JP2018168277A - Quick hardening adhesive and adhesion method using the adhesive - Google Patents

Abstract

To provide an adhesive and an adhesion method of an adhesive, to which an adherend is adhered and fixed in extremely short time when the adhesive is applied and the adherend is laminated, which has allowance of time by hardening before lamination, and further has followability to expansion and shrinkage of the adherend due to difference between hot and cold or moisture resistance, and is easy to use.SOLUTION: There is provided an adhesive which is manufactured by blending a seamless capsule 3 in which a compound having at least two isocyanate groups in a molecule is included 32 in a shell 31 with a liquid setting resin containing a hydrolyzable silyl group in a molecule as an adhesive resin component and an aminosilane oligomer having a primary or secondary amino group, can have sufficient time allowance from application of the adhesive to an adherend to lamination, can adhere and fix the adherend in extremely short time when laminated, and in which the cured article has wet heat resistance and flexibility capable of following motion of the adherend due to difference between hot and cold, and therefore can be used outdoor.SELECTED DRAWING: Figure 1

Description

  In the present invention, a liquid curable resin having a hydrolyzable silyl group in a molecule as a resin used for an adhesive, an aminosilane oligomer having a primary and / or secondary amino group, and two or more isocyanate groups in the molecule The present invention relates to a liquid adhesive composition capable of expressing initial adhesion in a very short time by blending a seamless capsule containing a compound in a shell, and an adhesion method using the adhesive.

  Adhesives have various types and uses of adherends, and some of them are used for vertical walls such as nameplates, hooks, and tiles. In that case, the adherend must be fixed until the adhesive has hardened to a certain extent so that the adherend does not move, and it is pressed manually for a long time, or temporarily fixed to fix the adherend. Such work is necessary. Therefore, when an adhesive is used, the adherend adheres and fits in as short a time as possible after bonding the adherend is a performance generally required as an easy-to-use adhesive.

  Conventionally, various methods have been taken as adhesives that enable bonding in a short time. For example, there is a cyanoacrylate adhesive as an instantaneous adhesive having an extremely fast curing speed (Patent Document 1). Since this cyanoacrylate adhesive has the property of being hard to cure when exposed to oxygen in the air, it adheres in a very short time by applying the adhesive and bonding the adherend, but before bonding, It is hard to cure, that is, it has a feature that it is easy to take open time. Therefore, it is widely used as a general-purpose quick-cure adhesive that is easy to use.

On the other hand, a cured product of a cyanoacrylate adhesive is inferior in moisture resistance and has a drawback that it cannot cope with expansion and contraction due to heat when different materials are bonded to each other due to lack of flexibility. Therefore, it is not very suitable for outdoor use where it is exposed to wind and rain or sunlight, that is, for use on a nameplate or the like.

  Further, as an adhesive resin that enables rapid curing, there is a moisture-curing resin having a flexible structure such as polyoxyalkylene in the main chain skeleton and a hydrolyzable silyl group at the terminal (Patent Documents 2 and 3). ). The cured product of the moisture-curing resin has a certain moisture resistance and is flexible so that it can follow the expansion and contraction of the adherend due to the difference in temperature.

  On the other hand, since moisture-curing resin is cured by moisture naturally present in the air, the speed of curing speed is directly linked to the short time that can be left before bonding, that is, the short open time. . For this reason, considering the convenience during use, the curing speed is naturally limited, and when used in such a way that the adherend naturally moves, such as bonding in the vertical direction, it is necessary to perform compression or temporary fixing until it adheres. A means such as a stop is required.

  In addition, in order to increase the curing speed while allowing an open time that is not excessive or insufficient for use, by adding a microcapsule in the adhesive and encapsulating a component that cures the adhesive in the capsule, There is a method in which curing is started immediately upon use. For example, in a two-component (meth) acrylic adhesive (Patent Document 4), a component necessary for curing is enclosed in a microcapsule, and the capsule is broken by external pressure to cause the liquid in the capsule to flow out. At that time, one liquid of two liquid components is enclosed in a microcapsule and added to the other liquid, whereby a one-liquid fast-curing (meth) acrylic adhesive can be obtained.

On the other hand, although the method of separating the components by the capsule is very useful, it is necessary to consider the risk of the capsule breaking due to an unexpected situation. In particular, since the (meth) acrylic adhesive is radical curing, there is a risk that the reaction proceeds in a chained manner when only a few microcapsules are broken before use. In addition, when using a volatile low-molecular (meth) acrylic monomer, there is a concern about odor, so it is necessary to pay attention to this point when applied to a general-purpose adhesive for general consumers.

  In addition, the use of an adhesive tape is the simplest method if the adhesiveness is immediately manifested when bonded. However, adhesives do not exhibit the same adhesive strength as adhesives, so they are not suitable for applications such as bonding of nameplates used outdoors, even if they are used for temporary fixing or applications that do not require much strength. .

JP 59-222462 A Japanese Patent No. 3161545 Japanese Patent No. 303303 Japanese Patent No. 5005273

  In the present invention, the adherend adheres and fits in a very short time when the adhesive is applied and the adherends are bonded together, that is, the adherends are maintained without shifting even if the adherend is not fixed. In addition, it provides an easy-to-use adhesive and bonding method that has a time delay before curing and that has a time delay before curing, and further has an ability to follow expansion and contraction of the adherend due to temperature difference and moisture resistance and moisture resistance. .

  The present inventors have intensively studied the development of an adhesive that solves the above-described problems. As a result, a liquid curable resin containing a hydrolyzable silyl group in the molecule as an adhesive resin component, an aminosilane oligomer having a primary and / or secondary amino group, and at least two or more isocyanate groups in the molecule As a result of blending seamless capsules containing the compound in the shell, before the adhesive is applied to the adherend and bonded, the curing speed of the adhesive resin is relatively gentle, so there is sufficient time to spare When bonded, the seamless capsule breaks and the isocyanate compound is discharged, so that it reacts with the aminosilane oligomer in the system to develop adhesion and can be stored in a very short time. Furthermore, the adherend adheres firmly as the adhesive resin hardens, but the cured product has moisture resistance and the flexibility to follow the movement of the adherend due to temperature differences, so it can be used outdoors. The present invention has been completed. The present invention is composed of the following first to seventh inventions.

That is, the first invention relates to a liquid curable resin (A) containing a hydrolyzable silyl group represented by the following general formula (Chemical Formula 1), an aminosilane oligomer (B) having a primary and / or secondary amino group, The present invention relates to a liquid adhesive composition in which a compound having at least two isocyanate groups in a molecule is blended with a seamless capsule (C) encapsulated in a shell.
(In Chemical Formula 1, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)

In the second invention, the aminosilane oligomer (B) is at least one selected from — (CH ₂ ) ₃ —NHR or — (CH ₂ ) ₃ {—NH— (CH ₂ ) ₃ } n—NH _2. It has the amino group of this invention, It is related with the adhesive composition which concerns on 1st invention. (In the formula, R is H, an alkyl group having 1 to 20 carbon atoms, a monovalent saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. And n represents 1 or 2.)

  In the third invention, 0.001 to 1 part by mass of boron trifluoride and / or its complex (D) is further added to 100 parts by mass of the mixture of the liquid curable resin (A) and the aminosilane oligomer (B). The present invention relates to a liquid adhesive composition according to the first or second invention. By blending boron trifluoride and its complex, the reaction rate of the hydrolyzable silyl group can be increased.

