WO2016047519A1

WO2016047519A1 - Curable composition and cured product thereof

Info

Publication number: WO2016047519A1
Application number: PCT/JP2015/076271
Authority: WO
Inventors: のどか太刀掛; 雄板野
Original assignee: 株式会社カネカ
Priority date: 2014-09-26
Filing date: 2015-09-16
Publication date: 2016-03-31
Also published as: JPWO2016047519A1; JP6716459B2

Abstract

The purpose of the present invention is to provide a curable composition which enables strong adhesion, without carrying out a primer treatment, to a metal, glass or coated surface, and especially to a porous base material such as mortar or stone, and in addition, the composition can minimize deterioration in adhesive properties when immersed in water and exhibits good storage stability. This curable composition is characterized by containing (A) a reactive silicon group-containing organic polymer (excluding component (B)) and (B) an organic polymer which has an aromatic ring structure and/or a hydrogenated aromatic ring structure, has a reactive silicon group at a terminal and has no hydroxyl group. Component (B) is preferably an alkylene oxide addition reaction product of a bisphenol compound.

Description

Curable composition and cured product thereof

The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxy group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. It relates to the curable composition containing this.

An organic polymer having at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group by moisture, and a rubber-like cured product is obtained. It is known to have the property of being Among organic polymers having reactive silicon groups, organic polymers whose main chain skeleton is composed of a polyoxyalkylene polymer, a polyisobutylene polymer, and a (meth) acrylate polymer have already been industrially used. Produced and widely used for sealing materials and adhesives (Patent Document 1).

Conventionally, in the curable composition, particularly in the field of sealants, it has been necessary to apply a primer in order to ensure sufficient adhesion between the substrate and the sealant. The application of such a primer requires the selection of an appropriate primer suitable for various sealants and various base materials, and is a cumbersome operation, so the sealant performance to adhere firmly to the base material even without primer treatment Has been required. So far, various studies have been made on techniques for imparting adhesiveness to the sealant itself, and for example, addition of an amino group-containing hydrolyzable silicon compound or a reaction product thereof with an epoxy compound has been proposed (for example, Patent Document 1 and (See Patent Document 2 etc.). However, even if these techniques are used, when the adherend is a porous substrate, water easily permeates through the pores. There was a problem that peeling occurred.

As one of methods for improving the water-resistant adhesion as described above, a method of adding a silicon-modified epoxy resin as an active ingredient has been proposed (Patent Document 3). However, even when this technique is used, a curable composition based on an oxyalkylene polymer having a silicon atom-containing group to which a hydroxyl group or a hydrolyzable group is bonded, such as a modified bisphenol A-epichlorohydrin type epoxy resin, etc. However, there was a problem that the compatibility with the oxyalkylene polymer was not good and sufficient water-resistant adhesion could not be obtained.

Furthermore, as one of the methods for improving the above problems, a silicon-modified epoxy resin obtained from a glycidyl ether having a polyalkylene glycol skeleton and a silicon compound having a functional group capable of reacting with an epoxy group is added. A method has been proposed (Patent Document 4). However, in the production method of this technology, since the silicone-modified epoxy resin has at least two hydroxyl groups in the molecule, transesterification with the polymer occurs during storage of the curable composition, and the curability is lowered. In contrast, there is a problem that three-dimensional crosslinking proceeds due to a pseudo-crosslinking reaction with a hydroxyl group, and the viscosity increases after storage and adhesiveness decreases.

JP 59-24771 A Japanese Patent Publication No.62-35421 Japanese Patent Publication No.62-28177 JP 2004-107652 A

The object of the present invention is not only to adhere firmly to a porous substrate such as mortar and stone, but also to a metal, glass and painted surface, not only with primer treatment, but also with adhesiveness even when immersed in water. An object of the present invention is to provide a curable composition capable of minimizing deterioration and having good storage stability.

As a result of intensive studies to solve the above problems, the present inventors have obtained a storage by blending a reactive silicon group-containing organic polymer and a reactive silicon group-containing organic polymer having a specific structure. It has been found that the strength of the curable composition, particularly the adhesiveness after immersion in mortar, is significantly improved while maintaining various physical properties such as curability before and after.

That is, the present invention
(I) (A) Reactive silicon group-containing organic polymer (excluding component (B) below), and (B) Aromatic ring structure and / or hydrogenated aromatic ring structure, reactive at the terminal A curable composition comprising an organic polymer having a silicon group and no hydroxyl group;
(II) The curable composition according to (I), wherein the component (B) has a bisphenol structure,
(III) The curable composition according to (I) or (II), containing 3 to 100 parts by weight of component (B) with respect to 100 parts by weight of component (A),
(IV) The curable composition according to any one of (I) to (III), wherein the component (B) contains an alkylene oxide addition reaction product of bisphenols,
(V) The curable composition according to (IV), wherein the alkylene oxide addition reaction product of bisphenol is an addition reaction product of bisphenol A and propylene oxide,
(VI) The curable composition according to (V), wherein the reaction amount of propylene oxide with respect to 1 mol of bisphenol A is 2 to 30 mol,
(VII) The curable composition according to (V), wherein the reaction amount of propylene oxide with respect to 1 mol of bisphenol A is 2 to 15 mol,
(VIII) The curable composition according to any one of (I) to (VII), wherein the main chain skeleton of the component (A) is a polyoxyalkylene polymer,
(IX) The curable composition according to any one of (I) to (VIII), wherein the component (B) is a modified product of a silicon compound having a hydrolyzable functional group on a silicon atom,
(X) The curable composition according to any one of (I) to (IX), wherein the component (B) has a structure represented by the following general formula (6) or the following general formula (7) at the end. ,
—O—R ⁸ —SiR ⁹ _b X ² _3-b (6)
(In the general formula (6), R ⁸ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R ⁹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ² each independently represents a hydroxyl group or a hydrolyzable group, and b represents 0 or 1.)
—W—R ¹⁰ —SiR ¹¹ _c X ³ _3-c (7)
(In the general formula (7), R ¹⁰ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R ¹¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ³ each independently represents a hydroxyl group or a hydrolyzable group, c represents 0 or 1, W represents —O—CO—N (R ¹² ) —, —N (R ¹² ) —CO—O—. , -N (R ¹² ) -CO-N (R ¹² )-, -N (R ¹² ) -CS-N (R ¹² )-or -S-, wherein R ¹² is hydrogen or halogen-substituted Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.)
(XI) The curable composition according to any one of (I) to (X), wherein the component (A) has a reactive silicon group represented by the following general formula (1):
-SiR ¹ _a X ¹ _3-a (1)
(In the general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ¹ independently represents a hydroxyl group or a hydrolyzable group. A represents 0 or 1. .)
(XII) a sealing material comprising as a component the curable composition according to any one of (I) to (XI),
(XIII) an adhesive comprising as a component the curable composition according to any one of (I) to (XI),
(XIV) A coating material obtained by curing the curable composition according to any one of (I) to (XI),
About.

The curable composition of the present invention is not primed for porous substrates such as mortars and stones, especially on metal, glass and painted surfaces, while maintaining various physical properties such as curability before and after storage. However, not only is it firmly bonded, but it is also possible to minimize the deterioration of the adhesiveness even during water immersion, and the storage stability is also good.

