JP5991056B2 - Curable composition and method for producing an adhesive structure with the curable composition interposed - Google Patents

Description

  The present invention relates to a curable composition and a method for producing an adhesive structure with the curable composition interposed therebetween.

  Conventionally, in order to achieve both low viscosity and adhesion to metal, it is known to add colloidal calcium carbonate having a fatty acid as a surface treatment agent to a curable composition (see, for example, Patent Document 1).

JP 2011-246643 A

  However, (1) increasing the workability of applying the curable composition to the adherend by reducing the viscosity of the curable composition, (2) large area especially when the adherend has a large area. When the curable composition contains a large amount of an organic solvent for the purpose of providing a sufficient bonding time enough to be bonded to the adherend, the curable composition containing the colloidal calcium carbonate is used for a long time. Storage can cause the phase separation during storage, resulting in the disadvantage that the curable composition must be agitated prior to use.

  The present invention has been made in view of the above circumstances, and its object is to improve storage stability while imparting thixotropy to a liquid curable composition while having low viscosity. It is to be. Another object of the present invention is to provide a high-quality adhesive structure with high workability in that no dripping portion is seen.

  The present inventor has made extensive studies to solve the above problems, and found that the above problems can be solved by using a surface-treated colloidal calcium carbonate having a fatty acid ester as a surface treatment agent, thereby completing the present invention. It came to do. Specifically, the present invention provides the following.

  (1) The present invention comprises (A) an organic polymer having a crosslinkable silicon group and the main chain of which is not polysiloxane, (B) a filler, and (C) an organic solvent having a boiling point of 150 ° C. or lower. The filler is a surface-treated colloidal calcium carbonate having a fatty acid ester as a surface treatment agent, and the organic solvent is 10 parts by weight or more with respect to 100 parts by weight of the organic polymer. It is.

  (2) Moreover, this invention is at least 1 type from which the said organic polymer is selected from a polyoxyalkylene type polymer, a (meth) acrylic acid ester type polymer, or a saturated hydrocarbon type polymer. It is a curable composition of description.

  (3) Moreover, this invention is a curable composition as described in (1) whose said organic polymer is a mixture of a polyoxyalkylene type polymer and a (meth) acrylic acid ester type polymer.

  (4) Moreover, this invention is a curable composition in any one of (1) to (3) whose said fatty acid ester is C3-C100 saturated fatty acid ester.

  (5) Moreover, this invention is a curable composition in any one of (1) to (4) whose said organic solvent is at least 1 type selected from methanol, ethanol, or isopropyl alcohol.

  (6) Moreover, this invention is a method of manufacturing an adhesion structure by interposing the curable composition in any one of (1) to (5).

  According to the present invention, it is possible to provide a curable composition having both high thixotropy and high storage stability while having low viscosity.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Curable composition>
The curable composition of the present invention comprises (A) a crosslinkable silicon group-containing organic polymer (hereinafter also referred to as “(A) component”), (B) a filler and (hereinafter also referred to as “(B) component”. ), (C) an organic solvent having a boiling point of 150 ° C. or lower (hereinafter also referred to as “component (C)”).

[(A) Crosslinkable silicon group-containing organic polymer]
The composition of this invention contains the organic polymer which has a crosslinkable silicon group and whose principal chain is not polysiloxane as (A) component.

  In the present invention, the crosslinkable silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (1) is suitable.

In Formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ _3. A triorganosiloxy group represented by SiO— (wherein R ¹ is the same as described above), and when two or more R ¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2, respectively.

ｎは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。 Moreover, b in n formula (2) does not need to be the same.

n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied.

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

  The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

（式（３）中、Ｒ^１，Ｘ，ａは前記と同じ） In addition, the crosslinkable silicon group represented by following formula (3) is preferable at a point with easy acquisition.

(In formula (3), R ¹ , X, and a are the same as above)

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a small number of carbon atoms have high reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

  In the case of the crosslinkable silicon group represented by the above formula (3), a is preferably 2 or more in consideration of curability. Usually, when a is 3, the curing rate is higher than when a is 2.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups (—Si (OR) ₃ ) such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. And a silyl group (—SiR ¹ (OR) ₂ ). Here, R is an alkyl group, preferably an alkyl group having 10 or less carbon atoms, and more preferably a methyl group or an ethyl group.

