JP5488242B2 - Moisture curable resin composition - Google Patents

Description

  The present invention relates to a moisture curable resin composition. More specifically, the present invention relates to a moisture curable resin composition suitable for various sealing material applications.

Conventionally, a moisture curable resin composition containing a modified polyoxyalkylene polymer having a hydrolyzable silyl group has been used as a main polymer such as an adhesive, a sealing agent, and a sealing material (for example, Patent Document 1). ).
For such a moisture curable resin composition, when the self-leveling property is to be improved, the molecular weight of the modified polyoxyalkylene polymer is reduced, or a large amount of volatile organic compound (VOC) or plasticizer is used. By adding, it is usual to lower the viscosity before curing of the composition.

However, when the molecular weight of the modified polyoxyalkylene polymer is reduced, the physical properties of the composition after curing are lowered and become brittle, and particularly the tearability is inferior, so that a desirable result cannot be obtained. In addition, when a large amount of a volatile organic compound or a plasticizer is added, the physical properties of the composition after curing are lowered and softened, and in particular, the tearability is inferior, so that a desirable result cannot be obtained. Moreover, the addition of a large amount of a volatile organic compound is particularly problematic when a low-boiling point solvent such as toluene or xylene is used. When used, the composition will cure and then bleed out on the surface of the cured product, so there are problems with residual tack and paintability after curing, and phthalates are listed as so-called environmental hormones. There are many environmental problems, such as being regarded as an environmental problem.
In addition, when the composition is cured, there are cases where a part of the surface is dented or wrinkled, etc., but such occurrence of abnormal appearance due to curing shrinkage is particularly used for sealing materials. In this case, there are great problems in appearance and aesthetics.

  Therefore, there is a need for a moisture curable resin composition that does not have such problems, has both excellent leveling performance before curing and physical properties after curing, and has good adhesion to metals, glass, and other inorganic members. ing.

Japanese Patent No. 4450107

  Therefore, the present invention has an excellent leveling property before curing, high hardness after curing, good adhesion to metal and glass, and moisture curing type in which appearance abnormality due to curing shrinkage is suppressed. It is an object to provide a resin composition.

The inventors of the present invention have made extensive studies to solve the above problems,
100 parts by mass of an organic polymer having a hydrolyzable silyl group, 3 to 100 parts by mass of an epoxy resin, a ketimine compound, and a curing catalyst for the hydrolyzable silyl group, the mole of imino group that the ketimine compound has The ratio of the equivalent of the epoxy group of the epoxy resin to the molar equivalent of the epoxy group (molar equivalent of imino group / molar equivalent of epoxy group) = 0.5 to 1.5, and at least 0.2 molar equivalent of the ketimine compound Moisture curing with a ketimine compound obtained by reacting a carbonyl compound with a polyamine compound having a melting point at 1013 hPa of 35 ° C. or lower and a boiling point of 100 ° C. or higher, and a viscosity at 23 ° C. of 0.1 to 100 Pa · s. The mold resin composition has excellent leveling properties before curing, and has a high hardness after curing, resulting in metal and glass. Adhesiveness is good, moreover, it becomes known that it is possible to moisture-curable resin composition abnormal appearance is suppressed due to the curing shrinkage, and completed the present invention.

Although the present inventors think that the problem may be solved by the harmony of the following mechanisms, it is not necessarily limited to these.
a) When a blend system of an organic polymer having a hydrolyzable silyl group and an epoxy resin is formed, a sea-island structure is formed, and it is flexible and well stretched after curing, and hardness can be imparted after curing.
b) When the epoxy resin and the ketimine compound are respectively an epoxy resin having a high reactivity with the ketimine compound and a high epoxy equivalent, and a ketimine compound having a high reactivity with the epoxy resin and a low amine value, the viscosity of the composition before curing. Can be drastically reduced.
c) When the ketimine compound is made from a liquid polyamine compound, deformation during curing can be reduced.

That is, the present invention provides the following (1) to ( 3 ).
(1) 100 parts by mass of an organic polymer (A) having a hydrolyzable silyl group, 3 to 100 parts by mass of an epoxy resin (B), a ketimine compound (C), and a curing catalyst for the hydrolyzable silyl group ( D) and
The ratio of the molar equivalent of the imino group of the ketimine compound (C) to the molar equivalent of the epoxy group of the epoxy resin (molar equivalent of imino group / molar equivalent of epoxy group) is 0.5 to 1.5,
A ketimine compound obtained by reacting at least 0.2 molar equivalent of at least one polyamine compound selected from 1,4-diaminobutane and 1,3-diaminopropane with a carbonyl compound in the ketimine compound (C). And
A moisture curable resin composition having a viscosity at 23 ° C. of 0.1 to 100 Pa · s.
(2) The organic polymer (A) is at least one alkoxysilyl selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as a hydrolyzable silyl group. The moisture curable resin composition according to the above (1), which comprises an alkoxysilyl group-modified polyoxyalkylene polymer having a group and a main chain being substantially polyoxyalkylene.
(3) The moisture-curable type according to (1) or (2) above, wherein the ketimine compound (C) comprises a ketimine compound obtained by reacting a carbonyl compound represented by the following formula (1) with a polyamine. Resin composition.
Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. R ¹ and R ² can be bonded to each other to form a ring structure, and R ¹ and R ⁴ are bonded to each other. Te can form a ring structure.)

