimethylvinylsiloxy group-blocked methylvinylsiloxane / dimethylsiloxane copolymer at 100 parts by mass in a kneader (kneader) 39.4 parts by weight of dry silica treated with chlorosilane [trade name Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] and 2.8 parts by weight of dimethylpolysiloxane having a degree of polymerization of dimethylhydroxysilyl group blocking at both ends are uniformly mixed. The mixture was mixed while being heated at 150 ° C. for 1 hour under a nitrogen aeration atmosphere, and cooled.

Subsequently, using a mixing roll, in a cooled state, 100 parts by mass of the kneaded product, dimethylsiloxane / methylhydrogensiloxane copolymer (the amount of methylhydrogensiloxane is 0.7 mol / 100 g) 1.72. Parts by mass, chloroplatinic acid solution (diluted 5 parts by mass of chloroplatinic acid in 2-ethylhexanol) 0.27 parts by mass (54 parts by mass in terms of platinum atoms with respect to 1 million parts by mass of the kneaded material), vinyl 1 part by mass of triethoxysilane and 0.05 part by mass of 3-methyl-1-butyn-3-ol were uniformly kneaded to prepare a composition. This composition was confirmed to have a plasticity of 187, a green strength of 0.03 N / mm ² , an adhesive strength of 1.82 N / mm ² and a hardness of 40.

In addition, the test method of adhesive strength was based on the tensile adhesiveness test described in JIS A1439: 1997 "Test method of sealing material for construction". The curing and bonding conditions were 23 ° C./50% RH / 7 days, and float glass was used as the adherend. The applied pressure at the time of preparing the test specimen for tensile adhesion was 0.04 N / mm ² .

  The plasticity test method was measured at 25 ° C. using a parallel plate plasticity meter (Williams Plastometer) according to the measurement method specified in JIS K 6249 “Testing method for uncured and cured silicone rubber”. That is, 2 g of the adhesive layer material was used as a spherical test piece, and this test piece was sandwiched between cellophane papers and set in a parallel plate plasticity meter with a dial gauge (manufactured by Ueshima Seisakusho: Williams Plastometer). The load was allowed to stand for 3 minutes, the dial gauge scale was read to millimeters, the thickness of the test piece was recorded, and this value was multiplied by 100 to obtain the plasticity.

Preparation of sealing material Using an extruder with a cylinder diameter of 50 mm cooled to 10 ° C., the prepared elastic body is covered with an uncured adhesive layer with a thickness of 2 mm as a core, and a round string-like sealing with a diameter of 4 mm in cross section The material was molded. Once the sealing material is formed in this way, it is laminated inline with an OPP carrier film having a width of 8 mm in-line, wound on a carrier reel, put in a polyethylene bag, heat sealed and packaged in a sealed state, and then −20 Frozen at ℃.

Production of kitchen sinks The sealability and workability of the system kitchen sinks were evaluated using a sealing material, the top plate (opening member) made of artificial marble and the sink made of stainless steel. The contents of the production work are as follows. First, a sealing material is applied to the peripheral edge of the artificial marble top plate made of artificial marble having an outer dimension of width 900 mm, depth 650 mm, thickness 20 mm, opening width 800 mm, opening depth 540 mm. Pasted along. After the sealing material was bonded in this way, a stainless steel sink having an outer width of 800 mm, a depth of 580 mm, a depth of 200 mm, and a flange width of 100 mm was positioned and pasted so that the sealing material would contact the flange portion.

  Next, press the metal fittings and tightening screws until the thickness of the sealing material reaches 1 mm, fix the top plate and sink, and remove the uncured adhesive layer of the sealing material protruding from between the top plate and sink. After that, the seal part was finished and an assembly of the top plate and the sink was obtained.

Evaluation of sealing property The above assembly was allowed to stand at 23 ° C. for 7 days, the uncured adhesive layer was cured and adhered, and water was poured into the sink to the height of the seal part and left for 7 days. Although three bodies were implemented, water leakage did not occur in all. Immediately after the assembly of the assembled product, a load of 100 kg was applied for 10 minutes and left to stand at 23 ° C. for 7 days to cure and bond the adhesive layer, and water was put into the sink to the height of the seal part and left for 7 days. Three of these were carried out, but all did not leak.

Evaluation of workability When the sealing material was bonded along the peripheral edge of the opening, problems such as deformation and cutting did not occur, and it was possible to bond the sealing material in good condition on the top plate. Further, when press-fitting until the thickness of the adhesive layer became 1 mm using a presser fitting and a tightening screw, it could be easily compressed and deformed to a predetermined thickness. Furthermore, in the finishing process of the seal part, the protruding part can be easily removed, and the finishing process can be performed without damaging the bonded part or soiling the top plate or the sink. I confirmed that

Comparative Example Regarding the uncured adhesive layer, an OPP carrier film with a width of 8 mm was formed in-line by forming a round string-like sealing material having a diameter of 4 mm using an extruder with a cylinder diameter of 50 mm cooled to 10 ° C. And then wound up on a carrier reel, placed in a polyethylene bag, heat sealed and packaged in a sealed state, and stored frozen at -20 ° C.
Preparation of kitchen sink A kitchen sink assembly was obtained in the same manner as in the example.

Confirmation of sealing property The above assembly was allowed to stand at 23 ° C. for 7 days to cure and bond the uncured sealing material, and water was poured into the sink to the height of the seal part and left for 7 days. Although three bodies were implemented, no water leakage occurred. Immediately after assembly, a load of 100 kg was applied to the assembled product for 10 minutes, left to stand at 23 ° C. for 7 days to cure and bond the uncured sealing material, put water into the sink to the height of the seal part, and left for 7 days. . When three bodies were implemented, water leakage occurred in two of them.

Evaluation of workability When a presser fitting and a tightening screw were used and the uncured sealant was pressure-bonded to a thickness of 1 mm, it could be easily compressed and deformed to a predetermined thickness. Further, in the finishing process of the seal part, the protruding part can be easily removed, and the finishing process can be performed without damaging the bonded part or soiling the top plate and the sink.
However, when the sealing material is bonded along the peripheral edge of the opening, deformation (elongation in the length direction) occurs, and there is a problem that the diameter of the sealing material decreases when bonded to the top plate. .

It is a perspective explanatory view showing an embodiment of a sealing material concerning the present invention. It is a perspective explanatory view showing an embodiment of a sealing material concerning the present invention. It is a perspective explanatory view showing an embodiment of a sealing material concerning the present invention. It is a perspective explanatory view showing an embodiment of a sealing material concerning the present invention. It is an isometric view explanatory drawing which shows the state which seals the joint between PC panels in embodiment of the sealing material which concerns on this invention. It is a perspective explanatory view showing other embodiments of the sealing material concerning the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Elastic body 2 Adhesion layer 10 PC panel (adherence body)
11 joints

Claims (4)

  A sealing material that is bonded and sealed to an adherend, and includes an elastic body and an uncured adhesive layer that covers at least part of the surface of the elastic body, and the uncured adhesive layer is adhered to the adherend. A sealing material characterized in that it is bonded and cured to seal.   The sealing material according to claim 1, wherein the elastic body is silicone rubber.   The sealing material according to claim 1, wherein the elastic body is a silicone foam. The sealing material according to claim 1, 2, or 3, wherein the uncured adhesive layer is made of silicone and its Williams plasticity is set in the range of 30 to 500.

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