  One type of crosslinkable silicon group may be used, or two or more types may be used in combination. The crosslinkable silicon group may be present in the main chain, the side chain, or both. It is preferable that a crosslinkable silicon group is present at the end of the molecular chain from the viewpoint of excellent cured product properties such as tensile properties of the cured product.

  At least one crosslinkable silicon group may be present in one molecule of the polymer, preferably 1.1 to 5. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited.

  As the main chain skeleton of the component (A), those having various main chain skeletons excluding polysiloxane can be used. Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymers of acrylonitrile and / or styrene, etc., and hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; adipic acid, terephthalic acid, oxalic acid Polyester polymers such as condensation polymers of polybasic acids of bisphenol A, polyhydric alcohols such as ethylene glycol and neopentyl glycol, and ring-opening polymers of lactones; nylon 6 by ring-opening polymerization of ε-caprolactam; Ring opening of nylon 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, nylon 11 by condensation polymerization of ε-aminoundecanoic acid, and ε-aminolaurolactam Nylon 12 by polymerization, a polyamide polymer such as copolymer nylon having two or more components among the above nylons; polyacrylic acid ester obtained by ion polymerization or radical polymerization of monomers such as ethyl acrylate and butyl acrylate, Ethyl acrylate, butyl acrylate Acrylic acid ester-based polymers such as acrylic acid ester copolymers of acrylic acid esters with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc .; graft weights obtained by polymerizing vinyl monomers in the organic polymer Examples of the polymer include polysulfide polymers; polycarbonate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride, diallyl phthalate polymers, and the like.

  Of the polymers having the main chain skeleton, polyester polymers, acrylate polymers, polyoxyalkylene polymers, saturated hydrocarbon polymers, polycarbonate polymers, and the like are preferable. In particular, it is easy to introduce a crosslinkable silicon group into the molecular chain end, is relatively low in viscosity and inexpensive, has a low glass transition temperature, and the resulting cured product has excellent cold resistance, heat resistance, An acrylic ester polymer excellent in weather resistance and adhesiveness, and a saturated hydrocarbon polymer excellent in heat resistance, weather resistance, durability, and moisture barrier properties are preferred.

  Furthermore, since the mixture of the polyoxyalkylene polymer and the acrylate ester polymer is excellent in the mechanical strength of the cured product, and has excellent heat resistance and adhesion to the adherend, Especially suitable. When a mixture of a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is used, the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer The total amount of the (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by weight, more preferably in the range of 10 to 45 parts by weight with respect to 100 parts by weight in total with the coalescence. When the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity is increased, and workability is deteriorated.

  The component (A) may be linear or branched, and the number average molecular weight is preferably about 500 to 50,000, more preferably 1,000 to 30,000. In the present embodiment, the number average molecular weight is a molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. When the number average molecular weight is less than 500, there is an inconvenient tendency in terms of adhesiveness of the cured product, and when it exceeds 50,000, the viscosity tends to be inconvenient because of high viscosity.

式（４）中、Ｒ^２は２価の有機基である。 The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the formula (4).

In formula (4), R ² is a divalent organic group.

R ² in Formula (4) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the formula (4) include the following repeating units.

  The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, it is preferably made of a polymer mainly composed of oxypropylene.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623 can be used. Polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and a porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336 Examples of the polymerization method using a catalyst include, but are not limited to, a polymerization method. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate and polyoxyalkylenes having a hydroxyl group; What can be obtained from this reaction can be mentioned.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. This can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter, this reaction method is referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. The unsaturated group-containing polyoxyalkylene polymer is reacted with a polyoxyalkylene polymer having a functional group such as a hydroxyl group and an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene polymer containing an unsaturated group can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained. The polymer reaction method can be applied to polymers other than polyoxyalkylene polymers.

  Polyoxyalkylene polymers having a crosslinkable silicon group are disclosed in JP-B-45-36319, JP-A-46-12154, JP-A-50-156599, JP-A-54-6096, JP-A-55-13767, and JP-A-57-164123. No. 3, 2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,960,844, JP-A-2005-213446, JP-A-2005-306871, International Patents It is described in each publication such as WO2007-040143.