  According to the present invention, the moisture-curing type has excellent leveling properties before curing, has high hardness after curing, has good adhesion to metals and glass, and has suppressed appearance abnormality due to curing shrinkage. A resin composition can be provided.

The present invention will be described in detail below.
The moisture curable resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”)
100 parts by mass of an organic polymer (A) having a hydrolyzable silyl group, 3 to 100 parts by mass of an epoxy resin (B), a ketimine compound (C), and a curing catalyst (D),
The molar equivalent of the imino group possessed by the ketimine compound (C) (when two or more ketimine compounds are contained, the total molar equivalent per each ketimine compound) The molar equivalent of the epoxy group possessed by the epoxy resin (two or more types) When the epoxy resin is contained, the ratio (molar equivalent of imino group / molar equivalent of epoxy group) relative to the total molar equivalent of each epoxy resin is 0.5 to 1.5,
At least 0.2 molar equivalent of the ketimine compound (C) is a ketimine compound obtained by reaction of a polyamine having a melting point of 35 ° C. or lower and a boiling point of 100 ° C. or higher at 1013 hPa with a ketone, and
It is a moisture curable resin composition having a viscosity at 23 ° C. of 0.1 to 100 Pa · s.

<Organic polymer (A)>
The organic polymer (A) having a hydrolyzable silyl group (hereinafter sometimes simply referred to as “organic polymer (A)”) will be described below.

  The polymer (A) contained in the composition of the present invention is not particularly limited as long as it is an organic polymer having a hydrolyzable silyl group, but is preferably an alkoxysilyl group-modified polyoxyalkylene polymer.

  The alkoxysilyl group-modified polyoxyalkylene polymer is a polymer having an alkoxysilyl group as a reactive group, and the main chain being substantially polyoxyalkylene. By containing the alkoxysilyl group-modified polyoxyalkylene polymer, the curing time at room temperature can be shortened without foaming.

  In the alkoxysilyl group, among the three hydrogen atoms (hydrogen groups) bonded to the silicon atom of the silyl group, 1 to 3 hydrogen atoms are substituted with alkoxy groups, and the remaining 0 to 2 hydrogen atoms Is not particularly limited as long as it is unsubstituted or substituted by a non-hydrolyzable group. The three hydrogen atoms are preferably substituted by two or more by an alkoxy group, more preferably all three are substituted. This is because the curing time is further shortened.

  As the alkoxy group, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is more preferable because of mild hydrolyzability.

  The non-hydrolyzable group is not particularly limited as long as it is a non-hydrolyzable substituent, and examples thereof include an alkyl group, an acyl group, and an alkenyl group. Among these, an alkyl group having 1 to 5 carbon atoms is included. Are preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.

  Examples of the alkoxysilyl group include a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group.

  The organic polymer (A) includes at least one alkoxysilyl group selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group as a hydrolyzable silyl group. An alkoxysilyl group-modified polyoxyalkylene polymer having a main chain that is substantially polyoxyalkylene is preferred.

  The main chain of the alkoxysilyl group-modified polyoxyalkylene polymer is substantially polyoxyalkylene. The polyoxyalkylene is not particularly limited. Examples thereof include polyoxyethylene and polyoxypropylene, which are selected in consideration of adhesion and water resistance.

  In the present invention, the fact that the main chain is substantially polyoxyalkylene means that the repeating unit constituting the main chain contains an oxyalkylene group in an amount of 50% or more of the total number of moles of the repeating unit.

  The repeating unit other than the oxyalkylene group that can be contained in the polyoxyalkylene is not particularly limited.

  In the trialkoxysilyl group-modified polyoxyalkylene polymer, the main chain may be a homopolymer or a copolymer.

  The main chain may be linear or branched. When the main chain is linear, the cured product is excellent in elongation. When the main chain is branched, a tougher cured product can be obtained.

  The alkoxysilyl group-modified polyoxyalkylene polymer has at least one alkoxysilyl group selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as a reactive group. It is preferable to have. The number of reactive groups is preferably 1 to 4 per molecule of the alkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of being excellent in rapid curability and excellent in the balance between viscosity and flexibility.

  The reactive group can be attached to the end of the main chain and / or as a side chain. From the viewpoint of excellent breaking strength and breaking elongation of the cured product, the reactive group is preferably bonded to at least both ends of the main chain.

  The reactive group can be bonded to the main chain directly or via an organic group. The organic group is not particularly limited. For example, the hydrocarbon group which may have a hetero atom like an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned.

