JP2814169B2 - Room temperature curable alkylene oxide polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing material for a building, a coating material, a sealing material for electric and electronic parts, a potting material, a fiber treatment agent, an adhesive for a vehicle, a building, an electric and electronic device, and the like. The present invention relates to a useful room temperature-curable alkylenoxide polymer composition.

[0002]

2. Description of the Related Art Conventionally, as a condensation-curable room-temperature-curable composition, the amount of a crosslinking agent has been reduced as much as possible, and the rate of crosslinking has been improved by hydrolysis of a hydrolyzable group introduced into the main component. A one-pack type and a two-pack type in which a crosslinking agent and a curing agent are separately packaged are known. However, the former requires a considerable amount of time for deep curing, although the curing speed from the surface is high, and the latter is excellent in deep curing.
Since the volume ratio or the weight ratio for mixing the liquids is not 1: 1, there are disadvantages that the workability of measuring and mixing is poor and that it is difficult to adapt to an automatic mixer. Furthermore, in the case of the two-pack type, since the appropriate range of the amount of the crosslinking agent and the curing agent necessary to completely cure the composition to the deep part is narrow, the amount of the addition is strictly controlled.
Alternatively, it was necessary to add water as a deep curing agent.

Recently, a curable composition containing a so-called crosslinkable silyl group-containing alkylene oxide polymer and an epoxy resin, which has a hydrolyzable silyl group and undergoes crosslinking upon hydrolysis thereof, has been developed. (Japanese Patent Laid-Open No. 61-268720)
JP-A-62-283120, JP-A-2-14567, JP-A-2-145675, and JP-A-2-228365. In this type of composition, crosslinking and curing of the crosslinkable silyl group-containing alkylene oxide polymer and the epoxy resin proceed separately. That is, the former crosslinkable silyl group-containing alkylene oxide polymer forms a siloxane bond by the action of moisture, resulting in crosslinking and curing, and the latter epoxy resin cures by crosslinking caused by the opening of the epoxy ring by a catalyst. These curable compositions are mainly used as an adhesive or the like for parts requiring earthquake-proof characteristics in the fields of electric / electronics and building materials. In such applications, it is required that the curing speed is high, the adhesive strength is strong, and the cured product is an elastic body.

[0004]

However, as described above, the curable composition containing a crosslinkable silyl group-containing alkylene oxide polymer and an epoxy resin as main components is as described above.
Since the crosslinkable silyl group-containing alkylene oxide polymer is cured by moisture in the air, a considerable amount of time is required for deep curing. In addition, if water is previously added to the system in order to shorten the deep curing time, there is a problem that the storage stability of the composition is reduced.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a room-temperature curable composition which is excellent in fast curability and deep curability. The present invention provides a curable composition containing a crosslinkable silyl group-containing <br/> alkylene oleate Kishido polymer and an epoxy compound as a main component, the former polymer crosslinking, water and a ketone required for curing, the The above problem could be solved by generating the compound in the composition by reaction with an organic compound having a primary amino group.

[0006] That is, according to the present invention, (A) Alkylene oxide polymers having a molecular chain terminus is blocked with a hydrolyzable silyl group, (B) an epoxy compound, (C) a ketone, (D) a primary the organic compound having an amino group, and Ri name contains a curing catalyst of component (E) (a), the ketone and the component (D) of the component (C) first
Deep curing due to reaction with organic compound having primary amino group
A room temperature curable alkylene oxide polymer-based composition is provided, which produces water acting as an agent .