（式（５）中、Ｒ^３は水素原子又はメチル基、Ｒ^４はアルキル基を示す） The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is essentially a polymer having a repeating unit represented by the formula (5).

(In Formula (5), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group)

R ⁴ in Formula (5) is an alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferable. R ⁴ may be linear or branched. Or the substituted alkyl group which has a rogen atom, a phenyl group, an epoxy group, an amino group, etc. may be sufficient. Examples of R ⁴ include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. it can.

  The molecular chain of the (meth) acrylic acid ester-based polymer consists essentially of the monomer unit of the formula (5), but the term “essentially” used here means a single unit of the formula (5) present in the polymer. It means that the total of the monomer units exceeds 50% by weight. The total of the monomer units of the formula (5) is preferably 70% by weight or more.

  Examples of monomer units other than formula (5) include acrylic acid such as acrylic acid and methacrylic acid; monomers containing amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  The (meth) acrylic acid ester polymer having a crosslinkable silicon group is used by mixing with a polyoxyalkylene polymer. In this case, the (meth) acrylic acid ester unit represented by the formula (6) has a molecular chain having a crosslinkable silicon group in that the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is high. A copolymer comprising a monomer unit and a (meth) acrylic acid ester monomer unit represented by the formula (7) is preferred.

（式（６）中、Ｒ^３は前記に同じ、Ｒ^５は炭素数１〜５のアルキル基を示す。）

(In Formula (6), R ³ is the same as above, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.)

（式（７）中、Ｒ^３は前記に同じ、Ｒ^６は炭素数６以上のアルキル基を示す。）

(In Formula (7), R ³ is the same as above, and R ⁶ is an alkyl group having 6 or more carbon atoms.)

As R < ⁵ > of Formula (6), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group etc., Preferably it is 1-4, More preferably, it is 1-2. And an alkyl group. Incidentally, R ⁵ may be a kind, or may be a mixture of two or more.

R ^{6 in the} formula (7) is, for example, a 2-ethylhexyl group, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, a behenyl group or the like having 6 or more carbon atoms, usually 7 to 30 and preferably 8 to 20 long. And an alkyl group of the chain. R ⁶ may be a single type or a mixture of two or more types. Moreover, the weight ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group can usually be obtained by radical copolymerization of a (meth) acrylic acid ester and a (meth) acrylic acid ester having a crosslinkable silicon group. Further, when an initiator having a crosslinkable silicon group or a chain transfer agent having a crosslinkable silicon group is used, the crosslinkable silicon group can be introduced into the molecular chain terminal.

  JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic ester polymers are described. Moreover, the synthesis example of Unexamined-Japanese-Patent No. 2005/082681 describes the (meth) acrylic acid ester-type polymer which has a crosslinkable silicon group by high temperature continuous polymerization.

  As disclosed in JP-A-2000-086999, a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, is also known. It has been. Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. In the present invention, a (meth) acrylic acid ester-based polymer as described above can be used.

  Specific examples of a mixture of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and an oxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A-59-122541, JP-A-63-112642, and JP-A-6-126. -172631, and JP-A-10-251552. JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. disclose oxyalkylene polymers having a crosslinkable silicon group. (Meth) acrylic acid ester-based monomer is polymerized in the presence of a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. The method of obtaining is described.

  Moreover, the saturated hydrocarbon polymer suitable for the composition of the present invention is a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) Polymerizing olefinic compounds having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as the main monomer, or (2) homopolymerizing diene compounds such as butadiene and isoprene, or It can be obtained by copolymerization with the olefinic compound, followed by hydrogenation. However, isobutylene-based polymers and hydrogenated polybutadiene-based polymers can easily introduce functional groups at the ends and control the molecular weight. This is preferable because the number of terminal functional groups can be increased, and an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, especially isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed., 1997, Vol. 15, It is known that it can be easily produced by using a polymer having a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends. .