  The alkoxysilyl group-modified polyoxyalkylene polymer is excellent in fast curability and storage stability, and from the viewpoint of excellent balance between viscosity and flexibility, a polyoxypropylene polymer having a trimethoxysilyl group at the terminal, and a terminal. A polyoxypropylene polymer having a triethoxysilyl group is preferred, a polyoxypropylene polymer having one trimethoxysilyl group at each of two or more terminals, and one triethoxysilyl group at each of two or more terminals A polyoxypropylene polymer is more preferable, a linear polyoxypropylene polymer having trimethoxysilyl groups at both ends, a linear polyoxypropylene polymer having triethoxysilyl groups at both ends, and both ends. 3 having a trimethoxysilyl group and having a trimethoxysilyl group at the end of the side chain Branched polyoxypropylene polymer ability branched polyoxypropylene polymer of trifunctional having terminal to triethoxysilyl group having side chains triethoxysilyl groups at both ends is more preferable.

Examples of the trialkoxysilyl group-modified polyoxyalkylene polymer include compounds represented by the following formula (2).

(In the formula, R ¹ and R ² are alkylene groups having 1 to 5 carbon atoms, R ³ is a methyl group or an ethyl group, n is an integer of 9 to 900, and m is an integer of 1 to 5) And A is the residue of the initiator used in the production of the polyoxyalkylene monool or polyoxyalkylene polyol used as a raw material.)

  When producing a trialkoxysilyl group-modified polyoxyalkylene polymer, polyoxyalkylene monool or polyoxyalkylene polyol can be used as a raw material, but when producing the polyoxyalkylene monool or polyoxyalkylene polyol. The initiator used for is not particularly limited. For example, a conventionally well-known thing is mentioned.

  The trialkoxysilyl group-modified polyoxyalkylene polymer is superior in storage stability and fast curability, can suppress thickening, and can have an appropriate viscosity of the composition. Those represented by 2) are preferred.

  The composition of the present invention has one alkoxysilyl group at one end with respect to a polyoxypropylene polymer having one alkoxysilyl group at each of two or more ends for the purpose of lowering the viscosity of the composition. One polyoxypropylene polymer can be mixed. The polyoxypropylene polymer having one alkoxysilyl group at one end may have a hydroxy group without having an alkoxysilyl group at another end.

  The amount of the polyoxypropylene polymer having one alkoxysilyl group at one end is 10% by mass or less based on the polyoxypropylene polymer having one alkoxysilyl group at two or more ends. It is preferable from the point that the physical properties (strength and elongation) of the cured product do not extremely decrease.

  The molecular weight of the alkoxysilyl group-modified polyoxyalkylene polymer is preferably 3,000 to 50,000 from the viewpoint of excellent balance between viscosity before curing (leveling property) and flexibility after curing. More preferably, it is 3,000 to 30,000.

  The alkoxysilyl group-modified polyoxyalkylene polymer may contain a urethane bond from the viewpoint of excellent physical properties (elongation and strength) after curing.

The production of the alkoxysilyl group-modified polyoxyalkylene polymer is not particularly limited. For example, a polyoxyalkylene monool and / or a polyoxyalkylene polyol (for example, a compound represented by A-[(OR ¹ ) _n —OH] _m may be mentioned. R ¹ , n, and m are the same as the above formula. And a halogenated unsaturated hydrocarbon group (for example, a compound represented by R ² —X, where R ² has an unsaturated bond having 1 to 10 carbon atoms). And a polyoxyalkylene compound having an unsaturated bond (for example, A-[(OR ¹ ) _n ), which is a hydrocarbon group and X is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. -O-R < ² >] _m .) Can be obtained.

Next, a polyoxyalkylene compound having an unsaturated bond is represented by a hydrotrialkoxysilane (for example, HSi (OR ³ ) ₃ in the presence of a platinum catalyst such as a platinum vinylsiloxane complex. R ³ represents the above formula. (It is synonymous with (V).) Or an alkoxysilyl group modified polyoxyalkylene polymer can be manufactured by making it react with hydrodialkoxyalkylsilane. The platinum catalyst is not particularly limited as long as it can be used for the reaction between a hydrosilane compound and an unsaturated hydrocarbon group.

  In the polymer (A) of the present invention, the alkoxysilyl group-modified polyoxyalkylene polymer can be used alone or in combination of two or more.

<Epoxy resin (B)>
The epoxy resin (B) will be described below.
By containing the epoxy resin (B) and the ketimine (C), the composition of the present invention can maintain physical properties (strength / elongation) after curing while lowering the viscosity before curing of the composition. In addition, the alkoxysilyl group-modified polyoxyalkylene polymer is excellent in moisture resistance and heat resistance as compared with a single polymer.

  The epoxy resin contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F Glycidyl ether type obtained by reaction of polyphenols such as bixylenol and epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc. Polyglycis obtained by the reaction of monohydric alcohol with epichlorohydrin Glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexa Polyglycidyl ester type derived from polycarboxylic acid such as hydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; glycidylamino derived from aminophenol, aminoalkylphenol, etc. Glycidyl ether type; Glycidylaminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane Glycidylamine type derived from bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and the like; and epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, and triglycidylcyanurate .