(A) Hydrolyzable silyl group-containing alkylene oxide polymer This alkylene oxide polymer has a molecular chain terminal blocked with a hydrolyzable silyl group and is a main component of the composition of the present invention. Examples of the hydrolyzable silyl group of the alkylene oxide polymer include, for example, general formula (1):

Embedded image (In the formula, R ¹ is an alkyl group such as a methyl group, an ethyl group, or a propyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; Represents a substituted or unsubstituted monovalent hydrocarbon group such as a group in which a hydrogen atom of a group is partially substituted with a halogen atom or the like;
R ² represents a divalent hydrocarbon group such as a methylene group, an ethylene group, a propylene group, a decene group, a —CH ₂ CH ₂ C ₆ H ₄ CH ₂ — group, and X represents an isopropenyloxy group, an isobutenyl group. An alkenyloxy group such as an oxy group; a ketoxime group such as a dimethyl ketoxime group or a methyl ethyl ketoxime group; an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group; an acyloxy group such as an acetoxy group; an N-butylamino group; An amino group such as a diethylamino group;
Represents an aminoxy group such as N-diethylaminoxy group; an amide group such as N-methylacetamido group; a hydrolyzable group selected from a carboxyl group and the like, and a represents an integer of 0 to 2. When two or more R ¹ and / or X are present, they may be the same or different. ). When a plurality of hydrolyzable groups exist at the terminal of the molecule, those hydrolyzable groups may be the same or different.

Among the hydrolyzable silyl groups represented by the general formula (1), those containing an alkenyloxy group as X are preferred. That is, a ketone as the component (C) is produced by hydrolysis and subsequent condensation. This makes it possible to reduce the amount of component (C) added and to control the amount of condensate generated during hydrolysis. Specifically, general formulas (2-2), (2-2), (2-3):

Embedded image (Wherein R ¹ , R ² and a are as described above, and R ³ is a C ₁ -C such as methyl, ethyl, propyl, iributyl, etc.)
₆ , an alkyl group, an aryl group such as a phenyl group, an alkenyl group such as a vinyl group, and the like. R ⁴ may be the same or different, and may represent a hydrogen atom, C ₁ to C ₄ such as methyl, ethyl, and propyl.
A C ₆ alkyl group, a phenyl group, etc., and R ⁵ is a C ₁ -C ₆ alkyl group such as methyl, ethyl, n-propyl, iso-propyl, t-butyl, a phenyl group, etc.
b is an integer of 1 to 3, c is an integer of 0 to 3, and
a + b + c = 3. ).
Among them, particularly preferred are the general formulas (2-1) and (2-3)
In the formula, R ¹ is methyl 2, R ² is —C ₃ H ₆ —, R ³
Is methyl, R ⁴ is a hydrogen atom, and R ⁵ is a methyl group. Such an alkylene oxide polymer having a hydrolyzable silyl group at the terminal represented by the general formulas (2-1), (2-2), and (2-3) can be obtained, for example, by the following two methods. Can be manufactured.

According to the first method, the terminal unsaturated group of the alkylene oxide polymer having an unsaturated bond such as a vinyl group or an allyl group at the terminal is represented by the general formula (3):

Embedded image (Wherein, R ¹ , R ^{3 to} R ⁵ , a, b, and c are as described above).
It is obtained by performing an addition reaction (hydrosilation) using a platinum-based catalyst.

According to the second method, general formula (4):

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and a are as described above, d is an integer of 1 to 3, provided that a + d is 3.)
Of an alkylene oxide polymer having a hydrolyzable silyl group at the terminal represented by the formula and an alcohol represented by the general formula R ⁵ —OH (where R ⁵ is as defined above) in the presence of a basic compound such as triethylamine It is obtained by reacting below.

Specific examples of the alkylene oxide unit constituting the main chain of the alkylene oxide polymer include:

Embedded image And the like. The main chain may be composed of only one of these structural units, or may be composed of two or more structural units. Particularly preferred structural _{units, -CH 2 CH (CH 3)} O- and the like. Further, in addition to the alkylene oxide unit, the main chain of the alkylene oxide polymer may contain other structural units in a range of 3 mol% or less.

Embedded image And other structural units. The molecular chain form of the alkylene oxide polymer may be linear, branched, cyclic, or a combination of these structures. The molecular weight of the alkylene oxide polymer is not particularly limited as long as the crosslinking by the crosslinkable silyl group proceeds, but from the viewpoint of availability, it may be generally in the range of 2,000 to 20,000.