The present invention will be described in detail below.
(A) Reactive silicon group-containing organic polymer (excluding the following component (B)) (hereinafter also referred to as the component (A)) is not particularly limited, and for example, an oxyalkylene type generally known as a main chain skeleton An organic polymer having a polymer, a (meth) acrylic acid alkyl ester polymer, a saturated hydrocarbon polymer, a polyester polymer, or the like can be used. Of these, oxyalkylene polymers are particularly preferred because of their low-temperature properties, flexibility, and compatibility with other components. In the following description of component (A), oxyalkylene polymers are used as main examples of main chain skeletons. Describe what to say.

The reactive silicon group-containing polyoxyalkylene polymer has a reactive silicon group represented by the following general formula (1).
-SiR ¹ _a X ¹ _3-a (1)
(In the general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ¹ independently represents a hydroxyl group or a hydrolyzable group. A represents 0 or 1. .)

Specific examples of R ¹ in the general formula (1) include an alkyl group such as a methyl group or 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; , R ′ is a methyl group, a phenyl group or the like; a triorganosiloxy group represented by —OSi (R ′) ₃ ; a fluoroalkyl group such as a fluoromethyl group or a difluoromethyl group; a chloromethyl group or a 1-chloroethyl group Chloroalkyl group; alkoxyalkyl group such as methoxymethyl group, ethoxymethyl group, phenoxymethyl group and 1-methoxyethyl group; aminoalkyl group such as aminomethyl group, N-methylaminomethyl group and N, N-dimethylaminomethyl group Group: acetoxymethyl group, methyl carbamate group, 2-cyanoethyl group and the like. Among these, a methyl group is preferable in view of availability of raw materials.

Examples of the hydrolyzable group represented by X ¹ in the general formula (1) include known hydrolyzable groups. Specific examples include hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group. Group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and the like. Among these, halogen, alkoxy group, alkenyloxy group, and acyloxy group are preferable because of their high activity, and alkoxy groups such as methoxy group and ethoxy group are more preferable because they are mildly hydrolyzable and easy to handle. The group is particularly preferred. In addition, the ethoxy group and the isopropenoxy group are preferably removed from the reaction by ethanol and acetone, respectively, from the viewpoint of safety.

Specific examples of the reactive silicon group represented by the general formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, A diethoxymethylsilyl group, diisopropoxymethylsilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, and (ethoxymethyl) dimethoxysilyl group are preferred. Among these, dimethoxymethylsilyl group and trimethoxysilyl group are preferable because a cured product having high strength can be obtained.

The polyoxyalkylene polymer has a relatively low glass transition temperature, and the resulting cured product is excellent in cold resistance. In addition, when it is made into a one-component composition with high moisture permeability, it has a feature that it is excellent in deep part curability and further excellent in adhesiveness.

Specific examples of the main chain skeleton of component (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene. Examples thereof include polyoxyalkylene polymers such as copolymers.

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, when used in sealants, adhesives, etc., an amorphous material is a polyoxypropylene polymer having a repeating unit of oxypropylene of 50% by weight or more, preferably 80% by weight or more of the polymer main chain skeleton. From the viewpoint of quality and relatively low viscosity.

The main chain skeleton of the component (A) may have a polymer structure other than the oxyalkylene structure as long as the effects of the invention are not impaired.

The main chain structure of component (A) may be linear or may have a branched chain. When it is desired to obtain a cured product with higher strength, it is preferable to have a branched chain. When it is desired to obtain a cured product having a higher elongation, it is preferably linear. When the component (A) has a branched chain, the number of branched chains is preferably 1 to 4, and more preferably 1.

As the polyoxyalkylene polymer, those obtained by ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator are preferable.

Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, it is particularly preferable to use propylene oxide because an amorphous and relatively low viscosity polyoxyalkylene polymer can be obtained.

Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, Examples include alcohols such as sorbitol; polyoxyalkylene polymers such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol having a number average molecular weight of 300 to 4,000. .

Examples of the method for synthesizing a polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound with porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. Polymerization method using double metal cyanide complex catalyst as shown in US Pat. No. 3,427,335, polymerization method using polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, can be mentioned, but not particularly limited, manufacturing cost and, because of such the polymer having a narrow molecular weight distribution is obtained, by the polymerization method is more preferred composite metal cyanide complex catalyst.

The molecular weight distribution (Mw / Mn) of the component (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and 1.4 or less. Is particularly preferred.

The number average molecular weight of the component (A) is in terms of polystyrene by GPC, and the lower limit is preferably 8,000 or more, more preferably 9,000 or more, and particularly preferably 10,000 or more. The upper limit is preferably 50,000 or less, more preferably 35,000 or less, and particularly preferably 30,000 or less. When the number average molecular weight of the component (A) is small, the viscosity is low and workability when using the curable composition is improved. On the other hand, the hardened | cured material obtained becomes hard and there exists a tendency for an elongation characteristic to fall. If the molecular weight is too large, the reactive silicon group concentration may be too low, and the curing rate may be slow. Also, the viscosity tends to be too high and handling tends to be difficult.

The method for introducing the reactive silicon group of the component (A) is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(I) Hydrosilylation: First, an unsaturated bond is introduced into a raw material polymer (sometimes referred to as a precursor polymer), and a hydrosilane compound is added to the unsaturated bond by a hydrosilylation reaction. . Any method can be used for introducing the unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is allowed to react with a compound having reactivity with this functional group and a compound having an unsaturated group. There are a method for obtaining an unsaturated group-containing polymer and a method for copolymerizing a polymerizable monomer having an unsaturated bond.
(Ii) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: reacting with the precursor polymer having a reactive group such as a hydroxyl group, an amino group, or an unsaturated bond, and the reactive group. And a compound having both a group capable of forming a bond and a reactive silicon group (also called a silane coupling agent). As a combination of the reactive group of the precursor polymer and the reactive group of the silane coupling agent, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, Examples include, but are not limited to, Michael addition of amino group and acrylic structure, carboxylic acid group and epoxy group, unsaturated bond and mercapto group.

The method (i) is preferable because the reaction is simple, the adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable. The method (ii) has many reaction options, and it is easy and preferable to increase the rate of introduction of reactive silicon groups.

A part of hydrosilane compound used by the method of (i) is illustrated. Halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, triethoxysilane, (chloromethyl) dimethoxysilane, (methoxymethyl) ) Alkoxysilanes such as dimethoxysilane; isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane, etc. .

Examples of the silane coupling agent that can be used in the method (ii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxy, which react with an unsaturated bond. Mercaptosilanes such as silane and mercaptomethyldimethoxymethylsilane; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyl which react with hydroxyl groups Isocyanate silanes such as triethoxysilane and isocyanate methyldimethoxymethylsilane; reacts with hydroxyl, amino and carboxylic acid groups, 3- Lysidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane Epoxysilanes such as: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) propyltrimethyl, which react with isocyanate groups and thioisocyanate groups Methoxysilane, 3- (2-aminoethyl) propyldimethoxymethylsilane, 3- (2-aminoethyl) propyltriethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 3 Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (3- Aminosilanes such as (trimethoxysilyl) propyl) amine; hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane. The above silane coupling agent is an example, and a silyl group can be introduced by utilizing or applying a similar reaction.