The fourth invention is the liquid adhesion according to any one of the first to third inventions, wherein the mixing ratio of the liquid curable resin (A) and the aminosilane oligomer (B) is 20/80 to 80/20 by mass ratio. It is related with an agent composition. The liquid curable resin (A) contributes to the adhesive strength and flexibility of the cured adhesive resin, and the aminosilane oligomer (B) contributes to the initial adhesion. The effect can be fully exhibited.

  5th invention is 1st-4th invention formed by mix | blending 2-15 mass parts of seamless capsules (C) with respect to 100 mass parts of mixtures of liquid curable resin (A) and an aminosilane oligomer (B). The liquid adhesive composition according to any one of the above. When the blending amount of the seamless capsule (C) is small, the adhesiveness developed at the time of pressing is reduced, and when the blending amount is large, the force required for pressing the adherend to break the capsule increases.

  The sixth invention relates to the liquid adhesive composition according to any one of the first to fifth inventions, wherein at least 50% by mass or more of the liquid curable resin (A) is composed of a resin component having a molecular weight of 10,000 or more. It is about things.

  In a seventh invention, the compound having at least two or more isocyanate groups in the molecule has a spherical particle size of 0.5 to 3 mm and the spherical shape of the seamless capsule (C) encapsulated in the shell. The present invention relates to a liquid adhesive composition according to any one of the first to sixth inventions, wherein the volume ratio of the content including the compound having an occupied isocyanate group is at least 30% or more.

  The liquid adhesive composition according to the present invention and the bonding method using the adhesive include a primary and / or secondary amino group in a liquid curable resin containing a hydrolyzable silyl group in the molecule as an adhesive resin component. When an adhesive is used by blending an aminosilane oligomer having a non-reactive shell and a seamless capsule containing a compound having at least two isocyanate groups in the molecule into a non-reactive shell. Adhesiveness can be expressed in a very short time after the adherend is pressed, and the cured product has the effect of obtaining moisture resistance and flexibility.

It is explanatory drawing which showed the manufacturing method of a seamless capsule (C).

  Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[Liquid curable resin (A)]
The liquid curable resin (A) of the present invention contains a hydrolyzable silyl group represented by the following general formula (Chemical Formula 2), and can be cured by hydrolysis, polycondensation with moisture in the air. .
(In Chemical Formula 2, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)

Commercially available liquid curable resins (A) can be used. Some of them are commonly called modified silicones. For example, Kaneka MS Polymer Series, Silyl Series, MA Series, EP Series, SA Series, OR Series from Kaneka Corporation, Exester Series from Asahi Glass Co., Ltd., Evonik Silane modified polyalphaolefins from Japan, KC series, KR series, X-40 series from Shin-Etsu Chemical Co., Ltd., XRP series from Toagosei Co., Ltd., Acroflow series from Soken Chemical Co., Ltd., etc. It is not done.

  The liquid curable resin (A) can be synthesized as described in, for example, Japanese Patent No. 303303 and Japanese Patent No. 4578166. In particular, the main chain skeleton is preferably polyoxyalkylene.

  The liquid curable resin (A) preferably has a molecular weight of 10,000 or more at least 50% by mass or more. Although it is known that a tough cured product can be obtained by crosslinking a higher molecular weight resin, it is practical as an adhesive by making the cured product of the adhesive composition in the present invention more tough. Strength can be obtained.

[About aminosilane oligomer (B)]
The aminosilane oligomer (B) of the present invention is an aminosilane oligomer having a primary and / or secondary amino group. Moreover, since it is a silane oligomer, it has a hydrolyzable silyl group and / or its condensed structure in a molecule | numerator as general knowledge. The primary and secondary amino groups possessed by the aminosilane oligomer (B) can react with the isocyanate group very quickly, and contribute to the initial adhesion which is the effect of the present invention.

Among the aminosilane oligomers (B) as described above, those that are particularly easily available are those obtained by condensing aminosilanes having primary and / or secondary amino groups that are commercially available and widely used for various applications, so-called silane coupling agents. This is an aminosilane oligomer. That is, the aminosilane oligomer (B) has at least one amino group selected from — (CH ₂ ) ₃ —NHR or — (CH ₂ ) ₃ {—NH— (CH ₂ ) ₃ } n—NH _2. It will be. (In the formula, R is H, an alkyl group having 1 to 20 carbon atoms, a monovalent saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In addition, n represents 1 or 2.) These aminosilane oligomers (B) are readily available and exhibit the effects of the present invention, and thus are industrially useful.

  What is marketed can be used for the aminosilane oligomer (B) in this invention. For example, dynasylan 1146, dynasylan VPS SIVO260, dynasylan VPS SIVO280, dynasylan SIVO203 from Evonik Japan Co., Ltd., KF-8010, X-22-161A, KF-393 from Chisso Co., Ltd. However, it is not limited to these.

  The liquid curable resin (A) makes the cured product tougher when the adhesive composition is cured, and the aminosilane oligomer (B) contributes to initial adhesion. Therefore, although these compounding ratios can be changed as necessary, in order to achieve the effects of the present invention more practically, the compounding ratio of the liquid curable resin (A) and the aminosilane oligomer (B) is The mass ratio is preferably 20/80 to 80/20, more preferably 30/70 to 70/30.

[Seamless capsule (C)]
The seamless capsule (C) of the present invention is one in which a compound having at least two or more isocyanate groups in the molecule is encapsulated in the shell, and when the shell is broken, the isocyanate compound becomes the aminosilane oligomer (B). The reaction can contribute to the initial adhesion.

  The seamless capsule (C) used in the present invention is composed of two layers, that is, an inner layer composed of the encapsulated compound (c) and an outer layer composed of a coating layer.

As the compound (c) which can be included in the seamless capsule (C) of the present invention, isocyanate compounds having various structures having at least two or more isocyanate groups in the molecule can be used. For example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,2, 4- or 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl- 3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohex Diisocyanate, methyl-2,6-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate {1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane}, isophorone diisocyanate, norbornene diisocyanate methyl, 1, 3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, triphenylmethane 4,4 ′, 4 ″ -triisocyanate, tris (p-isocyanate) There is Eniru) thiophosphate.

Further, a polyisocyanate compound having a polymethylene polyphenyl polyisocyanate, a uretdione skeleton, an isocyanurate skeleton, a biuret skeleton, etc. and having two or more isocyanate groups may be used.

Moreover, you may use together the compound which has one isocyanate group per molecule from uses, such as adjusting the physical property of hardened | cured material. Examples thereof include n-butyl isocyanate, t-butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.

  The compound (c) that can be encapsulated in the seamless capsule (C) can be further blended with an isocyanate compound as necessary. For example, polyether polyol represented by Preminol S4015 (manufactured by Asahi Glass Co., Ltd.), polyester polyol represented by Polylite OD-X2420 (manufactured by DIC Corporation), polycarbonate polyol represented by Nippon Poly 982R (manufactured by Tosoh Corporation), URIC There are polyols such as castor oil-based polyol represented by H-30 (manufactured by Ito Oil Co., Ltd.). Moreover, you may mix | blend the polyisocyanate which has an isocyanate group at the terminal with which these polyol, polythiol, etc. and the excess amount of the polyfunctional isocyanate compound reacted. Also, ester plasticizers such as phthalate ester, adipate ester, trimetate ester, benzoate ester, acetylcitrate ester, terephthalate ester, polyester plasticizer, epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid You may mix | blend plasticizers, such as epoxy plasticizers, such as ester. Also, silane coupling agents such as vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane are blended. May be.