(B) Epoxy Compound As the component (B), a known epoxy compound can be used without particular limitation. For example, glycidyl ether-bisphenol A type epoxy resin, glycidyl ether-bisphenol F type epoxy resin, glycidyl ether-tetrabromobisphenol A type epoxy resin,
Novolak type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, various aliphatic epoxy resins, N, N-diglycidylaniline, triglycidyl isocyanurate, Polyalkylene glycol glycidyl ether, polysiloxane glycidyl ether, polysilane glycidyl ether, epoxy-modified siloxane compound (KF105, X-22-163A, X-
22-163B, X-22-163C, KF100T, KF101, X-22-169AS,
X-22-169B, KF102, KF103. Shin-Etsu Chemical Co., Ltd.). Among them, Epikote 828 and 82
7 (trade name of Yuka Shell Co., Ltd.), KF100T and KF102 (trade name of Shin-Etsu Chemical Co., Ltd.) are preferable. Further, in order to smoothly progress three-dimensional crosslinking and obtain a good cured product, a resin containing at least two epoxy groups in a molecule is preferable.

The epoxy compound (B) is prepared by adding the component (A) to the component (B) when the sum of the components (A) and (B) is 100 parts by weight.
Is preferably mixed in the range of 1:99 to 99: 1, and 8
The range of 0:20 to 50:50 parts by weight is more preferable.

(C) Ketone having a ketone carbonyl group (C = 0) is a component (D)
Reacts with an organic compound having a primary amino group (NH ₂ group) to generate water acting as a deep curing agent. Take
Examples of the ketone include acetone, methyl ethyl ketone, acetophenone, etc. cyclohexanone and the like. Preferred among these compounds are acetone and cyclohexanone. The above ketones can be used alone or in combination of two or more.

The amount of component (C) in the composition is based on 100 parts by weight of the total of component (A) and component (B).
The range is preferably from 0.001 to 1 mol, particularly preferably from 0.01 to 0.1 mol. If the amount is too small, the composition does not show sufficient deep curability at the time of curing, and if the amount is too large, the elastic body obtained by curing the composition is softer and lower in strength than an appropriate amount. Becomes

(D) Organic Compound Containing Primary Amino Group The component (D) reacts with the ketone (C) to generate water acting as a deep curing agent, as described above, and the component (B) And a property of acting as a curing agent for the epoxy compound. Such organic compounds having a primary amino group include methylamine, ethylamine,
Amino groups such as primary amines such as butylamine, ethylenediamine, triethylenetetramine, aniline, and 4,4'-diaminodiphenyl ether; and silane coupling agents having a primary amino group such as γ-aminopropyltriethoxysilane as a functional group. Polymers and oligomers having primary amino groups, such as organic silicon compounds, aliphatic polyamines, primary amino group-containing alkylene oxide polymers, and primary amino group-containing polysiloxanes are exemplified.

Of these, amino group-containing organosilicon compounds are preferred in that particularly good rubber elastic properties can be obtained. As an example of such an amino group-containing silicon compound, the basic skeleton is represented by the general formula (5):

Embedded image (In each formula, R ⁶ is an alkyl group such as a methyl group and an ethyl group,
Examples include an aryl group such as a phenyl group, an alkenyl group such as a vinyl group and an allyl group, an alkoxy group such as a trifluoropropyl group, a methoxy group, an ethoxy group, and an iropropoxy group, an amino group, an aminooxy group, and an acetoxy group. And the like, in which a primary amino group is bonded to the basic skeleton via an appropriate linking group. The structure of the amino group-containing organosilicon compound may be linear, branched, cyclic, or a combination of these structures, and the molecular weight thereof is not particularly limited. In particular,

Embedded image

Embedded image KF393, KF859,
KF86, KF861, KF867, KF869, KF880, KF8002, KF800
4. Commercially available ones under the trade names KF8005, KF864, KF865, KF868 and KF8003 (Shin-Etsu Chemical Co., Ltd.).

The above-mentioned organic compound containing a primary amino group is also
One type may be used alone, or two or more types may be used in combination. In particular, a compound having one primary amino group in one molecule is preferably 2 per molecule in consideration of the curing speed of the composition.
Preferably, compound and併having more than five primary amino group. The amount of the component (D) is 100
The range is preferably 0.01 to 200 parts by weight, particularly 5 to 50 parts by weight in consideration of the curing speed of the composition, long-term storage stability in an uncured state, economic efficiency, and the like.