  Examples of the method for producing a saturated hydrocarbon polymer having a reactive silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The above saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

  Examples of other organic polymers having a crosslinkable silicon group include condensation polymers and polylactones of polybasic acids such as adipic acid, terephthalic acid, and succinic acid and polyhydric alcohols such as bisphenol A, ethylene glycol, and neopentyl glycol. Polyester polymers such as ring-opening polymers; nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6/6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6 by condensation polymerization of hexamethylenediamine and sebacic acid 10, polyamide 11 such as nylon 11 by condensation polymerization of ε-aminoundecanoic acid, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, copolymer nylon having two or more components among the above nylons; polysulfide Polymer; for example, polycondensation from bisphenol A and carbonyl chloride Polycarbonate-based polymer produced, diallyl phthalate polymers, and the like.

[(B) Filler]
The colloidal calcium carbonate surface-treated with the fatty acid ester (B) can impart thixotropy to the present composition and improve storage stability. In the present invention, colloidal calcium carbonate refers to calcium carbonate artificially synthesized by reacting carbon dioxide with slaked lime and having a primary particle size of less than 1 micron.

  Generally, the surface-treated colloidal calcium carbonate is said to have a great effect of imparting thixotropy (adhesive sag prevention property) to a liquid composition such as an adhesive composition. Therefore, when colloidal calcium carbonate surface-treated with a fatty acid ester is used, thixotropy can be imparted to the present composition, and storage stability can be improved. In particular, calcium carbonate having a primary particle size of 0.5 microns or less, more preferably 0.1 microns or less, is preferable because it has a low viscosity and a large effect of imparting thixotropy.

  On the other hand, the fatty acid ester used as the surface treatment agent for colloidal calcium carbonate may be a low molecular weight polymer or a high molecular weight compound. Specific examples thereof include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfone. Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters. In this case, the fatty acid preferably has 3 to 100 carbon atoms, more preferably 3 to 60 carbon atoms, still more preferably 12 to 18 carbon atoms, and particularly preferably 16 to 18 carbon atoms. Saturated fatty acids are preferred, and particularly preferred are glycerol saturated fatty acid esters.

  (B) Although the surface treatment state and surface treatment amount of the calcium carbonate surface-treated with the fatty acid ester of the component are not particularly limited, the fatty acid ester is not liberated due to a temperature change and is firmly treated on the surface of the calcium carbonate. The surface treatment amount is preferably the minimum amount that sufficiently satisfies the storage stability. More preferably, the surface treatment amount of the fatty acid ester is 0.5 to 15% by mass, particularly 1 to 7% by mass with respect to calcium carbonate.

  As the component (B), calcium carbonate that has been surface-treated with a fatty acid ester in advance may be used, or the surface of calcium carbonate may be treated by adding a fatty acid ester during the production of the present composition.

  (B) As a component, you may use what is marketed, for example, the brand name: Sealets 200 (made by Maruo Calcium Co., Ltd.) etc. which are the colloidal calcium carbonate surface-treated with the fatty acid ester type compound etc. be able to.

  In the composition, the content of the component (B) is 2 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the component (A). It is.

[(C) Organic solvent]
The boiling point of the organic solvent (C) used in the present invention is 150 ° C. or lower. Since the boiling point is 150 ° C. or lower, it volatilizes in a short time after application to the adherend, and has tackiness in a short time.

  The organic solvent is not particularly limited as long as the boiling point is 150 ° C. or lower. For example, methanol, ethyl acetate, methyl acetate, ethanol, isopropyl alcohol, toluene, acetone, methylcyclohexane, cyclohexane, normal hexane, dimethyl carbonate Normal paraffin or isoparaffin. One type of organic solvent may be sufficient and two or more types of mixed solvents may be sufficient.

  Among them, (1) after application to the adherend, it volatilizes in a short time and has adhesiveness in a short time, (2) it can increase the possible bonding time, and (3) there is little odor. From the viewpoint, alcohol is preferably used, and methanol is particularly preferably used. In the case of a hydrocarbon-based solvent, there is a possibility that the onset of tackiness is delayed (workability is lowered) as compared with alcohol, and there is a possibility that sufficient bonding time cannot be provided.

  The content of the (C) organic solvent is appropriately selected depending on the desired workability and viscosity of the adhesive composition, but is preferably 10 to 300 parts by weight with respect to 100 parts by weight of component (A), More preferably, it is 20-300 weight part, Most preferably, it is 30-200 weight part.

[Other ingredients]
The composition of the present invention can contain various additives such as a filler, an adhesion-imparting agent, and a tackifier as needed.