  These can be blended as necessary, for example, to adjust the viscosity of the isocyanate compound and to modify the physical properties and adhesiveness of the cured product.

  The outer layer in the seamless capsule (C) includes a water-permeable base material and a film composition that may contain other components as necessary. The substrate is preferably at least one of a gelling agent and a photocurable resin.

  Gelling agents that can be used for the base material include gelatin, carrageenan, agar, glucomannan, alginic acid, gellan gum, xanthan gum, locust bean gum, pectin, psyllium seed gum, guar gum, fur celeran, arabinogalactan, arabinoxylan, gum arabic , Dextrin, modified dextrin, starch, modified starch, pullulan, carboxymethylcellulose salt and the like. Gelatin, carrageenan, agar, glucomannan, and alginic acid are preferred. The gelling agent is preferably contained in the coating composition in an amount of 0.1 to 98% by mass, more preferably 0.3 to 95% by mass.

  The photocurable resin that can be used for the substrate is a resin that is cured by a reaction caused by light irradiation, and is usually a photopolymerizable monomer, a photopolymerizable oligomer, or a photopolymerizable monomer or photopolymerizable oligomer. These addition polymers are used. A photocurable resin may be used independently or may be used in combination of 2 or more types. The photo-curable resin is preferably used in combination with a polymerization initiator.

  Examples of the photopolymerizable oligomer include a photopolymerizable oligomer that is cured by radical polymerization and a photopolymerizable oligomer that is cured by a cationic polymerization reaction. The number average molecular weight of the photopolymerizable oligomer is 300 to 30,000, preferably 500 to 20,000.

  Photopolymerizable oligomers that are cured by radical polymerization include those having (meth) acryloyl groups, vinyl groups, and the like as functional groups. For example, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, ester (meth) acrylate oligomer, (meth) acrylate oligomer, unsaturated polyester oligomer, polyene / thiol oligomer, and cinnamic acid An oligomer is mentioned. Specifically, a resin (polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, alkyl chain having 4 to 10 carbon atoms) having a photopolymerizable ethylenically unsaturated group at both ends of polyalkylene glycol. Polyalkylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.), high acid value unsaturated polyesters, high acid value unsaturated polyepoxides, anionic unsaturated Examples include acrylic resins, cationic unsaturated acrylic resins, and unsaturated polyamides. The term “(meth) acrylate” indicates at least one of acrylate and methacrylate. For example, polyethylene glycol di (meth) acrylate refers to at least one of polyethylene glycol diacrylate and polyethylene glycol dimethacrylate.

  Some photopolymerizable oligomers that are cured by a cationic polymerization reaction have an epoxy group, a vinyl ether group, or the like as a functional group. For example, there are epoxy oligomers and vinyl ether oligomers.

  Among the above photopolymerizable oligomers, acrylate oligomers, unsaturated polyester oligomers, polyene / thiol oligomers, cinnamic acid oligomers, epoxy oligomers, and vinyl ether oligomers are particularly preferably used.

  Among the photocurable resins used as the base material, particularly ionic or nonionic hydrophilic groups sufficient to be uniformly dispersed in an aqueous medium, such as hydroxyl groups, amino groups, carboxyl groups, phosphate groups, sulfones. Resins containing acid groups, ether bonds and the like are preferably used. Such photo-curable resins are disclosed in, for example, Japanese Patent Publication No. 55-40, Japanese Patent Publication No. 55-20676, Japanese Patent Publication No. 62-19837, and the like. Specifically, hydrophilic resin compounds having at least two ethylenically unsaturated bonds in one molecule, high acid value unsaturated polyesters, high acid value unsaturated epoxides, anionic unsaturated acrylic resins, unsaturated Polyamide or the like is preferably used. Among these, hydrophilic resin compounds having at least two ethylenically unsaturated bonds in one molecule are preferably used.

  Examples of the hydrophilic resin compound having at least two ethylenically unsaturated bonds in one molecule include resins having a photopolymerizable ethylenically unsaturated group at both ends of the polyalkylene glycol. For example, (1) polyethylene glycol di (meth) acrylates in which both terminal hydroxyl groups of polyethylene glycol having a molecular weight of 400 to 6000 are esterified with 2 moles of (meth) acrylic acid; (2) both polypropylene glycol having a molecular weight of 200 to 4000 Polypropylene glycol di (meth) acrylates whose terminal hydroxyl groups are esterified with 2 mol of (meth) acrylic acid; (3) 1 mol of both end hydroxyl groups of polyethylene glycol having a molecular weight of 400 to 6000 are converted to diisocyanate compounds (tolylene diisocyanate, xylylene Urethanation with 2 moles of diisocyanate, isophorone diisocyanate, etc., and further unsaturated monohydroxy compounds (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic) (3) unsaturated polyethylene glycol urethanated product to which 2 moles of acid 3-hydroxypropyl, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.) are added; and (4) An unsaturated polypropylene glycol urethanized product in which 1 mol of polypropylene glycol having a molecular weight of 200 to 4000 is urethanated with 2 mol of a diisocyanate compound and 2 mol of an unsaturated monohydroxy compound is further added.

  Examples of the high acid value unsaturated polyesters include salts of unsaturated polyesters having an acid value of 40 to 200 obtained by esterification of a polyhydric carboxylic acid having an unsaturated bond and a polyhydric alcohol. Can be mentioned.

  Examples of the high acid value unsaturated epoxides include unsaturated epoxy resins having an acid value of 40 to 200. Such a resin can be prepared, for example, by preparing an addition reaction product of an epoxy resin and an unsaturated carboxyl compound ((meth) acrylic acid, etc.) and adding an acid anhydride to the hydroxyl group remaining in the addition reaction product. Obtained by.

  Examples of the anionic unsaturated acrylic resin are derived from at least two (meth) acrylic monomers of (meth) acrylic acid and (meth) acrylic ester, and also have a carboxyl group and a phosphate group. And / or a resin having a photopolymerizable ethylenically unsaturated group introduced into the copolymer having a sulfonic acid group.

  Unsaturated polyamides, for example, are adducts of diisocyanates (tolylene diisocyanate, xylylene diisocyanate, etc.) and ethylenically unsaturated hydroxy compounds (such as 2-hydroxyethyl acrylate) added to water-soluble polyamides such as gelatin. Can be obtained.

  The photocurable resin used as the substrate is contained in the coating composition as a solid content, preferably 10 to 99% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 90% by mass.

  In the outer layer of the seamless capsule (C), other components that can be contained in addition to the base material include, for example, a plasticizer, a gelling aid, a water-soluble compound having an unsaturated bond, a polymerization initiator, a photosensitizer, And colorants. When a gelling agent is used, it may be preferable to use a gelling aid. Moreover, when using a photocurable resin, it is preferable to use a polymerization initiator, especially a photopolymerization initiator.

The plasticizer may include a water-soluble polyhydric alcohol or a water-soluble derivative thereof (hereinafter collectively referred to as “polyhydric alcohol compound”), a sugar compound, or triethyl phosphate. Specific examples of water-soluble polyhydric alcohols or water-soluble derivatives thereof, which are polyhydric alcohol compounds, include glycerin, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, sugar Examples include esters, glycerides and sorbitan esters. Among these, glycerin is more preferably used.
Examples of the sugar compound include monosaccharides, oligosaccharides, sugar alcohols, and polysaccharides. Examples of monosaccharides include glucose. Examples of oligosaccharides include disaccharides such as sucrose (sucrose), lactulose, lactose, maltose, trehalose, cellobiose, dehydration condensates of these disaccharides, raffinose, panose, maltotriose, melezitose, gentianose, and the like. .
Examples of the sugar alcohol include sorbitol, mannitol, maltitol, erythritol, lactitol, xylitol and the like.