The main chain skeleton of the component (A) may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired. Although it does not specifically limit as a urethane bond component, The group (henceforth an amide segment) produced | generated by reaction with an isocyanate group and an active hydrogen group can be mentioned.

The cured product obtained by curing the curable composition containing the component (A) containing a urethane bond or an ester bond in the main chain skeleton can obtain high hardness or improve the strength due to the action of hydrogen bonds, etc. An effect may be obtained. On the other hand, the urethane bond may be cleaved by heat or the like. For the purpose of imparting such characteristics to the curable composition of the present invention, an amide segment can be introduced into the component (A) or the amide segment can be excluded. A polyoxyalkylene polymer having an amide segment tends to have a high viscosity. In addition, the polyoxyalkylene polymer having an amide segment may be improved in curability.

The amide segment has the following general formula (2):
—NR ² —C (═O) — (2)
(In general formula (2), R ² represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

Specifically, as the amide segment, a urethane group generated by a reaction between an isocyanate group and a hydroxy group or a reaction between an amino group and a carbonate; a urea group generated by a reaction between an isocyanate group and an amino group; an isocyanate group And a thiourethane group produced by the reaction of a mercapto group. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (2).

An example of an industrially easy production method of a polyoxyalkylene polymer having an amide segment and a reactive silicon group is illustrated by reacting an excess polyisocyanate compound with a polyoxyalkylene polymer having an active hydrogen-containing group at the terminal. After making the polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group has the following general formula (3):
ZR ³ —SiR ¹ _a X _3-a (3)
(In General Formula (3), R ¹ , X, and a are the same as described above. R ³ is a divalent organic group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxy group. Examples thereof include those produced by a method in which a Z group of a silicon compound represented by a group, a carboxy group, a mercapto group, and an amino group (primary or secondary) is selected, is reacted. it can.

Further, the polyoxyalkylene polymer having an active hydrogen-containing group at the terminal is represented by the following general formula (4):
O = C = N—R ³ —SiR ¹ _a X _3-a (4)
(In general formula (4), R < ³ >, R < ¹ >, X, a is the same as the above.) What is manufactured by making the reactive silicon group containing isocyanate compound represented by react can be mentioned.

The silicon compound represented by the general formula (3) is not particularly limited, but specific examples include γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- Amino such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxymethylsilane, (N-phenyl) -γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane Group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; Also, JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), JP-A 2000-169544, JP-A 2000-169545. As described in the above, Michael addition reaction products of various α, β-unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds, The Michael addition reaction product of can also be used as the silicon compound represented by the general formula (3).

The reactive silicon group-containing isocyanate compound represented by the general formula (4) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxy. Silylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, γ- (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (Methoxymethyl) dimethoxysilylmethyl isocyanate and the like.

When component (A) contains an amide segment in the main chain skeleton, the average number of amide segments is preferably 1 to 10, more preferably 1.5 to 5, more preferably 2 to 3 per molecule. preferable. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the component (A) may have a high viscosity and may be difficult to handle.

When aiming at lowering the viscosity of the curable composition or improving workability, the component (A) preferably contains substantially no amide segment.

The component (A) may contain an average of more than one reactive silicon group at one terminal site. Usually, when a reactive silicon group is introduced by the above method (i), the number is limited to one or less on average in one terminal site. In contrast, the precursor polymer is reacted with an epoxy compound having a carbon-carbon unsaturated bond, and the alcohol terminal is modified to an unsaturated group, thereby introducing more than one reactive silicon at one terminal site. It becomes possible to do.

Specific examples of the epoxy compound having a carbon-carbon unsaturated bond include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide. Glycidyl ether is more preferred. In the specification and claims, (meth) allyl represents allyl and / or methallyl.

The amount of the epoxy compound having a carbon-carbon unsaturated bond added may be any amount in consideration of the amount of carbon-carbon unsaturated bond introduced into the polyoxyalkylene polymer and the reactivity. In particular, the lower limit of the molar ratio of hydroxyl groups contained in the polyoxyalkylene polymer is preferably 0.2 or more, and more preferably 0.5 or more. The upper limit is preferably 5.0 or less, and more preferably 2.0 or less.

The reaction temperature for the ring-opening addition reaction of the epoxy compound having a carbon-carbon unsaturated bond to the precursor polymer is preferably 60 ° C. or higher and 150 ° C. or lower, and 110 ° C. or higher and 140 ° C. or lower. Is more preferable. If it is low, the reaction hardly proceeds, and if it is too high, the main chain of the polyoxyalkylene polymer may be decomposed.

The polymer structure having an unsaturated bond before introduction of the reactive silicon group obtained by the above method has a terminal site represented by the following general formula (5):

(In General Formula (5), R ⁴ and R ⁶ are each independently a divalent organic group, and the atom bonded to each adjacent carbon atom is any of carbon, oxygen, and nitrogen. R ⁵ , R ⁷ each independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10).

(A) The terminal structure having a reactive silicon group contained in one molecule of component (A) is preferably 0.5 or more on average, more preferably 1.0 or more, and 1.1 More preferably, it is more preferably 1.5 or more.

The lower limit of the average number of reactive silicon groups per component (A) is preferably 1.2 or more, more preferably 1.3 or more, and most preferably 1.5 or more. The upper limit is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. When the number of reactive silicon groups is less than 1.2, a cured product with high strength may not be obtained, which is not preferable. When the number of reactive silicon groups exceeds 6.0, it is not preferable because a cured product having a high elongation may not be obtained.

The average number of reactive silicon groups in component (A) is defined as the average number determined by a method of quantifying protons on carbon directly bonded with reactive silicon groups by high resolution ¹ H-NMR measurement. In the calculation of the average number of reactive silicon groups in the component (A) in the present invention, when the reactive silicon group is introduced into the precursor polymer, the precursor polymer and the secondary polymer in which no reactive silicon group is introduced. The average number of reactive silicon groups in a molecule is also calculated for the polymer obtained by the reaction, in which no reactive silicon group is introduced, as a part of the component (A) having the same main chain structure. The calculation is included in the population parameter (number of molecules).

The curable composition of the present invention comprises (B) a polymer having an aromatic ring structure and / or a hydrogenated aromatic ring structure, a reactive silicon group at the terminal, and no hydroxyl group (hereinafter referred to as ( B) also referred to as component). Examples of the aromatic ring structure and / or hydrogenated aromatic ring structure of component (B) include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), and isopropylidene bisphenol (bisphenol). A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), and these were hydrogenated Examples include structures derived from compounds and the like. Among these, a bisphenol structure is preferable from the viewpoints of adhesiveness and raw material availability.

Among these aromatic ring structures and / or hydrogenated aromatic ring structures, the use of a structure derived from bisphenol A significantly improves the strength of the curable composition, particularly the adhesiveness after immersion in mortar. preferable.