Of these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and naphthalene type epoxy resins are preferred from the viewpoint of low viscosity and high reactivity with ketimine compounds.
The epoxy resins can be used alone or in combination of two or more.

  In the present invention, the amount of the epoxy resin is 3 to 100 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer. From the viewpoint of excellent balance of storage stability, viscosity and flexibility, the amount of the epoxy resin is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer.

<Ketimine (C)>
The ketimine compound (C) (hereinafter sometimes simply referred to as “ketimine (C)”) will be described below.

  The ketimine compound (C) contained in the composition of the present invention is a ketimine compound obtained by the reaction of a carbonyl compound and a polyamine compound, and at least 0.2 molar equivalent of the carbonyl compound and 1013 hPa It is a ketimine compound obtained by reacting a polyamine compound having a melting point of 35 ° C. or lower and a boiling point of 100 ° C. or higher.

  The ketimine (C) preferably contains a ketimine compound obtained by reacting a carbonyl compound represented by the following formula (1) with a polyamine compound, and more preferably consists of this ketimine compound.

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. R ¹ and R ² can be bonded to each other to form a ring structure, and R ¹ and R ⁴ are bonded to each other. To form a ring structure.)

  One imino group (—N═) of the ketimine compound reacts with moisture to hydrolyze to become a primary amine, and can react with one or two epoxy groups.

The carbonyl compound used in the production of the ketimine (C) will be described below.
As said carbonyl compound, what is represented by Formula (1) is preferable.

In the formula (1), the alkyl group having 1 to 6 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1 -Dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methyl Propyl group, and a 1-ethyl-2-methylpropyl group. The alkyl group as R ⁴ is not particularly limited. For example, it is synonymous with said C1-C6 alkyl group.

Examples of the carbonyl compound include n in the formula (I) such as methyl isopropyl ketone (MIPK), methyl t-butyl ketone (MTBK), methyl cyclohexyl ketone, and methylcyclohexanone, and R ⁴ is an alkyl group. Ketone; ketone in which n in formula (I) is 2: an aldehyde compound in which n in formula (I) is 1 and R ⁴ is a hydrogen atom. Among these, from the viewpoint of being excellent in rapid curability and storage stability, a ketone in which n in the formula (1) is 1 and R ⁴ is an alkyl group is preferable, and methyl isopropyl ketone (MIPK), methyl t-butyl ketone ( MTBK), methyl cyclohexyl ketone, and methyl cyclohexanone are more preferable.

The polyamine compound used in the production of the ketimine (C) will be described below.
The above polyamine compound is a compound having at least 0.2 molar equivalents of ketimine (C) having two or more amino groups, the melting point at 1013 hPa is 35 ° C. or less, and the boiling point is Although it is limited to what is 100 degreeC or more, about manufacture of the remainder of ketimine (C), if it is a compound which has two or more amino groups, it can be used without being restrict | limited especially.

Examples of the compound having two or more amino groups include compounds represented by the following formula (3).
R— (CH ₂ —NH ₂ ) _n (3)
In the formula, R is a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and n is an integer of 2 or more.
R preferably has 1 to 10 carbon atoms from the viewpoint of excellent fast curability and storage stability.
n is preferably 1 to 4 which are easily available.

  Examples of polyamines include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, and 1,2-diaminopropane. A diamine having a polyether skeleton such as Jeffamine EDR148 manufactured by Sun Techno Chemical Co., Ltd .; 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl- Cyclohexylamine, norbornane skeleton typified by NBDA (norbornanediamine) manufactured by Mitsui Toatsu Chemicals, Ltd., alicyclic hydrocarbon such as N-aminoethylpiperazine A polyamine having a group; an aromatic polyamine; a polyamine having an aliphatic hydrocarbon group bonded to an aromatic hydrocarbon group such as metaxylylenediamine and tetramethylxylylenediamine; a polyamidoamine having an amino group at the molecular end of the polyamide Is mentioned.

  Examples of the “polyamine having a melting point at 1013 hPa of 35 ° C. or lower and a boiling point of 100 ° C. or higher” include 1,4-diaminobutane (DAB), 1,3-diaminopropane (DAP), norbornanediamine ( NBDA), 1,3-bisaminocyclohexane (1,3-BAC) and the like. Among these, DAB or DAP is preferable from the viewpoint that the adhesiveness of the composition of the present invention is more excellent.

  Polyamines that are not “polyamines having a melting point at 1013 hPa of 35 ° C. or lower and a boiling point of 100 ° C. or higher” are hexamethylenediamine (HMDA) from the viewpoint of rapid curing and excellent storage stability with epoxy resins. ) Is preferred.

  As a combination of a carbonyl compound and a polyamine, the resulting composition of the present invention has a lower viscosity (initial viscosity) before curing, higher adhesion performance after curing, and suppresses abnormal appearance due to curing shrinkage. In view of the above, a combination of methyl isopropyl ketone (MIPK) and 1,4-diaminobutane (DAB), a combination of methyl isopropyl ketone (MIPK) and 1,3-diaminopropane (DAP), methyl isopropyl ketone (MIPK) A combination of benzene and norbornane diketone (NBDA) and a combination of methyl isopropyl ketone (MIPK) and 1,3-bisaminocyclohexane (1,3-BAC) are preferred.