  The adhesive composition of the present invention may contain a flame retardant, a curing catalyst, an antioxidant, an ultraviolet absorber, an anti-aging agent, a plasticizer, a thixotropic agent, a dehydrating agent (preservation) in addition to the above-described compounding substances. Stability modifiers), diluents, adhesion-imparting agents, physical property modifiers, tackifiers, sag-preventing agents, colorants, radical polymerization initiators, etc. The coalescence may be blended.

  A known flame retardant can be used as the flame retardant, and is not particularly limited. For example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide; phosphorus flame retardants such as red phosphorus and ammonium polyphosphate Metal oxide-based flame retardants such as antimony trioxide; bromine-based flame retardants; chlorine-based flame retardants and the like, and metal hydroxides are preferred from the standpoint of toxicity. The metal hydroxide may be a metal hydroxide surface-treated with a surface treatment agent. The said flame retardant may be used independently and may be used together 2 or more types.

  As the curing catalyst, known curing catalysts can be widely used, and are not particularly limited. Examples thereof include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetate. Nert, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, reaction product of dibutyltin oxide and phthalate, dibutyl complex salt and orthoethyl silicate Divalent tin compounds such as tetravalent tin compounds such as reaction products with tin, tin octylate, tin naphthenate, tin stearate, tin dinedecanoate (tin versatate) Organotin compounds of the following: organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) Reaction products of bismuth salts such as carboxylic acid or organic amines; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Organic lead compounds such as lead octylate; Organic iron such as iron naphthenate Compound; Organic vanadium compound; Butylamine, Octylamine, Laurylamine, Dibutylamine, Monoethanolamine, Diethanolamine, Triethanolamine, Diethylenetriamine, Triethylenetetramine Oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4 -Amine compounds such as methylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; low molecular weight obtained from excess polyamine and polybasic acid Polyamide resin; reaction product of excess polyamine and epoxy compound, etc. are exemplified.

  These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, dibutyltin diacetylacetonate, and dioctyltin dineodecanate are preferred because of their high curing speed. Moreover, a dioctyl tin compound is preferable from the viewpoint of environmental problems. The curing catalyst is preferably used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of component (A).

  The antioxidant is used to prevent oxidation of the adhesive composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done.

  The ultraviolet absorber is used for preventing the photodegradation of the adhesive composition and improving the weather resistance. For example, the ultraviolet absorber such as benzotriazole type, triazine type, benzophenone type, benzoate type, etc. Agents and the like.

  The anti-aging agent is used for preventing heat deterioration of the adhesive composition and improving heat resistance. For example, an anti-aging agent such as an amine-ketone type and an aromatic secondary amine type are used. Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.

  The plasticizer is added for the purpose of improving elongation properties after curing or adjusting the hardness to reduce the modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly-α-methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1000 (Toagosei Co., Ltd.) ) Made) Acrylic plasticizers such as UP-1080 (manufactured by Toagosei Co., Ltd.), UP-1110 (manufactured by Toagosei Co., Ltd.) and UP-1061 (manufactured by Toagosei Co., Ltd.); UP-2000 (Toagosei Co., Ltd.) ), Hydroxyl group-containing acrylic plasticizers such as UHE-2012 (manufactured by Toagosei Co., Ltd.), etc .; carboxyl group-containing acrylic polymers such as UC-3510 (manufactured by Toagosei Co., Ltd.); UG Epoxy group-containing acrylic polymers such as -4000 (manufactured by Toagosei Co., Ltd.), etc .; 0.5 such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.) Examples include acrylic polymers containing less than silyl groups, oxyalkylene resins containing less than 0.5 silyl groups, and the like.

  Examples of the thixotropic agent include inorganic thixotropic agents such as fumed silica, precipitated silica, and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivatives, and fatty acid amide. Examples thereof include wax, aluminum stearylate, and barium stearylate.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimetholdimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, zeolite, and oxidation. Examples include calcium, magnesium oxide, and zinc oxide.

  Examples of the adhesion-imparting agent include known silane coupling agents such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl)- γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxy Amino group-containing silanes such as silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane; γ -Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, etc. Vinyl type unsaturated group-containing silanes; chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane Specific examples include hydrosilanes such as trimethoxysilane and methyldiethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product will be high, and if it is too little, the adhesiveness will be reduced. It is preferable to add 0.5 to 10 parts by weight.