Further, the component (B) may contain an alkyleneoxy post-addition reaction product of bisphenols, and examples thereof include a reaction product of ethylene oxide, propylene oxide, butylene oxide and a mixture thereof with a bisphenol type epoxy resin. It is done. In particular, an addition reaction product of bisphenol A and propylene oxide is preferable, but not limited thereto.

In addition, the higher the ratio of the bisphenol group to the alkylene oxide, the more effective the component (B) is in suppressing sufficient adhesiveness, in particular, deterioration of adhesiveness after water immersion. Specifically, the reaction amount of propylene oxide with respect to 1 mol of bisphenol is preferably 2 to 30 mol, and particularly preferably 2 to 15 mol.

In the curable composition of the present invention, the component (B) is preferably a modified product of a silicon compound having a hydrolyzable functional group on a silicon atom from the viewpoint of water-resistant adhesion. It is considered that the component (B) has a hydrolyzable functional group on the silicon atom, so that a crosslinked structure is formed in the cured product, and good water-resistant adhesion is developed over a long period of time.

The method for introducing the reactive silicon group (B) is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(I) Hydrosilylation: First, an unsaturated bond is introduced into a raw material polymer (sometimes referred to as a precursor polymer), and a hydrosilane compound is added to the unsaturated bond by a hydrosilylation reaction. The structure represented by the following general formula (6) can be introduced at the end.
—O—R ⁸ —SiR ⁹ _b X ² _3-b (6)
(In the general formula (6), R ⁸ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R ⁹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ² each independently represents a hydroxyl group or a hydrolyzable group, and b represents 0 or 1.)

Any method can be used for introducing the unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is allowed to react with a compound having reactivity with this functional group and a compound having an unsaturated group. There are a method for obtaining an unsaturated group-containing polymer and a method for copolymerizing a polymerizable monomer having an unsaturated bond.

(Ii) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: reacting with the precursor polymer having a reactive group such as a hydroxyl group, an amino group, or an unsaturated bond, and the reactive group. And a compound having both a group capable of forming a bond and a reactive silicon group (also called a silane coupling agent). The combination of the reactive group of the precursor polymer and the reactive group of the silane coupling agent includes hydroxyl group and isocyanate group, amino group and isocyanate group, amino group and thioisocyanate group, Michael addition of amino group and acrylic structure, Examples include, but are not limited to, saturated bonds and mercapto groups.

By the method (ii), the structure represented by the following general formula (7) can be introduced at the end of the component (B).
—W—R ¹⁰ —SiR ¹¹ _c X ³ _3-c (7)
(In the general formula (7), R ¹⁰ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R ¹¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X ³ each independently represents a hydroxyl group or a hydrolyzable group, c represents 0 or 1, W represents —O—CO—N (R ¹² ) —, —N (R ¹² ) —CO—O—. , -N (R ¹² ) -CO-N (R ¹² )-, -N (R ¹² ) -CS-N (R ¹² )-or -S-, wherein R ¹² is hydrogen or halogen-substituted Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.)

The lower limit of the average number of reactive silicon groups per component (B) is preferably 1.2 or more, more preferably 1.3 or more, and most preferably 1.5 or more. The upper limit is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. When the number of reactive silicon groups is less than 1.2, a cured product with high strength may not be obtained, which is not preferable. When the number of reactive silicon groups exceeds 6.0, it is not preferable because a cured product having a high elongation may not be obtained.

The average number of reactive silicon groups in component (B) is defined as the average number obtained by a method of quantifying protons on carbon directly bonded with reactive silicon groups by high resolution ¹ H-NMR measurement. In the calculation of the average number of reactive silicon groups in the component (B) in the present invention, when the reactive silicon group is introduced into the precursor polymer, the precursor polymer and the secondary polymer in which no reactive silicon group is introduced. The polymer obtained by the reaction and having no reactive silicon group introduced is also regarded as a part of the component (B) having the same main chain structure, and the average number of reactive silicon groups in one molecule is calculated. The calculation is included in the population parameter (number of molecules).

In the curable composition of the present invention, the content of the component (B) is not particularly limited, but is preferably 3 to 100 parts by weight with respect to 100 parts by weight of the component (A), and 5 to 30 parts by weight. More preferably. When the content of the component (B) is less than 3 parts by weight, sufficient water-resistant adhesion may not be exhibited, and when it exceeds 100 parts by weight, the brittleness of the cured product may be extremely reduced.

The curable composition of this invention may contain the curing catalyst as a silanol condensation catalyst of (A) component and (B) component. Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dimethyltin diacetate, dimethyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate) , Dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis (benzyl maleate) Dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetate) Natto), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin bis (acetyl) Tetravalent organotin compounds such as acetonate); organics such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate Aluminum compounds; zirconium compounds such as zirconium tetrakis (acetylacetonate) and the like. Moreover, carboxylic acid and / or carboxylic acid metal salt can also be used as a curing catalyst. Moreover, an amidine compound as described in International Publication No. 2008/077864 can also be used. Examples of amidine compounds include 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo [4.4. .0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo [5.4.0] -7- Although undecene (DBU) etc. can be mentioned, it is not restricted to these. Some amidines are solid at room temperature, but if there is a problem that they are difficult to disperse, use a means to disperse or dissolve in advance using a solvent or plasticizer suitable for each compound. Can do. Considering the working environment, a high boiling point solvent is preferable.

Of the curing catalysts listed above, dibutyltin-based curing catalysts have a good balance of curability and adhesiveness and are most commonly used. In recent years, however, dibutyltin-based curing catalysts are concerned about adverse effects on the human body. In such cases, dioctyltin-based curing catalysts can be used. As the dioctyltin-based curing catalyst, dioctyltin dilaurate, dioctyltin bisacetylacetonate, and a reaction product of dioctyltin salt and ethyl silicate are industrially available and preferable. Moreover, since a titanium catalyst as a non-tin catalyst has high activity, it is preferable in the case of industrial adhesives and electrical / electronic adhesives that require rapid curing. Among the titanium catalysts, diisopropoxytitanium bis (ethyl acetocetate) is particularly preferable because of excellent curability and storage stability of the blend. This catalyst is sold under the trade name Tyzor PITA and is easily available and can be suitably used.

When the curable composition of the present invention contains a curing catalyst, the blending amount is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). 0.05 to 15 parts by weight is more preferable, and 0.1 to 10 parts by weight is most preferable. When the blending amount of the curing catalyst is within this range, the curable composition has excellent curability, and has an appropriate curing time, and therefore has excellent workability.

The curable composition of the present invention may contain a plasticizer. The plasticizer has a function of adjusting the viscosity and slump property of the curable composition, and a function of adjusting mechanical properties such as tensile strength and elongation property of the obtained cured product.

Specific examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate Non-aromatic dibasic acid esters such as; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate, polyethylene glycol, polypropylene glycol, Polyether polyol or hydroxyl ester groups of these polyether polyols such as polytetramethylene glycol, polyethers such as derivatives obtained by converting such an ether group.

Among these, polypropylene glycol, di (2-ethylhexyl) phthalate, diisodecyl phthalate and the like are preferable from the viewpoints of compatibility with the components (A) and (B), mechanical properties, cost, and the like.