  Further, the gelling aid is used for the purpose of increasing the strength of the film containing the gelling agent. The gelling aid can be appropriately selected depending on the type of gelling agent. Examples of the gelling aid include alkali metal salts, alkaline earth metal salts, and ammonium salts. Gelling aids may be used alone or in combination of two or more. In particular, when alginic acid, gellan gum, pectin, or carrageenan is included as the gelling agent, it is preferable to use an alkali metal salt, alkaline earth metal salt, ammonium salt, or the like as the gelling aid. The gelling aid is contained in the coating composition at a solid content concentration of preferably 0.1 to 30% by mass, preferably 0.5 to 20% by mass.

  Moreover, the water-soluble compound which has an unsaturated bond is used in order to raise the intensity | strength of the film | membrane containing photocurable resin. From the viewpoint of suppressing polymerization that does not depend on the active species generated from the photopolymerization initiator, a substance that dissolves in an aqueous solvent at 80 ° C. or lower is preferably used. Specifically, itaconic acid, N, N′-methylenebisacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N, N′-methylenebisacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, acryloylmorpholine, N, N'-dimethylacrylamide, N-vinylformamide, (meth) acrylate and the like can be mentioned. The water-soluble compounds having an unsaturated bond may be used alone or in combination of two or more. The water-soluble compound having an unsaturated bond is contained in the coating composition in a solid content concentration of 0.01 to 30% by mass, preferably 0.1 to 25% by mass.

  The polymerization initiator is not particularly limited, but a photopolymerization initiator is preferably used. The photopolymerization initiator is a compound that generates a polymerization initiating species by light irradiation and promotes polymerization or a crosslinking reaction. Typical examples include benzoin, acetoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, benzyl, Michler's ketone, xanthone, chlorothioxanthone, isopropyl thioxanthone, benzyl dimethyl ketal, naphthol, anthraquinone, hydroxyanthracene, acetophenone. Examples include diethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenylpropanone, aromatic iodonium salt, aromatic sulfonium salt, iodonium salt, sulfonium salt, triarylsulfonium salt, trifluorocarbon sulfonium salt, and the like. . The polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is contained in the coating composition in a solid content concentration of 0.001 to 20% by mass, preferably 0.1 to 10% by mass.

  Moreover, a photosensitizer is contained when using a photocurable resin as a base material. Examples of photosensitizers include ruthenium complexes and porphyrin compounds. Such a photosensitizer imparts sufficient sensitivity in the visible light region.

  The colorant is not particularly limited, and natural colorants, synthetic colorants, and the like are appropriately used as necessary.

[Method for producing seamless capsule (C)]
A two-layer seamless capsule (C) composed of an inner layer and an outer layer is produced, for example, by a submerged dropping method using the production apparatus shown in FIG. In order to improve the uniformity of the size of the resulting seamless capsule, vibration may be applied to the jet stream. Specifically, using a capsule manufacturing apparatus including the concentric double nozzle 1 having the first nozzle 11 and the second nozzle 12 from the innermost side, the encapsulated liquid 32 is discharged from the first nozzle 11 and from the second nozzle. It is prepared by a method including a step of simultaneously extruding the film portion forming solution 31 into the carrier fluid 2. As the carrier fluid 2, a liquid oily substance (liquid oil), for example, an oily substance that is liquid at 0 to 40 ° C. is used. As the cooling liquid, for example, medium chain fatty acid triglyceride (MCT), vegetable oil (such as coconut oil, sunflower oil, safflower oil, sesame oil, rapeseed oil, grape seed oil, and a mixture thereof), liquid paraffin and a mixture thereof are used. be able to. This liquid is preferably used after being cooled.

Next, in order to form a film on the surface of the droplet, the droplet 3 ejected from the injection nozzle 1 is cooled in the carrier fluid 2, or the carrier fluid 2 or the carrier fluid 2 is separated. Light the drop. When the film forming solution 31 includes a gelling agent, a film is formed by sol-gel transition when cooled. On the other hand, when the film portion forming solution 31 contains a photocurable resin, a film is formed by light irradiation. When alginic acid, gellan gum, pectin, or carrageenan is used as a gelling agent, it may be added dropwise to a divalent or higher metal ion solution. In this way, a two-layer seamless capsule is obtained.

When the film forming solution 31 contains a gelling agent, the temperature of the carrier fluid 2 is set in the range of −10 to 30 ° C., preferably 0 to 20 ° C.

  When the film portion forming solution 31 contains a photocurable resin, the wavelength of the actinic ray necessary for curing the photocurable resin is generally in the range of about 200 nm to about 600 nm. It is advantageous to irradiate with a light source that emits. Examples of such a light source include a mercury lamp, a fluorescent lamp, a xenon lamp, a carbon arc lamp, and a metal halide lamp. It is preferable that a photosensitizer is contained in the above-described film part forming solution in that sufficient sensitivity is imparted to the visible light region. Depending on the type of the photocurable resin, it can be cured using an actinic ray having a short wavelength in the ultraviolet region. The irradiation time varies depending on the intensity and distance of the light source, but is generally in the range of 0.05 seconds to 10 minutes, preferably 0.5 seconds to 2 minutes.

  The particle size range of the seamless capsule (C) is usually 0.1 mm to 10 mm, preferably 0.3 mm to 8 mm. The prepared capsules may be used without being dried and with moisture remaining in the capsules depending on the use, or may be used after being dried by a normal pressure or vacuum drying method.

  In the present invention, by making the particle size of the seamless capsule (C) 0.5 mm to 3 mm, it is easy to mix in the adhesive, and the seamless capsule can be easily broken by pressing when using the adhesive. . Moreover, it is preferable that the compound (c) included is at least 30% or more by volume ratio, and more preferably 50% or more. Thereby, when the seamless capsule (C) is broken, the compound (c) to be included can contribute to the initial adhesion more efficiently.

  The seamless capsule (C) has no seam and has a uniform size and film thickness. As the seamless capsule (C), a capsule having desired characteristics can be prepared in the same manner as a conventional capsule by using a film composition containing various additives such as a colorant.

[About boron trifluoride and / or its complex (D)]
The boron trifluoride and / or its complex (D) of the present invention can accelerate the curing rate of the liquid curable resin (A) by adding it.

  Boron trifluoride and / or its complex (D) are preferably those having a complex structure because they are easy to handle. Examples of the complex structure include, but are not limited to, an amine complex, an alcohol complex, and an ether complex. Examples of the amine compound used in the amine complex include ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine. It is not something. Examples of alcohols used in the alcohol complex include, but are not limited to, primary alcohols such as methanol, ethanol, propanol, and n-butanol, and secondary alcohols such as isopropanol and 2-butanol. Examples of ethers used in the ether complex include, but are not limited to, dimethyl ether, diethyl ether, and n-dibutyl ether. Of these boron trifluoride complexes, amine complexes are particularly preferred from the standpoint of stability and catalytic activity.