Moreover, a ketimine compound can be used individually or in combination of 2 or more types, respectively.
The ketimine compounds by the above combination can be used alone or in combination of two or more. However, in the case of 0.2 molar equivalents or more of ketimine (C), the melting point at 1013 hPa is 35 ° C. or less. And a ketimine compound using a polyamine having a boiling point of 100 ° C. or higher.
Examples of ketimine compounds using polyamines that are not “polyamines having a melting point at 1013 hPa of 35 ° C. or lower and a boiling point of 100 ° C. or higher” include, for example, methyl isopropyl ketone (MIPK) and hexamethylene diamine (HMDA). Examples include ketimine compounds in combination.

In the present invention, the ratio of the molar equivalent of the imino group of the ketimine (C) to the molar equivalent of the epoxy group of the epoxy resin (B) (molar equivalent of imino group / molar equivalent of epoxy group) is 0.5. ~ 1.5.
The above (molar equivalent of imino group / molar equivalent of epoxy group) depends on the reactivity of the epoxy resin at the curing temperature, and since all imino groups do not react with the epoxy group near room temperature, the theoretical value of 1.0 It is preferably slightly lower than 0.7 to 1.0.

<Curing catalyst (D)>
The curing catalyst (D) for the hydrolyzable silyl group (hereinafter sometimes simply referred to as “curing catalyst (D)”) will be described below.

  The curing catalyst (D) contained in the composition of the present invention is not particularly limited as long as it is used as a silanol condensation catalyst. Examples thereof include titanium-based esters, tin compounds, organoaluminum compounds, organozirconium compounds, bismuth compounds, and amine compounds. Among these, a tin compound is preferable and a tetravalent tin compound is more preferable from the viewpoints of fast curability and relatively difficult discoloration of the cured product.

  Examples of the tetravalent tin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, and tin laurate; dibutyltin oxide and phthalate Dialkylstannoxane dicarboxylates; dialkyltin alcoholates such as dibutyltin dimethoxide; (dialkylstannoxane) disilicate compounds; chelates such as dibutyltin diacetylacetonate. Of these, dialkyltin alcoholates, chelates, and (dialkylstannoxane) disilicate compounds are preferred from the viewpoint of being excellent in fast curing properties and storage stability, and stable to polyethers, and include dibutyltin salts and orthosilicates. A reaction product of ethyl or a reaction product of dioctyltin salt and normal ethyl silicate is more preferable.

  The said curing catalyst (D) can be used individually or in combination of 2 or more types, respectively.

  The amount of the curing catalyst (D) contained in the composition of the present invention is excellent in rapid curability, excellent in heat resistance, and excellent in storage stability, with respect to 100 parts by mass of the organic polymer (A), More preferably, it is 0.1-3.0 mass parts.

<Alkyl silicate (E)>
The composition of the present invention may further contain an alkyl silicate compound (E) having an alkyl group having 1 to 5 carbon atoms (hereinafter sometimes simply referred to as “alkyl silicate (E)”) as desired. it can.
Moreover, you may utilize the said alkyl silicate compound as alkyl silicate (E) individually by 1 type or in combination of 2 or more types.

The alkyl silicate (E) is an alkyl silicate monomer represented by the general formula: Si (OR) ₄ (wherein R represents an alkyl group having 1 to 5 carbon atoms) and partially hydrolyzed polycondensation thereof. In addition, a low condensate (oligomer) having a low degree of condensation can be used.

  As the alkyl silicate (E), a commercially available low-condensate (oligomer) of an alkyl silicate having a weight average molecular weight of about 200 to 2,000 may be used. The oligomer can be obtained by, for example, a method in which an alkyl silicate monomer or a commercially available low condensate (oligomer) is mixed with water and a solvent and, if necessary, an acid catalyst and stirred for a predetermined time before gelation.

  As a commercial item of the said alkylsilicate (E), MKC silicate MS-39, MS-56, MS-60 (above, Mitsubishi Chemical Corporation make; methyl silicate) etc. can be used, for example.

  Although content of the alkyl silicate (E) in the composition of this invention is not specifically limited, It is preferable that it is 0.5-15 mass parts with respect to 100 mass parts of said organic polymers (A), 0.5 More preferably, it is 10 mass parts.

  When the composition of the present invention contains the above alkyl silicate (E), the composition of the present invention has an appropriate thixotropy before curing due to the silica produced by hydrolysis and polycondensation of the alkyl silicate (E). Can be obtained, and excellent toughness can be obtained after curing.

SiO ₂ composition amount of alkyl silicate to be contained in the composition of the present invention (E) is not particularly limited, it may include those from 30 to 60 wt%.