These plasticizers may be blended alone or in combination of two or more. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

When the curable composition of the present invention contains a plasticizer, the blending amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the total amount of the components (A) and (B). Preferably, 10 parts by weight or less is particularly preferable. If the blending amount of the plasticizer exceeds 30 parts by weight, the strength and adhesiveness of the cured product tend to decrease.

In addition to these plasticizers, a polymer plasticizer can be added. Compared with the addition of a low molecular weight plasticizer, which is a plasticizer that does not contain a polymer component in the molecule, the curable composition can maintain the initial characteristics over a long period of time. The effect of improving the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product is exhibited.

The polymer plasticizer is not particularly limited, and vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polystyrene and poly -Polystyrenes such as -α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.

Among these polymer plasticizers, vinyl polymers are preferred because they have high compatibility with the components (A) and (B), and the resulting cured products have good weather resistance and heat resistance. More preferred are polymer and / or methacrylic polymers, and more preferred are acrylic polymers such as polyacrylic acid alkyl esters.

The method for producing the polyacrylic acid alkyl ester is not particularly limited, but a living radical polymerization method is preferable and an atom transfer radical polymerization method is more preferable because the molecular weight distribution is narrow and viscosity can be reduced. A method of continuous bulk polymerization of an alkyl acrylate ester compound disclosed in JP-A-2001-207157 called SGO process under high temperature and high pressure is particularly preferable.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000. 3,000 to 3,000 is most preferred. If the molecular weight of the polymer plasticizer is too low, the plasticizer will flow out from the cured product over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time, which may cause contamination due to dust adhesion. Yes, alkyd paintability tends to be inferior. On the other hand, if the molecular weight is too high, the viscosity of the curable composition tends to be high and workability tends to be poor.

The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, less than 1.80, preferably 1.70 or less, more preferably 1.60 or less, further preferably 1.50 or less, and 1.40 or less. Is particularly preferred, with 1.30 or less being most preferred.

The number average molecular weight is measured by a terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

The polymer plasticizer may or may not have a reactive silicon group in the molecule, but when a polymer plasticizer having a reactive silicon group was added, the polymer plasticizer was incorporated into the curing reaction and obtained. This is preferable because migration of the plasticizer from the cured product can be prevented.

When blending a polymeric plasticizer having a reactive silicon group, the number of reactive silicon groups is preferably 1 or less on average per molecule, and more preferably 0.8 or less.

Only one type of polymer plasticizer may be added, or a plurality of types may be added in combination. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. In addition, you may add these plasticizers at the time of manufacture of (A) and (B) component.

The amount of the polymer plasticizer added is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the components (A) and (B). If it exceeds 30 parts by weight, the mechanical strength of the cured product tends to be insufficient.

Aminosilane can be added to the curable composition of the present invention. Aminosilane is a compound having a reactive silicon group and amino group in the molecule, and is usually referred to as an adhesion-imparting agent. By using this, various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc. When used, it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. In addition, it is a compound that can function as a physical property modifier, an inorganic filler dispersibility improver, and the like.

Specific examples of the reactive silicon group of aminosilane include the groups already exemplified, but methoxy group, ethoxy group and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ -(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) amino Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) amino Propyltrimethoxysilane 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ -Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2 -Aminoethyl) amino group-containing silanes such as aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) -3- ( Triethoxysilyl) -1- It may be mentioned ketimines type silanes such Ropan'amin.

Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane are used. preferable. Only one type of aminosilane may be used, or two or more types may be used in combination. It has been pointed out that γ- (2-aminoethyl) aminopropyltrimethoxysilane is irritating compared to other aminosilanes, and instead of reducing this aminosilane, γ-aminopropyltrimethoxysilane should be used in combination. Can alleviate irritation.

When the curable composition of the present invention contains aminosilane, the blending amount is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B), and 2 to 10 parts by weight. Is more preferable. If the amount of aminosilane is less than 1 part by weight, sufficient adhesion may not be obtained. On the other hand, if the amount of aminosilane exceeds 20 parts by weight, the cured product becomes brittle and sufficient strength cannot be obtained, and the curing rate may be slow.

An adhesion imparting agent other than aminosilane can be used in the curable composition of the present invention. Specific examples of adhesion-imparting agents other than aminosilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxy Epoxy group-containing silanes such as cyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyl Isocyanate group-containing silanes such as diethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane; γ-mercaptopropi Mercapto group-containing silanes such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; β-carboxyethyltriethoxysilane, Carboxysilanes such as β-carboxyethylphenylbis (2-methoxyethoxy) silane and N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ- Vinyl type unsaturated group-containing silanes such as methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing γ-chloropropyltrimethoxysilane Orchids; can be exemplified tris isocyanurate silanes such as (trimethoxysilyl) isocyanurate.

Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferred in order to ensure good adhesion.

Moreover, the condensate which condensed the said silane partially can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives obtained by modifying these, can also be used as an adhesion-imparting agent.

In the curable composition of the present invention, the adhesion-imparting agent includes various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, vinyl chloride, acrylic, polyester, polyethylene, polypropylene, When used for an organic base material such as polycarbonate, it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. As the adhesion-imparting agent, compounds other than the silane compounds listed above can also be used. Although it does not specifically limit as a specific example, For example, an epoxy resin, a phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate etc. are mentioned. Only one type of adhesion promoter may be used, or two or more types may be used in combination. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

When the curable composition of the present invention contains an adhesion-imparting agent, the content thereof is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). About 1 to 10 parts by weight is more preferable, and about 1 to 7 parts by weight is particularly preferable. If the content of the adhesion-imparting agent is less than this range, sufficient adhesion may not be obtained. On the other hand, if the content of the adhesion-imparting agent exceeds this range, practical deep curability may not be obtained.

When the curable composition of the present invention contains an epoxy resin, the epoxy resin may reduce the catalytic activity depending on the addition amount, and therefore the addition amount of the epoxy resin is preferably small. The amount of the epoxy resin used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially contains 100 parts by weight of the total amount of the components (A) and (B). It is particularly preferred not to.

An antioxidant (antiaging agent) can be used in the curable composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF Japan Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by ADEKA Corporation); hindered amines shown by Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Corporation) A system light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

When the curable composition of the present invention contains an antioxidant, the content thereof is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). 0.2 to 5 parts by weight is more preferable.

A light stabilizer can be used in the curable composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. Specific examples of the light stabilizer are also described in JP-A-9-194731.

When the curable composition of the present invention contains a light stabilizer, the amount used is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of components (A) and (B). 0.2 to 5 parts by weight is more preferable.

When a photocurable substance is used in combination with the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all of these are manufactured by BASF Japan Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (all of which are stocks) Examples include Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by BASF Japan Ltd.).

An ultraviolet absorber can be used in the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable.

When the curable composition of the present invention contains an ultraviolet absorber, the amount used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B). 0.2 to 5 parts by weight is more preferable. It is preferable to use a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber in combination.

A filler can be added to the curable composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as glass fibers and filaments.

When the curable composition of the present invention contains a filler, the content thereof is 1 to 250 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B), and 10 to 200 parts by weight. Preferably there is.