The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something.
It is preferable to add 1-100 mass parts of tackifier with respect to 100 mass parts of (A) component, and it is more preferable to add 5-50 mass parts.

  Moreover, a well-known filler can also be used together besides the colloidal calcium carbonate surface-treated with the fatty acid ester as said (B) component. Known fillers include, for example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, silicic anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, Zeolite etc. are mentioned, Of these, calcium carbonate is preferred. Further, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, and the like can also be used.

  As the calcium carbonate, any of heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, ground calcium carbonate and the like can be used. These calcium carbonates may be used alone or in combination of two or more. In the present invention, heavy calcium carbonate means calcium carbonate obtained by pulverizing limestone, and light calcium carbonate is calcium carbonate artificially synthesized by reacting carbon dioxide with slaked lime and has a primary particle size. Means colloidal calcium carbonate, which is artificially synthesized by reacting carbon dioxide with slaked lime and having a primary particle diameter of less than 1 micron.

<Method for producing composition>
The method for producing the curable composition of the present invention is not particularly limited. For example, the composition can be produced by blending a predetermined amount of the compounding substance and degassing and stirring. Moreover, the curable composition of this invention can prevent a thickening and can improve storage stability by heating the composition after mixing.

  The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The curable composition of the present invention can be cured at room temperature by atmospheric moisture, and is suitably used as a room temperature moisture curable adhesive composition. You may let them.

  The curable composition of the present invention is suitably used as an adhesive, but can also be used as a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all in these description.

<Synthesis of Crosslinkable Silicon Group-Containing Acrylic Polymer A>

  270 parts by mass of ethyl acetate was placed in a flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, and heated to 80 ° C. In another container, 400 parts by weight of methyl methacrylate, 118 parts by weight of stearyl methacrylate, 66.6 parts by weight of n-butyl acrylate, 22.5 parts by weight of methacryloxypropylmethyldimethoxysilane, 18.0 parts by weight of mercaptopropylmethyldimethoxysilane, azo By mixing 8.20 parts by mass of bisisobutylnitrile (AIBN), dropping it over 3 hours, and reacting at 80 ° C. for 6 hours, the number average molecular weight in terms of polystyrene determined by GPC using THF as a solvent is An acrylic ester polymer A having a molecular weight of 6000 and having an average of 2.0 methyldimethoxysilyl groups per molecule was obtained.

<Contrast of curable composition>

Compositions in Examples, Reference Examples and Comparative Examples were obtained with the following ingredients as shown in Tables 2 and 3. The content of the crosslinkable silicon group-containing acrylic polymer A is a value in terms of solid content.
1) Acrylic polymer containing a crosslinkable silicon group A) Polymer obtained in the above synthesis example B) XMAP SA120S (trade name, (meth) acrylic acid ester copolymer having a methyldimethoxysilyl group, manufactured by Kaneka Corporation)
2) Crosslinkable silicon group-containing oxyalkylene polymer: EST280 (trade name, polyoxypropylene polymer having dimethoxymethylsilyl group, manufactured by Kaneka Corporation)
3) Colloidal calcium carbonate A) Sealets 200 (trade name, surface-treated colloidal calcium carbonate using a fatty acid ester as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
B) Sealets 500 (trade name, surface-treated colloidal calcium carbonate using a fatty acid ester as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
C) Sealets 700 (trade name, surface-treated colloidal calcium carbonate using a fatty acid ester as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
D) Calfine N350 (trade name, surface-treated colloidal calcium carbonate using a fatty acid soap as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
E) Calfine 500 (trade name, surface-treated colloidal calcium carbonate using a fatty acid as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
F) MS-2000 (trade name, surface-treated colloidal calcium carbonate using a fatty acid as a surface treatment agent, manufactured by Maruo Calcium Co., Ltd.)
4) Surface treatment heavy calcium carbonate: Ryton A5 manufactured by Bihoku Flour Chemical
5) Fatty acid amide: Disparon 6500 manufactured by Enomoto Kasei Co., Ltd.
6) Hydrophobic silicon dioxide (fumed silica): Aerosil RY-200S manufactured by Nippon Aerosil Co., Ltd.
7) Organic solvent A) Methanol (boiling point: 64.7 ° C)
B) Ethanol (boiling point: 78.4 ° C)
C) Methylcyclohexane (boiling point: 101 ° C.)
D) Normal paraffin N-11 (trade name, normal paraffin having 11 carbon atoms, boiling point: 195 ° C., manufactured by JX Nippon Oil & Energy Corporation)
8) Organotin-based curing catalyst: Neostan U700ES (trade name, reaction product of dibutyl complex salt and normal ethyl silicate, manufactured by Nitto Kasei Co., Ltd.)
9) Dehydrating agent: KBM1003 (trade name, vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
10) Adhesion imparting agent: KBM603 (trade name, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Evaluation items and methods]
The results of the following evaluation are summarized in Table 4 and Table 5. Unless otherwise specified, the evaluation was performed in an RH environment at 23 ° C. and 50%.
(1) Viscosity The compositions according to Examples, Reference Examples and Comparative Examples were allowed to stand for 24 hours after adjustment, and the viscosity at 23 ° C. using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., BH rotor No. 6 20 rpm) Was measured.