Boron trifluoride complexes are commercially available, such as boron trifluoride ethyl ether, boron trifluoride methyl ether, boron trifluoride n-butyl ether, boron trifluoride tetrahydrofuran, boron trifluoride from Stella Chemifa Corporation. Phenol, boron trifluoride monoethylamine, and boron trifluoride piperidine are on the market. These can be used in the present invention.

  Said boron trifluoride and / or its complex (D) may be used independently and may use 2 or more types together. The blending ratio is preferably 0.001 part by mass to 1 part by mass, more preferably 0.01 part by mass to 0.2 part by mass with respect to 100 parts by mass of the mixture of the liquid curable resin (A) and the aminosilane oligomer (B). Part.

[Other ingredients]
In the present invention, various additives can be added to the adhesive composition as necessary. For example, fillers, silane coupling agents, titanate coupling agents, aluminum coupling agents, Lewis acids and their derivatives, organometallic catalysts, tackifiers, thixotropic agents, anti-aging agents and UV absorbers, diluents, There are plasticizers, pigments and the like, but the invention is not limited to these, and these are general additives to be added to the adhesive, and can be used according to applications within the scope of the present invention.

  Examples of fillers include calcium carbonate, various treated calcium carbonate, magnesium carbonate, clay, talc, hydrophilic silica, hydrophobic silica, fumed silica, fused silica glass, and organic polymer. These include, but are not limited to, balloon systems such as glass balloons and plastic balloons, metal oxide systems such as aluminum hydroxide and magnesium hydroxide, acicular crystal fillers, and fibrillated fiber systems.

  Examples of the organic polymer filler include polyester powder, polycarbonate powder, urethane resin powder, polymethylsilsesquioxane powder, acrylic resin powder, styrene resin powder, and vinyl chloride. Resin powder, SBR powder, chloroprene powder, NBR powder, acrylic rubber powder, polyolefin powder, silicone powder and the like are not limited thereto.

  Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltri Methoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- ( 6-aminohexyl) aminopropyl Trimethoxysilane, N- (2- aminoethyl) -11-Amino undecyl trimethoxysilane and the like.

  Further, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and the like can be given.

  Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycid Examples include xylpropylmethyldiethoxysilane.

  Further, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Examples include methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane.

  Moreover, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, etc. are mentioned.

  Also, bis (3-trimethoxysilylpropyl) tetrasulfane, bis (3-methyldimethoxysilylpropyl) tetrasulfane, bis (3-triethoxysilylpropyl) tetrasulfane, bis (3-methyldiethoxysilylpropyl) ) Tetrasulfane, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-methyldiethoxysilylpropyl) disulfide, etc. Is mentioned.

  Also, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanurate silane, 1,3,5- Examples include isocyanurate silane compounds such as N-tris (3-triethoxysilylpropyl) isocyanurate silane and 1,3,5-N-tris (3-methyldiethoxysilylpropyl) isocyanurate silane. However, it is not necessarily limited to these.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tri (N- Aminoethyl-aminoethyl) titanate and the like.

  Examples of the aluminum coupling agent include (alkylacetoacetato) aluminum diisopropylate such as (methylacetoacetoxy) aluminum diisopropylate, (ethylacetoacetoxy) aluminum diisopropylate, (isopropylacetoacetoxy) aluminum diisopropylate, etc. Is mentioned.

  Examples of Lewis acids and their derivatives include Lewis acids such as titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, antimony chloride and other metal halides and boron tribromide. And boron halide. Examples of Lewis acid derivatives include amine complexes, alcohol complexes, and ether complexes of the above Lewis acids. Examples of the amine compound used for the amine complex include ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine. Examples of alcohols used in the alcohol complex include primary alcohols such as methanol, ethanol, n-propanol and n-butanol, and secondary alcohols such as isopropanol and 2-butanol. Examples of ethers used for the ether complex include dimethyl ether, diethyl ether, and di (n-butyl) ether.

  Examples of the organometallic catalyst include octyl tin compounds, bismuth compounds, and metal complexes.

  Examples of the octyltin compound include dioctyltin distearate, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dineodecate, dioctyltin bisethylmalate, dioctyltin bisoctylmalate, dioctyltin bisisooctylthio Examples include glycolate, octyl tin maleate, and dioctyl tin dimethoxide. Moreover, these commercial products made by Nitto Kasei Co., Ltd., trade names: Neostan U-500, Neostan U-800, Neostan U-810, Neostan U-830, Neostan U-820, Neostan U-840, Neostan U-850, Neostan U-860, Neostan U-870, etc. can also be used.

  An example of the bismuth compound is bismuth (2-ethylhexanoate). Commercially available products mainly made of bismuth (2-ethylhexanoate) manufactured by Nitto Kasei Co., Ltd., trade names: U-600, U-660 and the like can also be used.

  Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetylacetate, and the like. Examples thereof include metal acetylacetonate complexes such as nato and vanadium acetylacetonate.

  Examples of tackifiers, so-called tackifiers, include phenolic resins, modified phenolic resins (eg cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, Maron indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, hydrocarbon resin, hydrogenated petroleum resin, terpene resin, DCPD resin, etc. However, it is not limited to these.

  Examples of the thixotropic agent include, but are not limited to, anhydrous silica, amide wax, fatty acid bisamide, hydrogenated castor oil, and the like.

  Antiaging agents and ultraviolet absorbers include compounds having a primary amino group, secondary amino group, tertiary amino group, hydroxyl group, carboxyl group and / or mercapto group in the molecule, and deterioration of various resins. Those widely used as an inhibitor are included.

  Specific examples of the anti-aging agent and the ultraviolet absorber include triacetonediamine, poly [(6-morpholino-s-triazine-2,4-diyl) {2,2,6,6-tetramethyl-4-piperidyl. } Imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N, N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-pheny Diamine, N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, mixed N, N′-diallyl-p-phenylenediamine, alkylated diphenylamine, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro- 1,3 5-triazine condensate, diphenylguanidine, di-o-tolylguanidine, N-cyclohexylbenzothiazyl-sulfenamide, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2 -Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone trihydrate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate trihydrate, 4-dodecyloxy- 2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- Octoxyben Zophenone, 2-hydroxy-4-octoxybenzophenone, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methyl) Enyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5) -Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl -2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) Nzotriazole, 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole N-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2 ′, 4′-di-t-butyl Phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, tris (3,5 -Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate Phosphoric acid, ethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3 (3 ', 5'-di-t-butyl-4'-hydroxy) Phenyl) propionate] methane, n-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydro Xylphenyl) propionate], 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 2,2'- Butylidene-bis (4-ethyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-methyl-6- t-butylphenol), 2,2'-methylene-bis (4-methyl-t-butylphenol), 2,2'-methylene-bis (4-ethyl-t-butylphenol), 6- (2-benzotriazolyl) ) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylpheno 2,4-dimethyl-6- (1-methylcyclohexyl) phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 (Octyloxy) phenol, 2,6-di-t-butyl-4-ethylphenol, 2- (2H-benzotriazol-2-yl) -4-menthyl-6- (3,4,5,6-tetrahydro Phthalimidylmethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,5-di-t-butylhydroquinone, Poly (2,2,4-trimethyl-1,2-dihydroquinone), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone, 2,5-di-t-amylhydroquinone, 4, 4'- Tylidene-bis (6-t-butyl-m-cresol), 2,2'-methylene-bis [6- (1-methylcyclohexyl) -p-cresol], 1- [2- {3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6 -Tetramethylpiperidine, S- (3,5-di-t-butyl-4-hydroxybenzyl) -2-ethyl-n-hexyl-thioglycolate, 4,4'-thiobis (6-t-butyl-m -Cresol), p-benzoquinonedioxime, 1,6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, sari Phenyl tyrrate, 4-t-butylphenyl salicylate, 1,1,3-tris (2-methyl-t-butyl-4-hydroxy-5-t-butylphenyl) butane, 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, dimethyl succinate -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, methyl-3- [3-t-butyl-5- (2H-benzotriazol) -2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol (Irganox E201), a mixture of Irganox E201, glycerin and low density polyethylene, a mixture of Irganox E201 and stearic acid, bis (3,5-di-t-butyl-4 -Ethyl hydroxybenzylsulfonate) mixture of calcium and polyethylene wax, 2,4-bis [(octylthio) methyl] -o-cresol, N, N'-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphos Nate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (3,5-di-tert-butyl) -4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,3-bis [{3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyl}] propionohydrazide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5- Triazine, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, mercaptobenzothiazole, 2-mercaptobenzimidazole, manufactured by Sankyo Lifetech Co., Ltd., trade name: SANOL LS-765, SANO LS-292, Sanol LS-944, Sanol LS-440, Sanol LS-770, Sanol LS-744, manufactured by Ciba Specialty Chemicals, Inc., trade names: Tinuvin 123, Tinuvin 292, Tinuvin 144, etc. .