When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and it is preferable to use in a range of 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Results are obtained. If you want to obtain a cured product with low strength and high elongation at break, mainly from calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When the selected filler is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

In order to improve the workability (such as sharpness) of the curable composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. The particle size of the balloon is preferably 0.1 mm or less from the viewpoint of improving workability (such as sharpness), and preferably from 5 to 300 μm from the viewpoint of making the surface of the cured product matt.

The curable composition of the present invention is a sizing board, especially a ceramic sizing board, and the like because of the good chemical resistance of the cured product. However, it is preferably used for an adhesive in which the adhesive remains as it is, but it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When a flaky or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm is blended with the curable composition of the present invention, the cured product has such a high-grade outer wall. The cured product has an excellent curable composition that lasts for a long time because of its excellent chemical resistance. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

As described in JP-A-9-53063, preferred diameters, blending amounts, materials and the like of the scaly or granular substance are as follows.

The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and those having an appropriate size are used according to the material and pattern of the outer wall. Those of about 0.2 to 5.0 mm or about 0.5 to 5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

About 1 to 200 parts by weight of the scaly or granular substance is blended with 100 parts by weight of the curable composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.

Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. Preferred diameters, blending amounts, materials, etc. of the balloon are as follows as described in JP-A-10-251618.

The balloon is a spherical filler with a hollow inside. As a material for this balloon, an inorganic or organic balloon or a combination of these balloons can be used. Specific examples include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. A composite material and an organic material can be combined, or can be laminated to form a plurality of layers. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface treated with an adhesion-imparting agent.

The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. Those of about 0.2 to 5.0 mm or about 0.5 to 5.0 mm can also be used. When the amount is less than 0.1 mm, even when blended in a large amount, only the viscosity of the curable composition is increased, and a rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in volume concentration in the curable composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

When a balloon is used, the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state. An amine compound for obtaining a state, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

Specific examples of the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A No. 2000-154368, JP-A No. 2001-164237, and International Publication No. 97/05201.

Even when the curable composition of the present invention contains sealing material cured particles, the cured product can form irregularities on the surface to improve the design. Preferred diameters, blending amounts, materials and the like of the cured sealant particles are as follows as described in JP-A No. 2001-115142.

The diameter is preferably 0.1 to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

Moreover, a silicate can be used for the curable composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product of the curable composition of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When silicate is used, the amount used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B).

Specific examples of the silicate include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the effect of improving the resilience, durability, and creep resistance is greater than that of tetraalkoxysilane.

Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by subjecting it to partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

A tackifier resin can be added to the curable composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrene block copolymers, hydrogenated products thereof, phenol resins, modified phenol resins (for example, cashew oil modified phenol resin, tall oil modified phenol resin, etc.), terpene phenol resins, xylene-phenol resins, cyclohexane Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more.

Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifier resins may be used alone or in combination of two or more.

When the curable composition of the present invention contains a tackifying resin, the content thereof is 5 to 1,000 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). It is preferably from ˜100 parts by weight.

A solvent or a diluent can be added to the curable composition of the present invention. The solvent or diluent is not particularly limited, and aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used. When using a solvent or diluent, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and more preferably 250 ° C. or higher because of the problem of air contamination when the curable composition is used indoors. Particularly preferred. A solvent or a diluent may be used independently and may be used together 2 or more types.

You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. The physical property modifier is not particularly limited, but examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkylisopropenoxysilanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using a physical property modifier, the hardness when the curable composition of the present invention is cured can be increased, or conversely, the hardness can be decreased and elongation at break can be produced. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521. Further, derivatives of alkyl alcohols such as hexanol, octanol, decanol, etc., which produce a silicon compound that produces R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029 Examples thereof include compounds that are derivatives of polyhydric alcohols having 3 or more hydroxy groups such as propane, glycerin, pentaerythritol, sorbitol and the like, and that generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis.

When the curable composition of the present invention contains a physical property modifier, the content thereof is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of (A) and (B). The amount is preferably 5 to 10 parts by weight.

A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle diameter of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A curable composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

When the curable composition of the present invention contains a thixotropic agent, the content thereof is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B).

In the curable composition of the present invention, a compound containing an epoxy group can be used. When a compound containing an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound containing an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred.

When the curable composition of the present invention contains a compound containing an epoxy group, the content thereof is 0.5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). .

To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. A flame retardant may be used independently and may be used together 2 or more types.

When the curable composition of the present invention contains a flame retardant, the content thereof is 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and 10 to 100 parts by weight. It is preferable that

Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in this specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

When the curable composition of the present invention is a one-component type, all the ingredients are pre-blended. Therefore, the water-containing ingredients are used after dehydration and drying, or by reducing the pressure during compounding and kneading. It is preferable to dehydrate. In the case where the curable composition of the present invention is a two-component type, it is not necessary to add a curing catalyst to the main agent containing a polymer having a reactive silicon group, so even if some moisture is contained in the compounding agent. Although there is little concern about gelation, dehydration and drying are preferred when long-term storage stability is required. For dehydration and drying methods, heat drying method or vacuum dehydration method for solid materials such as powders, dehydration method using vacuum zeolite or activated zeolite, silica gel, quick lime, magnesium oxide for liquid materials The method is preferred. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- An alkoxysilane compound such as glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound improves storage stability.

The amount of silicon compound that can react with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B), The amount is preferably 0.5 to 10 parts by weight.

The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

The curable composition of the present invention is preferably in a liquid state at normal temperature (23 ° C.), and forms a three-dimensional network structure by the action of moisture when exposed to the atmosphere, to a solid having rubbery elasticity. And cured.

The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material Can be used for etc. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among them, it can be used as a sealing material or an adhesive, particularly an adhesive that is not a hot melt adhesive. More preferred.

Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or with the help of a primer, it can also be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, It can also be used as a waterproof material combined with asphalt.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Polyoxypropylene diol having a molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 15,000 having a terminal hydroxyl group (Tosoh Corporation as a liquid feeding system) A bifunctional polypropylene oxide polymer having a polystyrene equivalent molecular weight measured using TSK-GEL H type manufactured by Tosoh Corporation and a solvent using THF was obtained using HLC-8120GPC manufactured by Tosoh Corporation. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and 1.8 parts by weight of dimethoxymethylsilane was added while stirring. It was dripped slowly. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby a terminal was a dimethoxymethylsilyl group and an average of 1.6 silicon groups per molecule. A reactive silicon group-containing polyoxypropylene polymer (polymer A-1) having a number average molecular weight of 15,000 was obtained.

(Synthesis Example 2)
3 parts by weight of toluene is added to 100 parts by weight of a diol having an aromatic ring structure (trade name: BPX-55, manufactured by ADEKA, molecular weight 1104, OHV 2.53 mmol / g), and azeotropic dehydration is performed at 110 ° C. under reduced pressure for 1.5 hours. Went. After the temperature was lowered to 90 ° C., 30 ppm of Neostan U-360 (manufactured by Nitto Kasei Co., Ltd.), a mercaptotin-based catalyst, was added, and 3-isocyanatopropyltrimethoxysilane (manufactured by Momentive Performance Materials Co., Ltd.) Name: A-LINK35) 51.9 parts by weight were added and reacted. The disappearance of the isocyanate group peak (2272 cm ⁻¹ ) was confirmed by FT-IR, and the reaction was terminated to obtain an aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group.