(2) Thixotropic (TI value)
The compositions according to Examples, Reference Examples and Comparative Examples were allowed to stand for 24 hours after adjustment, and the viscosity at 23 ° C. was measured using the above viscometer. The measurement was performed at 2 rpm and 20 rpm, and the ratio of 2 rpm / 20 rpm was defined as thixotropy (TI value).

(3) Storage stability After leaving the compositions according to Examples, Reference Examples and Comparative Examples to stand for 24 hours in an environment of 23 ° C. and 50% RH, the results measured using the above viscometer are the initial values, and then 50 After being left in a dryer at 1 ° C. for 1 week, it was left in an environment of 23 ° C. and 50% RH for 24 hours to adjust the liquid temperature to 23 ° C., and the viscosity was measured in the same manner. The values after storage / initial are shown in Tables 4 and 5.

(4) Change in viscosity with time In the above “(3) Storage stability”, 1.00 or more and less than 1.15 is “◎”, 0.90 or more and less than 1.00 or 1.15 or more and less than 1.35. “O”, 0.80 or more and less than 0.90, or 1.35 or more and less than 1.75, “△”, and less than 0.80 or 1.75 or more, “X”.

(5) Separation state The compositions according to Examples, Reference Examples and Comparative Examples were allowed to stand in a 50 ° C environment for 1 week and then left at 23 ° C and 50% RH for 1 day to confirm the state of phase separation. When the phase separation is not observed, “◎” is given. When the phase separation is seen only a little, “◯” is given. When the phase separation is not clear, the phase separation is seen as “△”. When the layer interface was clear and it was confirmed that the layers were clearly separated, “x” was given.

(6) Workability The workability was evaluated for the compositions according to Examples and Comparative Examples. As an adherend, a slate of 300 × 150 × 5 mm is used as a base material, and a 25 × 150 × 2.5 mm multi-layer vinyl floor tile FT, Sangetsu floor tile IS-344 (trade name, manufactured by Sangetsu Co., Ltd.) )It was used. First, the above composition was applied to the slate in a comb shape using a comb iron, and then the finishing material was pasted after 30 minutes had passed as an open time. The adhesion area was 25 mm × 100 mm. Thereafter, a load of 50 N was applied with a hand roller according to JIS A5536.5.3.3, pressure was applied by reciprocating twice, and immediately after that, the strength in the shear direction was measured using only a spring. The evaluation was “◯” when the value was 15N or more, “Δ” when the value was 10N or more and less than 15N, and “X” when the value was less than 10N.

(7) Bonding possible time The bonding possible time was measured with respect to the composition which concerns on an Example and a comparative example. As the adherend, the above slate was used as a base material, and the above IS-344 of 40 × 40 × 2.5 mm was used as a finishing material. First, the composition was applied to the slate in a comb shape using a comb iron, and then a finishing material was pasted after a predetermined time had elapsed. The adhesion area was 40 mm × 40 mm. Thereafter, a 1 kg weight was placed for 10 seconds for pressure bonding, and immediately thereafter, the finishing material was peeled off from the base material. The adhesive surface of the finishing material after peeling was visually observed to confirm the state in which the composition was transferred. Then, the “predetermined time” at which 50% or more of the combs appear was defined as the “bondable time”. The evaluation was “◯” when the time was 50 minutes or more, “Δ” when the time was 40 minutes or more and less than 50 minutes, and “X” when the time was less than 40 minutes.