  As the diluent, any solvent that does not inhibit the effect of the present invention and has a dilution effect can be preferably used.

  Examples of the plasticizer include aromatic carboxylic acid esters such as dioctyl phthalate and dibutyl phthalate, aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, or polyalkylene glycol, polyalkylene glycol modified product, (meth) acrylic Liquid tackifier, naphthenic, aromatic, paraffinic, silicone, etc. oils such as terpene monomer polymer, terpene or terpene phenol copolymer with low polymerization degree, etc., but are not limited to these Absent.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

[Liquid curable resin A]
100 parts by mass of KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) was charged into a 1 liter flask equipped with a stirrer, and 84 parts by mass of methyl acrylate was added to this for 1 hour. The mixture was added dropwise with stirring. Thereafter, it was cured at 50 ° C. for 7 days to obtain a silylating agent.

  Preminol S4015 (manufactured by Asahi Glass Co., Ltd., polyether polyol, MW = 15,000, OHV = 7.5 mgKOH / g) 98 parts by mass, PR-3007 (manufactured by ADEKA Corporation, polyether polyol, OHV = 37.8) 2 parts by mass, Desmodur I (manufactured by Sumika Covestrourethane Co., Ltd., isophorone diisocyanate) 2.6 parts by mass, Neostan U-830 (manufactured by Nitto Kasei Co., Ltd., dioctyltin) 0.005 parts by mass A portion was charged and stirred at 100 ° C. for 3 hours. Thereafter, 3.7 parts by mass of the silylating agent was added and stirred for 1 hour to obtain a liquid curable resin A.

[Liquid curable resin B]
Preminol S4015 (manufactured by Asahi Glass Co., Ltd., polyether polyol, MW = 15,000, OHV = 7.5 mgKOH / g) 100 parts by mass in a 1 liter flask equipped with a stirrer, Desmodur I (manufactured by Sumika Covestro Urethane Co., Ltd.) 2.5 parts by mass of isophorone diisocyanate), 0.005 parts by mass of neostan U-830 (manufactured by Nitto Kasei Co., Ltd., dioctyltin) were charged and stirred at 100 ° C. for 3 hours. Thereafter, 4 parts by mass of the silylating agent was added and stirred for 1 hour to obtain a liquid curable resin B.

[Liquid curable resin C]
Preliminol S4012 (manufactured by Asahi Glass Co., Ltd., polyether polyol, MW = 10,000, OHV = 11.7 mgKOH / g) 100 parts by mass in a 1 liter flask equipped with a stirrer, Desmodur I (manufactured by Sumika Covestro Urethane Co., Ltd.) (Isophorone diisocyanate) 3.5 parts by mass, Neostan U-830 (manufactured by Nitto Kasei Co., Ltd., dioctyl tin) was charged in 0.005 parts by mass and stirred at 100 ° C. for 3 hours. Thereafter, 4.5 parts by mass of the silylating agent was added and stirred for 1 hour to obtain a liquid curable resin C.

[Seamless capsule A]
Desmodur I (manufactured by Sumika Covestrourethane Co., Ltd., isophorone diisocyanate) was prepared as a compound having two or more isocyanate groups in the molecule, and this was used as inclusion liquid a-1.

Further, 80 parts by mass of gelatin and 20 parts by mass of glycerin were added to 400 parts by weight of ion-exchanged water and dissolved by heating at 65 ° C. to obtain a film part forming solution a-2.

Next, using the concentric double nozzle, the inclusion liquid a-1 and the coating portion forming solution a-2 from the inner nozzle are simultaneously discharged into rapeseed oil cooled to 10 ° C. and flowing down to a particle size of 1 A 5 mm two-layer seamless capsule was produced. Thereafter, rapeseed oil was removed and the capsules were dried, and then seamless capsule A was obtained.

[Seamless capsule B]
Into a 1-liter flask equipped with a stirrer, 90 parts by mass of Desmodur I (manufactured by Sumika Covestrourethane Co., Ltd., isophorone diisocyanate) and 10 parts by mass of Takenate 600 (Mitsui Chemical Co., Ltd., 1,3-bisisocyanate methylcyclohexane) were charged. It stirred for 30 minutes and the inclusion liquid b-1 was obtained.

90 parts by weight of gelatin and 10 parts by weight of polyethylene glycol 400 were added to 400 parts by weight of ion-exchanged water and dissolved by heating at 65 ° C. to obtain a film part forming solution b-2.

  Then, using the concentric double nozzle, the inclusion liquid b-1 from the inner nozzle and the film forming solution b-2 from the outer nozzle are simultaneously discharged into rapeseed oil cooled to 10 ° C. and flowing down. A 5 mm 2-layer seamless capsule was produced. Thereafter, after removal of rapeseed oil and drying of the capsules, seamless capsule B was obtained.

[Seamless capsule C]
A 1 liter flask equipped with a stirrer was charged with 50 parts by mass of Takenate 600 (Mitsui Chemicals Co., Ltd., 1,3-bisisocyanate methylcyclohexane) and 50 parts by mass of Desmodur N3200A (manufactured by Sumika Covestrourethane Co., Ltd., polyisocyanate compound). For 30 minutes to obtain inclusion liquid c-1.

95 parts by weight of gelatin and 5 parts by weight of triethyl phosphate were added to 400 parts by weight of ion-exchanged water and dissolved by heating at 65 ° C. to obtain a film part forming solution c-2.

Then, using the concentric double nozzle, the inclusion liquid c-1 from the inner nozzle and the film forming solution c-2 from the outer nozzle are simultaneously discharged into the flowing palm oil cooled to 10 ° C. A 0 mm two-layer seamless capsule was produced. Then, after removing palm oil and drying the capsule, seamless capsule C was obtained.

[Seamless capsule D]
A 1-liter flask with a stirrer was charged with 90 parts by mass of Desmodur I (manufactured by Sumika Covestrourethane Co., Ltd., isophorone diisocyanate) and 10 parts by mass of Desmodule N3400 (manufactured by Sumika Covestrourethane Co., Ltd., polyisocyanate compound), 30 The mixture was stirred for a minute to obtain inclusion liquid d-1.