(Synthesis Example 3)
A trimethoxysilyl group was synthesized in the same manner as in Synthesis Example 2 except that 100 parts by weight of BPX-33 (manufactured by ADEKA, molecular weight 817, OHV 3.48 mmol / g) was used instead of BPX-55 in Synthesis Example 2. An aromatic ring structure-containing organic polymer (B-2) was obtained.

(Synthesis Example 4)
In the same manner as in Synthesis Example 2 except that 100 parts by weight of BPX-21 (manufactured by ADEKA, molecular weight 640, OHV 5.06 mmol / g) was used instead of BPX-55 in Synthesis Example 2, the trimethoxysilyl group was An aromatic ring structure-containing organic polymer (B-3) was obtained.

(Synthesis Example 5)
In the same manner as in Synthesis Example 2 except that 100 parts by weight of BPX-2000 (manufactured by ADEKA, molecular weight 2778, OHV 1.01 mmol / g) was used instead of BPX-55 in Synthesis Example 2, a trimethoxysilyl group was added. An aromatic ring structure-containing organic polymer (B-4) was obtained.

(Synthesis Example 6)
Trimethoxy in the same manner as in Synthesis Example 2 except that 100 parts by weight of AC006 (manufactured by Ito Oil Co., Ltd., aromatic-containing castor oil-based polyol, OHV 1.01 mmol / g) was used instead of BPX-55 in Synthesis Example 2. An aromatic ring structure-containing organic polymer (B-5) having a silyl group was obtained.

(Synthesis Example 7)
Trimethoxy in the same manner as in Synthesis Example 2 except that 100 parts by weight of AC009 (produced by Ito Oil Co., Ltd., aromatic-containing castor oil-based polyol, OHV 3.91 mmol / g) was used instead of BPX-55 in Synthesis Example 2. An aromatic ring structure-containing organic polymer (B-6) having a silyl group was obtained.

(Example 1)
90 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (Polymer A-1) obtained in Synthesis Example 1 and the aromatic ring structure-containing organic polymer having the trimethoxysilyl group obtained in Synthesis Example 2 ( B-1) 10 parts by weight, surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiruka CCR) as filler, vinyltrimethoxysilane (manufactured by Momentive Performance Materials, A-171) as dehydrating agent, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, A-1120) as an adhesion-imparting agent, and dibutyltin diacetacetonate (Nitto Kasei Co., Ltd.) as a curing catalyst Manufactured by Neostan U220H) were mixed in a predetermined amount and kneaded to obtain a curable composition.

(Example 2)
The reactive silicon group-containing polyoxypropylene polymer (polymer A-1) in Example 1 was used in an amount of 60 parts by weight, and the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group was used in an amount of 40 parts by weight. Except for this, a curable composition was obtained in the same manner as in Example 1.

(Example 3)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 3 (B-2) ) Was used in the same manner as in Example 1 except that 10 parts by weight were used.

Example 4
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 2, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 3 (B-2) ) Was used in the same manner as in Example 2 except that 40 parts by weight was used.

(Example 5)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 4 (B-3) ) Was used in the same manner as in Example 1 except that 10 parts by weight were used.

(Example 6)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 2, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 4 (B-3) ) Was used in the same manner as in Example 2 except that 40 parts by weight was used.

(Example 7)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 5 (B-4) ) Was used in the same manner as in Example 1 except that 10 parts by weight were used.

(Example 8)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 2, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 5 (B-4) ) Was used in the same manner as in Example 2 except that 40 parts by weight was used.

Example 9
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 6 (B-5) ) Was used in the same manner as in Example 1 except that 10 parts by weight were used.

(Example 10)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 2, the aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 6 (B-5) ) Was used in the same manner as in Example 2 except that 40 parts by weight was used.

(Example 11)
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer (B-6) having a trimethoxysilyl group obtained in Synthesis Example 7 was used. ) Was used in the same manner as in Example 1 except that 10 parts by weight were used.

Example 12
Instead of the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1, the aromatic ring structure-containing organic polymer (B-6) having a trimethoxysilyl group obtained in Synthesis Example 7 was used. ) Was used in the same manner as in Example 2 except that 40 parts by weight was used.

(Comparative Example 1)
Using 100 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (polymer A-1) without adding the aromatic ring structure-containing organic polymer (B-1) having a trimethoxysilyl group in Example 1 Except having done, it carried out similarly to Example 1, and obtained the curable composition.

Table 1 shows the compounding ratios of the above Examples and Comparative Examples.

Using the curable composition obtained as described above, an H-type test piece was used as an adherend according to JIS5758, and was prepared without a primer. Using the obtained test piece, a tensile test was conducted at a speed of 50 mm / min after aging for 7 days at room temperature and further for 7 days at 50 ° C. and immediately after being immersed in warm water at 50 ° C. for 7 days. The results are shown in Table 1. In addition, as a comparative example, the result in the case where the aromatic ring structure-containing organic polymer having a trimethoxysilyl group was not added is also shown.

In Table 1, CF and AF indicate cohesive failure and interfacial failure, respectively. The cohesive failure is a case where, in a tensile test, a fractured portion is not a bonding surface with an adherend but a cured product portion when a test piece is broken. Interfacial fracture is when the fracture location is an adhesive surface with the adherend. In addition, MF indicates that the substrate has been destroyed (material failure) during the tensile test. When the fracture mode is cohesive fracture or interface fracture, the occupation ratio in the fracture area is shown after the initial of each fracture mode. For example, C100 is indicated when cohesive failure is 100%, and C50A50 is indicated when cohesive failure and interface failure occur 50% each. Moreover, Tb is a breaking strength, and it shows that adhesive strength is so high that this value is large. As shown in Table 1, it can be seen that Examples 1 to 6 and 9 to 12 show better water-resistant adhesive strength than the comparative example. In addition, when BPX-2000 in which the reaction amount of propylene oxide with respect to 1 mol of bisphenol A as the component (B) was 30 mol or more was used, the above effect could not be obtained.

(Synthesis Example 8)
Polyoxypropylene diol having a molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 15,000 having a terminal hydroxyl group (Tosoh Corporation as a liquid feeding system) A bifunctional polypropylene oxide polymer having a polystyrene equivalent molecular weight measured using TSK-GEL H type manufactured by Tosoh Corporation and a solvent using THF was obtained using HLC-8120GPC manufactured by Tosoh Corporation. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and 1.8 parts by weight of dimethoxymethylsilane was added while stirring. It was dripped slowly. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby a terminal was a dimethoxymethylsilyl group and an average of 1.6 silicon groups per molecule. A reactive silicon group-containing polyoxypropylene polymer (polymer A-2) having a number average molecular weight of 28,000 was obtained.