For the purpose of accelerating the curing of the epoxy compound of the component (B), a compound capable of curing the epoxy compound may be added, if necessary, in addition to the component (D). . Specifically, amine compounds not containing primary amines, such as aliphatic polyamines, polyamide resins, dicyandiamide, imidazole tertiary amines, and amino group-containing organosilicon compounds, acid anhydride compounds, phenol resins, mercaptan compounds Dicyandiamide, Lewis acid complex compound and the like. These can be used alone or in combination of two or more.

Of these, amino group-containing organosilicon compounds are particularly suitable for providing rubber elasticity. An example of such an amino group-containing organosilicon compound is such that the basic skeleton is composed of one or more of the structures exemplified by the general formula (5), and a primary amino group is directly attached to the basic skeleton. Or via an appropriate linking group. The amino group may be a primary amino group protected by a Schiff base, or any of secondary and tertiary amino groups. The structure of the amino group-containing organosilicon compound may be linear, branched, cyclic, or a combination of these structures, and the molecular weight thereof is not particularly limited. Examples of the basic form of the amino group bonded to the above basic skeleton include, for example,

Embedded image And the form of a piperidine group. These amino groups are bonded to the above-mentioned basic skeleton through alicyclic, aromatic, aliphatic, or a combination thereof. Specifically preferred are:

Embedded image

Embedded image And the like.

When a compound capable of curing these epoxy compounds is added, the compounding amount is 100 parts (B).
The total amount is preferably in the range of 0.01 to 200 parts by weight based on the weight of the component (D) based on the weight of the component (D). The range of parts is preferred.

(E) Hydrolyzable silyl group-containing alkyleneo
The curing catalyst component (E) of the oxide polymer (A) is a curing catalyst for the alkylene oxide polymer (A), and for example, a tin catalyst and a titanium catalyst can be used. Specifically, tin naphthenate, tin caprylate, tin oleate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltindiolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) ) Tin, organic tin compounds such as dibutyltin benzylmalate, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonato) titanium,
Examples thereof include titanates such as titanium isopropoxyoctylene glycol and titanium chelate compounds.

Further, in order to increase the activity of the catalyst, a basic compound may be used in combination. Specifically, amines such as octylamine and laurylamine, cyclic amines such as imidazoline, tetrahydropyrimidine, 1,8-diazabicyclo (5,4,0) undecene-7 and guanidinepropyltris (trimethylsiloxy) silane Examples thereof include guanidyl group-containing silane compounds and partial hydrolysates thereof, and guanidyl group-containing siloxanes. This catalyst
The amount of (E) is 0.1 to 10 parts by weight per 100 parts by weight of component (A).
It is preferably in the range of 0.5 to 5 parts by weight in consideration of the curing speed, long-term storage stability in an uncured state, economic efficiency, and the like.

Other Components In addition to the components (A) to (E), various components can be added to the room temperature-curable composition of the present invention, if necessary. For example, storage stabilizers such as methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoximesilane, methyltriacetoxysilane, fumed silica, precipitated silica, aluminum oxide, quartz powder, carbon powder, talc and bentonite Reinforcing agents, fibrous fillers such as asbestos, glass fibers and organic fibers, coloring agents such as pigments and dyes, heat resistance improvers such as red iron oxide and cerium oxide, cold resistance improvers, dehydrating agents, γ-glycidoxypropyl Adhesion improvers such as triethoxysilane, and liquid reinforcing agents such as network polysiloxanes composed of triorganosiloxy units and SiO ₂ units are exemplified. These may be added in predetermined amounts as needed.

Preparation of Composition The composition of the present invention is prepared by uniformly mixing the required amounts of each of the components (A) to (E) and optionally added optional components in a dry atmosphere. It is obtained as a moldable room temperature curable composition. At that time, by mixing the components (C) or (D) in a microencapsulated state, a one-part room temperature curable composition having improved storage stability can be obtained.
It is also possible to use a two-pack type, which is divided into two liquids and packed, and mixed at the time of use. In the case of a two-pack type, it is easy to make the mixing ratio of the two packs 1: 1 and the workability is good.