60 parts by mass of nona (ethylene glycol) diacrylate, 20 parts by mass of EBECRYL2000 (manufactured by Daicel Ornex Co., Ltd.) and 0.6 parts by mass of benzoin isobutyl ether were mixed to prepare a film part forming solution d-2. Using a concentric double nozzle, the encapsulated liquid d-1 is discharged to the inner nozzle, and the film forming solution d-2 is simultaneously discharged from the outer nozzle into rapeseed oil cooled to 13 ° C. Body).

  The droplet was irradiated with ultraviolet rays (wavelength: 320 to 400 nm) using a high-pressure mercury lamp (manufactured by GS Yuasa Lighting Co., Ltd., HAL200L), and the droplet was once gel set. After removing rapeseed oil, seamless capsules D were obtained. The particle diameter of the obtained seamless capsule D having a two-layer structure was 1.5 mm.

[Example 1]
100 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 100 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), 6 parts by mass of Aerosil # 200 (Nippon Aerosil Co., Ltd., hydrophilic silica), 0.05 parts by mass of boron trifluoride monoethylamine was charged, and dehydration was performed for 1 hour with stirring in a reduced pressure environment at 100 ° C. Thereafter, the whole amount was transferred to a rotation and revolution type stirring device, and further 20 parts by mass of seamless capsule A was added and mixed to obtain an adhesive composition 1.

SUS304 (25 mm × 100 mm × 1.5 mm) is prepared as the adherend, and the adhesive composition 1 is placed on one end of the adherend in a range of 25 mm × 20 mm so that the number of capsules is about 3 / cm ^2. After applying, the other end of the adherend was bonded to the applied region and pressed for 20 seconds so that the capsule was broken. Thereafter, the resistance in the shear direction was measured using a digital force gauge to measure the initial adhesion.

[Example 2]
An adhesive composition 2 was obtained in the same manner as in Example 1 except that the seamless capsule B was used instead of the seamless capsule A.

  Further, the initial adhesiveness of the adhesive composition 2 was measured in the same manner as in Example 1.

Example 3
An adhesive composition 3 was obtained in the same manner as in Example 1 except that the seamless capsule C was used instead of the seamless capsule A.

SUS304 (25 mm × 100 mm × 1.5 mm) is prepared as an adherend, and the adhesive composition 3 is applied to one end so that the number of capsules is about 10 / cm ² , and the other is bonded together. Clamped for 20 seconds. Thereafter, the resistance in the shear direction was measured using a digital force gauge to measure the initial adhesion.

Example 4
Adhesive composition 4 was obtained in the same manner as in Example 1 except that seamless capsule D was used instead of seamless capsule A.

  Further, the initial adhesiveness of the adhesive composition 4 was measured in the same manner as in Example 1.

Example 5
100 parts by mass of liquid curable resin A in a 1 liter flask with a stirrer, 80 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), dynasylan VPS SIVO 260 (Evonik Japan Co., Ltd., aminosilane oligomer) 20 parts by mass and Aerosil # 200 (Nippon Aerosil Co., Ltd., hydrophilic silica) 6 parts by mass were charged and dehydrated for 1 hour with stirring in a 100 ° C. vacuum environment. went. Thereafter, the whole amount was transferred to a rotation and revolution stirrer, and 20 parts by mass of seamless capsule A was further added and mixed to obtain an adhesive composition 5.

  Further, the initial adhesiveness of the adhesive composition 5 was measured in the same manner as in Example 1.

Example 6
80 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 20 parts by mass of Exester S2410 (Asahi Glass Co., Ltd., modified silicone), 100 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), Aerosil RY200 6 parts by mass (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica) and 0.05 part by mass of boron trifluoride monoethylamine were charged, and dehydration was performed for 1 hour with stirring in a 100 ° C. reduced pressure environment. Thereafter, the whole amount was transferred to a rotation and revolution type stirring device, and further 20 parts by mass of seamless capsule A was added and mixed to obtain an adhesive composition 6.

  Further, the initial adhesiveness of the adhesive composition 6 was measured in the same manner as in Example 1.

Example 7
In a 1 liter flask equipped with a stirrer, 80 parts by mass of liquid curable resin B, 120 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), 1 part by mass of CRAYVALLAC SLX (manufactured by Arkema Co., Ltd., thixotropic agent), 3 0.05 parts by mass of monoethylamine borohydride was charged, and dehydration was performed for 1 hour with stirring under a reduced pressure environment at 100 ° C. Thereafter, the whole amount was transferred to a rotation and revolution stirrer, and 20 parts by mass of seamless capsule A was further added and mixed to obtain an adhesive composition 7.

  Further, the initial adhesiveness of the adhesive composition 7 was measured in the same manner as in Example 1.

Example 8
100 parts by mass of liquid curable resin C in a 1 liter flask equipped with a stirrer, 100 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), 6 parts by mass of Aerosil # 200 (Nippon Aerosil Co., Ltd., hydrophilic silica), 0.05 parts by mass of boron trifluoride monoethylamine was charged, and dehydration was performed for 1 hour with stirring in a reduced pressure environment at 100 ° C. Thereafter, the whole amount was transferred to a rotation and revolution type stirring device, and further 20 parts by mass of seamless capsule A was added and mixed to obtain an adhesive composition 8.

  Further, the initial adhesiveness of the adhesive composition 8 was measured in the same manner as in Example 1.

[Comparative Example 1]
100 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 100 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), 6 parts by mass of Aerosil # 200 (Nippon Aerosil Co., Ltd., hydrophilic silica), 0.05 parts by mass of boron trifluoride monoethylamine was charged, and dehydration was performed for 1 hour with stirring under a reduced pressure environment at 100 ° C. to obtain a composition 1 for comparison.

SUS304 (25 mm × 100 mm × 1.5 mm) is prepared as an adherend, and about 100 g / m ^{2 of the} composition 1 for comparison is applied to one end using a spatula with a comb, and the other is bonded. Clamped for 20 seconds. Thereafter, the resistance in the shear direction was measured using a digital force gauge to measure the initial adhesion.

[Comparative Example 2]
170 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 30 parts by mass of Shellsol TK (manufactured by Shell Chemicals Japan, hydrocarbon diluent), Aerosil # 200 (manufactured by Nippon Aerosil Co., Ltd., hydrophilic) Silica) 6 parts by mass and boron trifluoride monoethylamine 0.05 parts by mass were charged and stirred for 1 hour in a nitrogen atmosphere at 100 ° C. Thereafter, the whole amount was transferred to a rotation and revolution type stirring device, and further 20 parts by mass of seamless capsule A was added and mixed to obtain a composition 2 for comparison.

  In addition, the initial adhesion of the comparative composition 2 was measured in the same manner as in Example 1.

[Comparative Example 3]
100 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 100 parts by mass of KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane), Aerosil # 6 parts by mass of 200 (manufactured by Nippon Aerosil Co., Ltd., hydrophilic silica) and 0.05 part by mass of boron trifluoride monoethylamine were charged, and dehydration was performed for 1 hour with stirring in a 100 ° C. reduced pressure environment. Thereafter, the whole amount was transferred to a rotation and revolution stirrer, and 20 parts by mass of seamless capsule A was further added and mixed to obtain a composition 3 for comparison.

  Moreover, the initial adhesiveness of the comparative composition 3 was measured in the same manner as in Example 1.