(Synthesis Example 9)
100 parts by weight of bisphenol A type alkylene oxide-added diglycidyl ether (manufactured by ADEKA, trade name: Adeka Resin EP4000, molecular weight 640) was placed in an eggplant flask, and 112 parts by weight of aminopropyltrimethoxysilane was added under a nitrogen stream. The temperature was raised to 80 ° C. and stirring was continued for 1 hour. By confirming the disappearance of the epoxy group by NMR, an aromatic ring structure-containing organic compound (B-7) having a terminal trimethoxysilyl group and having a hydroxyl group in the molecule was obtained. Since the aromatic ring structure-containing organic polymer (B-7) has a hydroxyl group, it does not correspond to the component (B) used in the curable composition of the present invention.

(Synthesis Example 10)
100 parts by weight of BPX-33 (manufactured by ADEKA, molecular weight 817, OHV 3.48 mmol / g) was added to the reaction vessel, and then a methanol solution of NaOMe 1.1 times equivalent to the hydroxyl group was added to distill methanol. Then, 3-chloro-1-propene was further added to convert the terminal hydroxyl group into an allyl group. Next, 100 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and 23.2 parts by weight of dimethoxymethylsilane was added while stirring. It was dripped slowly. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby an aromatic ring structure-containing organic polymer having a dimethoxymethylsilyl group at the terminal (B-8) Got.

(Comparative Example 2)
70 parts by weight of a reactive silicon group-containing polyoxypropylene polymer (Polymer A-2) obtained in Synthesis Example 8 and an aromatic ring structure-containing organic polymer having a trimethoxysilyl group obtained in Synthesis Example 9 ( B-7) 30 parts by weight, 90 parts by weight of diisononyl phthalate as a plasticizer, 160 parts by weight of colloidal calcium carbonate (manufactured by Takehara Chemical Industries, NeolightSP) as a filler, 54 parts by weight of heavy calcium carbonate (manufactured by Maruo Calcium, LM2200) Parts, 5 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., R820), 5 parts by weight of thixotropic agent (Arkema, craylarrac SL), 1 part by weight of UV absorber (manufactured by BASF, Tinuvin 770), light stabilizer 1 part by weight (manufactured by BASF, Tinuvin 326), vinyltrimethoxysilane (momentive performance) as a dehydrating agent Mans Materials Co., Ltd., A-171) 3 parts by weight, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Momentive Performance Materials Co., A-1120) as an adhesion-imparting agent As a curing catalyst, 3 parts by weight, 0.5 parts by weight of dibutyltin diacetacetonate (Nitto Kasei Co., Ltd., Neostan U220H) is blended in a predetermined amount, kneaded and filled into a cartridge to prepare a one-pack curable composition. Obtained. The one-part curable composition was stored in an oven at 50 ° C. for 4 weeks. The curable composition of Comparative Example 2 was damped enough to be visually confirmed after storage for 4 weeks.

(Example 13)
Comparative Example 2 except that 30 parts by weight of the aromatic ring structure-containing organic polymer (B-1) obtained in Synthesis Example 2 was used instead of the aromatic ring structure-containing organic polymer (B-7) in Comparative Example 2. In the same manner as in Example 2, a one-component curable composition was prepared and evaluated.

(Example 14)
Comparative Example 2 except that 30 parts by weight of the aromatic ring structure-containing organic polymer (B-8) obtained in Synthesis Example 10 was used instead of the aromatic ring structure-containing organic polymer (B-7) in Comparative Example 2. In the same manner as in Example 2, a one-component curable composition was prepared and evaluated.

The curable composition of the present invention is a cured product that exhibits good adhesion even when cured after storage. In order to verify this, using a curable composition after being stored for 4 weeks at 50 ° C. in a sealed state in a cartridge, using a mortar with an H-type test piece as an adherend according to JIS5758, a primer Made without. The obtained test piece was subjected to a tensile test at a speed of 50 mm / min after aging for 7 days at room temperature and further for 7 days at 50 ° C., and further immersed in warm water at 50 ° C. for 7 days. Moreover, the viscosity in 10 rotations was measured before and after storage using a B type viscometer, and the viscosity change rate was measured. The results are shown in Table 2.

Example 13 has a higher adhesive strength after immersion in 50 ° C. warm water than Comparative Example 2, and Example 14 has a higher adhesive strength maintenance ratio after immersion in 50 ° C. warm water than Comparative Example 2. I understood. The reason for this is that in Comparative Example 2, the rate of change in viscosity after storage is higher than in Examples 13 and 14, and the three-dimensional crosslinking proceeds, and the wettability with the adhesive interface is insufficient. It is done.

Claims

(A) Reactive silicon group-containing organic polymer (excluding the following component (B)), and
(B) A curable composition comprising an organic polymer having an aromatic ring structure and / or a hydrogenated aromatic ring structure, having a reactive silicon group at a terminal and no hydroxyl group .
The curable composition according to claim 1, wherein the component (B) has a bisphenol structure.
The curable composition according to claim 1 or 2, comprising 3 to 100 parts by weight of component (B) with respect to 100 parts by weight of component (A).
The curable composition according to any one of claims 1 to 3, wherein the component (B) contains an alkylene oxide addition reaction product of bisphenols.
The curable composition according to claim 4, wherein the alkylene oxide addition reaction product of bisphenol is an addition reaction product of bisphenol A and propylene oxide.
The curable composition according to claim 5, wherein the reaction amount of propylene oxide with respect to 1 mol of bisphenol A is 2 to 30 mol.
The curable composition according to claim 5, wherein the reaction amount of propylene oxide with respect to 1 mol of bisphenol A is 2 to 15 mol.
The curable composition according to any one of claims 1 to 7, wherein the main chain skeleton of the component (A) is a polyoxyalkylene polymer.
The curable composition according to any one of claims 1 to 8, wherein the component (B) is a modified product of a silicon compound having a hydrolyzable functional group on a silicon atom.
The curable composition according to any one of claims 1 to 9, wherein the component (B) has a structure represented by the following general formula (6) or the following general formula (7) at a terminal.
—O—R 8 —SiR 9 b X 2 3-b (6)
(In the general formula (6), R 8 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R 9 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X 2 each independently represents a hydroxyl group or a hydrolyzable group, and b represents 0 or 1.)
—W—R 10 —SiR 11 c X 3 3-c (7)
(In the general formula (7), R 10 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. R 11 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X 3 each independently represents a hydroxyl group or a hydrolyzable group, c represents 0 or 1, W represents —O—CO—N (R 12 ) —, —N (R 12 ) —CO—O—. , -N (R 12 ) -CO-N (R 12 )-, -N (R 12 ) -CS-N (R 12 )-or -S-, wherein R 12 is hydrogen or halogen-substituted Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.)
The curable composition according to any one of claims 1 to 10, wherein the component (A) has a reactive silicon group represented by the following general formula (1).
-SiR 1 a X 1 3-a (1)
(In the general formula (1), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X 1 independently represents a hydroxyl group or a hydrolyzable group. A represents 0 or 1. .)
A sealing material comprising the curable composition according to any one of claims 1 to 11 as a component.
An adhesive comprising the curable composition according to any one of claims 1 to 11 as a component.
A coating material obtained by curing the curable composition according to any one of claims 1 to 11.