  Moreover, it is preferable that at least 60 mol% or more of the alkoxysilyl groups of the alkylsilicate (E) is a methoxysilyl group. That is, in the case where the alkyl silicate (E) is composed of one kind of alkyl silicate compound or the case where it is composed of two or more kinds of alkyl silicate compounds, the alkoxysilyl group possessed by the one kind or two or more kinds of alkyl silicate compounds. It is preferable that at least 60 mol% or more of the total number of methoxysilyl groups.

<Silane modified product (F)>
If desired, the composition of the present invention may further contain a silane-modified product (F) of an alicyclic skeleton resin (hereinafter sometimes simply referred to as “silane-modified product (F)”).
The silane-modified product (F) is not particularly limited as long as the alicyclic resin is modified with a silyl group, and examples thereof include silyl group-modified alicyclic skeleton resins such as rosin resins and terpene resins. Can be mentioned.
Although content of the said silane modified material (F) is not specifically limited, It is preferable to contain 0.5-15 mass parts with respect to 100 mass parts of said organic polymers (A), 0.5-10 mass parts containing More preferably.
One type of the silane-modified product (F) may be used alone, or two or more types may be used in combination.

As said silane modified material (F), what was manufactured by the conventionally well-known manufacturing method may be used, but a commercial item can also be used.
Examples of commercially available products of the silane-modified product (F) include Y-primer 404 and Y-primer 405 (manufactured by Yamaichi Chemical Industries, Ltd .; silyl group-modified terpene resin).

  When the composition of this invention contains the said silane modified material (F), adhesive force will improve.

<Colloidal calcium carbonate (G)>
The composition of the present invention may further contain a fatty acid-treated colloidal calcium carbonate (hereinafter sometimes simply referred to as “colloidal calcium carbonate (G)”) as desired.
Although the average particle diameter of the colloidal calcium carbonate (G) is not particularly limited, it is preferably 0.05 to 0.20 μm, and more preferably 0.05 to 0.10 μm.
Although content of the said colloidal calcium carbonate (G) is not specifically limited, It is preferable that it is 5-50 mass parts with respect to 100 mass parts of said organic polymers (A), and it is 5-30 mass parts. More preferred.
Moreover, the said colloidal calcium carbonate (G) can be contained in the composition of this invention individually by 1 type or in combination of 2 or more types.

As said colloidal calcium carbonate (G), what was manufactured by the conventionally well-known manufacturing method may be used, but a commercial item may be used.
Examples of commercially available colloidal calcium carbonate (G) include neolite SP (average particle size = 0.08 μm), neolite P (average particle size = 0.08 μm), neolite SP-T (average particle size 0.15 μm). ), Neolite SP-TT (average particle size = 0.15 μm), neolite SP-60 (average particle size = 0.08 μm), neolite SP-100 (average particle size = 0.08 μm), neolite SP-300 (average) Particle diameter = 0.15 μm) (above, manufactured by Takehara Chemical Industry Co., Ltd.).

  When the composition of the present invention contains the colloidal calcium carbonate (G), the viscosity and thixotropy (thixotropic properties), viscosity, curing speed, and curing of the composition of the present invention are adjusted by appropriately adjusting the type and content thereof. The later modulus, shear strength, etc. can be adjusted.

<Other components that may be contained>
The composition of the present invention can further contain additives in addition to the above components as long as the object of the present invention is not impaired as required.
Examples of the additive include carbon black, fused silica, silica sand, calcium silicate, etc., fillers such as mica, talc, alumina, montmorillonite; thermal conductive fillers such as aluminum nitride and boron nitride; glass balloons, various types Hollow fillers such as resin balloons; Various resin fillers made by miniaturizing polymethacrylic acid, etc .; Plasticizers; Dehydrating agents such as vinyl silanes and silicate compounds; Silane coupling agents such as epoxy silanes, amino silanes and methacryl silanes; Thixotropy imparting agents; pigments such as titanium oxide; dyes; anti-aging agents, antioxidants; antistatic agents; adhesion imparting agents; dispersants; solvents;

[Initial viscosity]
The initial viscosity of the composition of the present invention before curing is 0.1 to 100 Pa · s at 23 ° C. Here, the above-mentioned viscosity is the initial viscosity of the composition of the present invention measured using a cone plate type (E type) viscometer (rotor # 1, 0.5 rpm) at 23 ° C. It is a thing.

  When the initial viscosity is within this range, the composition of the present invention has excellent leveling properties and self-leveling, so that it can be a moisture-curable resin composition particularly suitable for sealing materials.

  The initial viscosity is not particularly limited as long as it is within the range of 0.1 to 100 Pa · s, but is preferably within the range of 0.1 to 70 Pa · s from the viewpoint of improving the leveling property. The pressure is more preferably 50 Pa · s, and further preferably 0.1 to 30 Pa · s.

[Production method]
The composition of the present invention is not particularly limited for its production. For example, the above-mentioned components are decompressed and sufficiently kneaded using a stirring device such as a mixing mixer in a nitrogen atmosphere and uniformly dispersed.
The composition of the present invention can be produced as a one-pack type or a two-pack type.
From the viewpoint of excellent storage stability when the composition of the present invention further contains water, it contains an alkoxysilyl group-modified polyoxyalkylene polymer, an epoxy resin, a ketimine compound, a polyether, a flame retardant filler, and a curing catalyst. One preferred embodiment is a two-component type having a main agent and a curing agent containing at least water. Fumed silica, surface-treated calcium carbonate, and additives can be added to the main agent and / or the curing agent, respectively.