(8) Plane Tensile Strength Test A plane tensile strength test was performed on the compositions according to Examples 1 and 2 and Comparative Examples 1 to 3 according to JIS A5536 method 5.3.2. In this standard, the modified silicone-based curable composition is not defined as a polymer-based stretch flooring material. However, in this example, the standard was used and tested. Moreover, curing was performed in an environment of 23 ° C. and 50% for 168 hours. As an adherend, a mortar board of 70 × 70 × 20 mm is used as a base material, and a 40 × 40 × 2.5 mm multi-layer vinyl floor tile FT, Sangetsu floor tile GT-701 (trade name, Sangetsu Co., Ltd.) Made).

(9) Peeling adhesive strength test A peeling adhesive strength test (90 degree peeling) was performed on the compositions according to Examples 1 and 2 and Comparative Examples 1 to 3 according to JIS A5536 method 5.3.3. It was. In this standard, the modified silicone-based curable composition is not defined as a polymer-based stretch flooring material. However, in this example, the standard was used and tested. Moreover, curing was performed in an environment of 23 ° C. and 50% for 168 hours. As an adherend, a mortar board of 150 × 70 × 10 mm is used as a base material, and a vinyl floor sheet of 25 × 200 × 2.5 mm, Sangetsu Non-Skid PX-121 (trade name, manufactured by Sangetsu Co., Ltd.) is used as a finishing material. used.

  (A) Curability containing an organic polymer having a crosslinkable silicon group and the main chain of which is not polysiloxane, and (B) a filler which is a surface-treated colloidal calcium carbonate having a fatty acid ester as a surface treating agent. Although the composition has low viscosity, it has both high thixotropy and high storage stability, and even when the composition contains a large amount of organic solvent, it may not cause phase separation during storage. It was confirmed (Examples 1-8). In particular, it was confirmed that it is preferable to use alcohol in terms of excellent balance between workability and possible bonding time (Examples 1 to 7).

  On the other hand, even if the filler is surface-treated calcium carbonate, when it is surface-treated calcium carbonate using a substance different from the fatty acid ester as a surface treating agent, (1) Adhesion by reducing the viscosity of the curable composition To improve the workability of applying the curable composition to the body, (2) In particular, when the adherend has a large area, allow sufficient time for bonding to the adherend having a large area. It is confirmed that the inclusion of a large amount of organic solvent in the curable composition for the purpose of, etc., may cause phase separation during storage, resulting in inconvenience that the curable composition must be stirred before use (Comparative Examples 1 to 6). Moreover, when the boiling point of the organic solvent exceeded 150 degreeC, it was confirmed that sufficient pasting time cannot be obtained (comparative example 7). This is considered to be because the time from application to the adherend to volatilization of the organic solvent is long, and the time until the adhesiveness is developed is long.

Claims (6)

Component 1: an organic polymer having a crosslinkable silicon group and having a main chain that is not polysiloxane;
Component 2: Surface-treated colloidal calcium carbonate having a fatty acid ester as a surface treatment agent ;
Component 3: Other calcium carbonate different from the component 2,
Component 4: contains an alcohol having a boiling point of 150 ° C. or less,
The surface-treated colloidal calcium carbonate is 2 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the organic polymer.
The said alcohol is 20 mass parts or more with respect to 100 mass parts of said organic polymers, and is a normal temperature moisture curable composition. The organic polymer is polyoxyalkylene polymer, (meth) is at least one selected from acrylic acid ester polymer or a saturated hydrocarbon polymer, curable composition according to claim 1. The organic polymer is a mixture of the polyoxyalkylene polymer and (meth) acrylic ester polymer, curable composition according to claim 1. Wherein the fatty acid ester has a carbon number of the saturated fatty acid ester of 3 or more and 100 or less, the curable composition according to any one of claims 1 to 3. The alcohols include methanol, is at least one selected from ethanol or isopropyl alcohol, curable composition according to any one of claims 1 to 4.   A method for producing an adhesive structure by interposing the curable composition according to claim 1.