[Comparative Example 4]
SUS304 (25 mm x 100 mm x 1.5 mm) is prepared as an adherend, and an ultra-multipurpose SU clear (manufactured by Konishi Co., Ltd., moisture-curing adhesive) is used at one end with a combed spatula at 100 g / m. ^{About 2 were} applied, and seamless capsule A was added so as to be about 3 / cm ² . The other end portion was applied with about 100 g / m ^{2 of an} ultra-multipurpose SU clear using a spatula with a comb, and then pressed and pressed for 20 seconds. Thereafter, the resistance in the shear direction was measured using a digital force gauge to measure the initial adhesion.

[Initial adhesion test]
Each example in the table satisfies a seamless capsule (C) containing a liquid curable resin (A), an aminosilane oligomer (B), and a compound having at least two isocyanate groups, which are essential components of the present invention. In both cases, initial adhesion was developed.

  On the other hand, since Comparative Example 1 did not have a seamless capsule and Comparative Example 2 had no aminosilane oligomer, none of the initial adhesiveness was expressed. In Comparative Example 3, aminosilane was used in place of the aminosilane oligomer. However, since it was not an oligomer, the crosslinking of the isocyanate compound did not progress so much and did not contribute to the expression of adhesion. In Comparative Example 4, a seamless capsule was added to a commercially available moisture-curing adhesive, but the initial adhesion was not exhibited because the requirement of the present invention was not satisfied.

Example 9
100 parts by mass of liquid curable resin A in a 1 liter flask equipped with a stirrer, 100 parts by mass of dynasylan 1146 (Evonik Japan Co., Ltd., aminosilane oligomer), 1 part by mass of CRAYVALLAC SLX (manufactured by Arkema Co., Ltd., thixotropic agent), 3 0.05 parts by mass of monoethylamine borohydride was charged, and dehydration was performed for 1 hour with stirring under a reduced pressure environment at 100 ° C. Thereafter, the whole amount was transferred to a rotation and revolution type stirring device, and further 20 parts by mass of seamless capsule A was added and mixed to obtain an adhesive composition 9.

  For the wet heat resistance test, SUS304 (25 mm × 100 mm × 1.5 mm) was prepared as an adherend. Adhesive composition 9 was applied to one end, the other was bonded together, and cured for 10 days under conditions of 23 ° C. and 50% relative humidity, to obtain a moisture and heat resistance test specimen 9 for blanks and tests. In the test, first, the tensile shear bond strength of the test specimen 9 for heat and moisture resistance for a blank was measured in a 23 ° C. environment, and the value was used as a blank. Next, the test specimen 9 for heat and humidity resistance was cured in an environment of 85 ° C. and 85% relative humidity for 170 hours, then cooled to 23 ° C. and the tensile shear bond strength was measured under the same conditions. The moisture and heat resistance was confirmed.

  In the follow-up test by temperature difference, SUS304 (25 mm × 100 mm × 1.5 mm) and PMMA (polymethacrylate, 25 mm × 100 mm × 1.5 mm) were prepared as adherends. Adhesive composition 9 is applied to one end of the adherend, the other is bonded, and cured for 10 days under conditions of 23 ° C. and 50% relative humidity. Obtained. In the test, first, the tensile shear adhesive strength of the follow-up test specimen 9 for blank was measured in a 23 ° C. environment, and the value was used as a blank. Next, the test specimen 9 for test was repeated for 5 cycles of 80 ° C. for 3 hours and 5 ° C. for 3 hours, and then the tensile shear adhesive strength was measured under the same conditions. confirmed.

[Comparative Example 5]
Aron Alpha (registered trademark) for general use (manufactured by Toa Gosei Co., Ltd., cyanoacrylate adhesive) was prepared as an instantaneous adhesive, and the follow-up test was conducted in the same manner as in Example 9 by heat and humidity resistance and temperature difference.

[Moisture and heat resistance and followability of temperature difference]
In Example 9, the adhesive strength was maintained at a high level even in an environment at 85 ° C. and a relative humidity of 85%, which suggests that the adhesiveness can be maintained even when exposed to a high temperature and high humidity environment in an actual outdoor environment. doing. In addition, adherends with different linear expansion coefficients such as metal (SUS304) and plastic (PMMA) are bonded together, and the adhesiveness is maintained even after repeated thermal expansion and contraction at 80 ° C to 5 ° C. This suggests that the adhesiveness can be maintained even with the difference in temperature between summer and winter.

  On the other hand, in Comparative Example 5, a cyanoacrylate adhesive which is an instantaneous adhesive is used. In the wet heat resistance test, the strength decreased to 20% or less compared to the blank in the test under the same conditions as in Example 9. In the follow-up test based on the difference in temperature, the specimen was peeled off after 5 cycles of 80 ° C. to 5 ° C., and the strength could not be measured.

It can be seen that the adhesive in the present invention is not only settled by the initial adhesion, but also its cured product is rich in moisture and heat resistance and has flexibility, and is excellent in followability to the movement of the adherend.

  Seamlessly encapsulating a liquid curable resin containing a hydrolyzable silyl group, an aminosilane oligomer having a primary and / or secondary amino group, and a compound having at least two isocyanate groups in the molecule. The liquid adhesive composition composed of capsules adheres in a very short time when they are pasted together, even though there is sufficient time to apply the adhesive to the adherend and stick it together. And fit. Further, after being cured, it is excellent in moisture and heat resistance, and also excellent in followability to the movement of the adherend due to thermal expansion and contraction. These characteristics can be said to be industrially useful as an adhesive for general consumers requiring ease of use and versatility.

DESCRIPTION OF SYMBOLS 1 Injection nozzle 2 Carrier fluid 3 Droplet 11 1st nozzle 12 2nd nozzle 31 Film part formation solution 32 Inclusion liquid

Claims (7)

The liquid curable resin (A) containing a hydrolyzable silyl group represented by the following general formula (Formula 1) (A), an aminosilane oligomer (B) having a primary and / or secondary amino group, and at least two in the molecule A liquid adhesive composition comprising a seamless capsule (C) in which a compound having an isocyanate group is incorporated in a shell.
(In the formula, X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)
The aminosilane oligomer (B) has at least one amino group selected from — (CH ₂ ) ₃ —NHR or — (CH ₂ ) ₃ {—NH— (CH ₂ ) ₃ } n—NH _2. The adhesive composition according to claim 1, wherein (In the formula, R is H, an alkyl group having 1 to 20 carbon atoms, a monovalent saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. And n represents 1 or 2.)
Further, boron trifluoride and / or its complex (D) is blended in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the mixture of the liquid curable resin (A) and the aminosilane oligomer (B). Or the liquid adhesive composition of 2.
The liquid adhesive composition according to claim 1, wherein a mixing ratio of the liquid curable resin (A) and the aminosilane oligomer (B) is 20/80 to 80/20 by mass ratio.
The liquid adhesive composition according to claim 1, wherein 2 to 15 parts by mass of the seamless capsule (C) is blended with respect to 100 parts by mass of the mixture of the liquid curable resin (A) and the aminosilane oligomer (B). .
The liquid adhesive composition according to claim 1, wherein at least 50% by mass or more of the liquid curable resin (A) is composed of a resin component having a molecular weight of 10,000 or more.
  Compound having an isocyanate group in which the particle size of the seamless capsule (C) in which the compound having at least two or more isocyanate groups in the molecule is encapsulated in the shell is 0.5 mm to 2 mm and spherical. The liquid adhesive composition according to claim 1, wherein the volume ratio of the content including the content is at least 30% or more.