[how to use]
The composition of the present invention can be cured at room temperature (5-35 ° C.).
Moreover, the composition of the present invention can be cured by moisture contained in components such as moisture in the atmosphere and a filler that can be contained in the composition.

The adherend to which the composition of the present invention can be applied is not particularly limited. For example, metal, plastic, rubber, glass, and ceramic are mentioned.
The method for applying the composition of the present invention to an adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.

Applications of the composition of the present invention include, for example, sealing materials, adhesives, coating materials, primers, paints, and potting materials.
The composition of the present invention can be used for various electric / electronic fields, buildings, automobiles, civil engineering and the like.
The composition of the present invention can be used for an air conditioner, a fan heater, a blower, a dehumidifier, and a humidifier.
Moreover, the composition of this invention can be used for the components adhesion | attachment of a flame-retardant product. Examples of flame retardant products include speakers, video cassette players, televisions, radios, vending machines, refrigerators, personal computers, card-type batteries, video cameras, cameras, automobile parts, precision equipment, and the like.
Further, the composition of the present invention can be applied to high-voltage parts, adhesion of circuits that can be high voltage and parts used in the vicinity thereof, and adhesion in electrical appliances that are operated continuously for a long time. Specific examples of these parts include connectors, switches, relays, electric cables, flyback transformers, and deflection yokes.

  Hereinafter, the present invention will be specifically described with reference to examples. However, it goes without saying that the present invention is not limited to these examples.

1. Manufacture of moisture curable resin composition Each component shown in Table 1 is kneaded according to each formulation , and moisture curable resins of Examples 1 , 2, 5 and 6, Examples 3 and 4, and Comparative Examples 1 to 3 are used. A composition was prepared.
The ketimine compound was synthesized from a polyamine compound and a carbonyl compound by a conventionally known method.

2. Test of moisture curable resin composition (1) Viscosity (initial viscosity)
For each of the compositions of Examples 1 , 2, 5 and 6, Examples 3 and 4, and Comparative Examples 1 to 3, the initial viscosity (unit: Pa · s) was measured using an E-type viscometer (TV20 viscometer, rotor # 1, 0.5 rpm), and measurement was performed under the condition of 23 ° C.
Those having a viscosity in the range of 0.1 to 100 Pa · s were evaluated as “O” as acceptable, and those exceeding 100 Pa · s were evaluated as “x” as unacceptable.

(2) Appearance For each composition of Examples 1 , 2, 5 and 6, Examples 3 and 4, and Comparative Examples 1 to 3 , the obtained compositions were subjected to conditions of 20 ° C. and 55% RH for 7 days. Then, the surface of the composition was observed, and it was observed whether or not an appearance abnormality due to curing shrinkage occurred.
Those in which no appearance abnormality occurred were evaluated as “O” as acceptable, and those that occurred were evaluated as “x” as unacceptable.

(3) Hardness About each composition of Example 1 , 2, 5 and 6, Example 3 and 4, and Comparative Examples 1-3, each obtained composition was 7 days on the conditions of 20 degreeC and 55% RH. After curing, the hardness of each composition was measured according to the hardness test method of JIS K 6253: 2006 using each type A durometer.
Those having a hardness in the range of A50 to A80 were evaluated as “◯” as acceptable, and those outside this range were evaluated as “x” as rejected.
(4) Glass adhesion / anodized aluminum adhesion For each of the compositions of Examples 1 , 2, 5 and 6, Examples 3 and 4, and Comparative Examples 1 to 3, the obtained compositions were either glass plates or anodes. After applying in a bead shape on an aluminum oxide plate so as to have a film thickness of about 10 mm, it was cured under conditions of 20 ° C. and 55% RH for 7 days to obtain a test specimen.
About the obtained test body, the bead part was peeled by hand and the destruction mode was observed.
Cohesive fracture (CF) and interfacial fracture (AF) were recorded, and CF and AF were mixed to the same extent, and the CF area larger than the AF area was recorded as CF / AF.
CF and CF / AF were evaluated as passing, and “◎” and “◯” were evaluated, respectively, and AF was rejected, and “×” was evaluated.
(5) Comprehensive evaluation The thing which did not have "x" evaluation in any of a viscosity, surface tack, hardness, glass adhesiveness, and anodized aluminum adhesiveness was evaluated as "(circle)" as a comprehensive pass.

In Table 1, each component is as follows. In addition, content of each component is represented by a mass part.
Polymer 1: Organic polymer having trimethoxysilyl group (SAX 510, manufactured by Kaneka Corporation; number average molecular weight = 29000, linear)
Epoxy resin 1: bisphenol A type epoxy resin (Adeka Resin EP-4100E (YD-128), manufactured by Adeka Co., Ltd .; epoxy equivalent = 188)
Ketimine compound 1: Ketimine compound represented by the following formula (A) (ketimine compound produced from hexamethylenediamine and methyl isopropyl ketone)
Ketimine compound 2: Ketimine compound represented by the following formula (B) (ketimine compound produced from 1,4-diaminobutane and methyl isopropyl ketone)
Ketimine compound 3: Ketimine compound represented by the following formula (C) (ketimine compound produced from 1,3-diaminopropane and methyl isopropyl ketone)
Ketimine compound 4: Ketimine compound represented by the following formula (D) (ketimine compound produced from norbornane diketone and methyl isopropyl ketone)
Ketimine compound 5: Ketimine compound represented by the following formula (E) (ketimine compound produced from 1,3-bisaminocyclohexane and methyl isopropyl ketone)
Curing catalyst 1: Dioctyltin (Neostan S1, Nitto Kasei Co., Ltd.)
・ Silicate 1: Methyl silicate (MKC silicate MS-56, manufactured by Mitsubishi Chemical Corporation)
Silane modified product 1: Silane modified product of alicyclic skeleton resin (Y primer 405, manufactured by Yamaichi Chemical Co., Ltd.)
・ Calcium carbonate 1: Fatty acid-treated colloidal calcium carbonate (Neolite SP, manufactured by Takehara Chemical Co., Ltd.)
Silane coupling agent 1: Epoxy silane (KBM 403, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent 2: Vinylsilane (KBM 1003, Shin-Etsu Chemical Co., Ltd.)
In Table 1, the "molar equivalent ratio" means the molar equivalent of the imino group possessed by the ketimine compound (when two or more ketimine compounds are contained, the total molar equivalent per each ketimine compound). It represents the ratio of the epoxy group to the molar equivalent (molar equivalent of imino group / molar equivalent of epoxy group), and the “molar equivalent” is a ketimine compound having a melting point at 1013 hPa of 35 ° C. or less and a boiling point of 100 ° C. The molar equivalent of the ketimine compound obtained by reaction of a polyamine compound and a carbonyl compound is represented.

3. Explanation of test results (Examples 1 , 2, 5 and 6 and Examples 3 and 4 )
The moisture curable resin compositions of Examples 1 , 2, 5 and 6 were evaluated as “◯” or “◎” in terms of all of viscosity, surface tack, hardness, glass adhesion and anodized aluminum adhesion. As a good evaluation .
(Comparative Examples 1-3)
Comparative Example 1 is an example not containing an epoxy resin, a ketimine compound and a specific silicate.
The initial viscosity was high and poor, and both hardness and adhesiveness were poor, but appearance abnormality due to curing shrinkage was suppressed.
Comparative Example 2 is an example containing only a ketimine compound that is not "a ketimine compound obtained from at least one polyamine compound selected from 1,4-diaminobutane and 1,3-diaminopropane and a carbonyl compound". is there.
Although the initial viscosity was low and the hardness was high, each was good, but appearance abnormality due to curing shrinkage occurred, and the adhesiveness was not sufficient.
In Comparative Example 3, the composition of Comparative Example 2 contains a specific silicate compound.
Compared with the test result of Comparative Example 2, the adhesion was improved, but an appearance abnormality due to curing shrinkage occurred, and it was generally rejected.
As a ketimine compound, "a ketimine compound obtained from at least one polyamine compound selected from 1,4-diaminobutane and 1,3-diaminopropane and a carbonyl compound" contains at least 0.2 molar equivalent or more of the ketimine compound It is understood that it is essential to suppress appearance abnormality due to curing shrinkage.

  The moisture curable resin composition of the present invention is particularly suitable for various sealing material applications.

Claims (3)

100 parts by mass of an organic polymer (A) having a hydrolyzable silyl group, 3 to 100 parts by mass of an epoxy resin (B), a ketimine compound (C), and a curing catalyst (D) for the hydrolyzable silyl group, Including
The ratio of the molar equivalent of the imino group of the ketimine compound (C) to the molar equivalent of the epoxy group of the epoxy resin (molar equivalent of imino group / molar equivalent of epoxy group) is 0.5 to 1.5,
A ketimine compound obtained by reacting at least 0.2 molar equivalent of at least one polyamine compound selected from 1,4-diaminobutane and 1,3-diaminopropane with a carbonyl compound in the ketimine compound (C). And
A moisture curable resin composition having a viscosity at 23 ° C. of 0.1 to 100 Pa · s.   The organic polymer (A) has at least one alkoxysilyl group selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as a hydrolyzable silyl group. The moisture curable resin composition according to claim 1, further comprising an alkoxysilyl group-modified polyoxyalkylene polymer whose main chain is substantially polyoxyalkylene. The moisture-curable resin composition according to claim 1 or 2, wherein the ketimine compound (C) includes a ketimine compound obtained by reacting a carbonyl compound represented by the following formula (1) with a polyamine.

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. R ¹ and R ² can be bonded to each other to form a ring structure, and R ¹ and R ⁴ are bonded to each other. To form a ring structure.)