Applications The composition is, for example, a sealing material for architectural materials, a coating material, a sealing material for electric and electronic parts, a potting material, a fiber treatment agent, an automobile, and a building material in view of its rapid curing property and deep curing property. And adhesives for electric and electronic applications.
In particular, it can be effectively used in an oil seal material for automobiles requiring high quick-curing property and deep-curing property in a manufacturing process, a sealing material for electric and electronic devices, and a potting material for which streamlining of the process has recently been required.

[0027]

Upon curing the composition of the present invention, the primary amino group with component (C) a carbonyl group having the a component (D) has the following formula:

Embedded image Reacts to produce water, which is utilized in the system formed as a deep curing agent, to greatly improve the fast-curing and deep-curing properties of the composition. this is,
In the case where the two-package is used by mixing them at the time of use, there is an advantage that the two-package can be easily mixed at a ratio of 1: 1. Further, a component added to generate the water, that is, Both ketones having a C = 0 group and organic compounds having a primary amino group are easily available, and are therefore excellent in practicality.

[0028]

Examples of the present invention will be described below.

Synthesis Example 1 Polypropylene glycol having a terminal capped with an allyl group (molecular weight: 8,0, azeotropically dehydrated with 100 g of toluene)
00) To 100 g, 6.2 g of diisopropenyloxymethylsilane and 0.5 g of H ₂ PtCl ₆ as a catalyst were added.
For 4 hours. The reaction is Si-H by the alkali decomposition method.
After confirming that 95% of Si-H in the raw material silane was consumed by valence measurement, the process was terminated. The product was obtained as a transparent viscous liquid by removing volatile components in the obtained reaction solution by heating under reduced pressure. The molecular weight of the obtained product was 8,300. Also, when isopropenyloxysilyl groups were measured and analyzed by nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and alkali decomposition method, 95% of the starting silane hydroxysilyl groups were added to the polypropylene glycol terminal allyl groups. I confirmed that. Hereinafter, the product obtained in Synthesis Example 1 is referred to as polymer A for convenience.

Synthesis Example 2 100 g of Polymer A was reacted with 100 g of methanol and 50 g of triethylamine while heating under reflux for 10 hours. The product is
The volatile components in the reaction solution were removed by heating under reduced pressure to obtain a transparent viscous liquid. The molecular weight of the obtained product was 8,200. Further, when the amounts of isopropenyloxysilyl group and methoxysilyl group were measured and analyzed by nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and alkali decomposition method, the terminal hydrolyzable group was found to be isopropenyloxysilyl group / methoxysilyl. The molar ratio of the groups was determined to be 52/48. Hereinafter, the product obtained in Synthesis Example 2 is referred to as polymer B for convenience.

Synthesis Example 3 4.1 g of dimethoxymethylsilane and 0.5 g of a catalyst were mixed with 100 g of polypropylene glycol (molecular weight: 8,000) which was azeotropically dehydrated with 100 g of toluene and capped with an allyl group. H ₂ PtCl ₆ was added and reacted at 80 ° C. for 4 hours. The reaction was terminated after confirming that 95% of the Si-H in the raw material silane had been consumed by Si-H value measurement by an alkali decomposition method. The product was obtained as a transparent viscous liquid by removing the volatile components in this reaction solution by heating under reduced pressure. The molecular weight of the obtained product was 8,200. Further, by measuring and analyzing the amount of methoxysilyl group by nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and alkali decomposition method, 95% of the hydroxysilyl group in the raw material silane was added to the allyl group at the end of polypropylene glycol. It was confirmed. Hereinafter, the product obtained in Synthesis Example 3 is referred to as polymer C for convenience.

Examples 1 to 12; Comparative Examples 1 to 4 In each of Examples and Comparative Examples, the polymers A, B and C obtained in Synthesis Examples 1 to 3 were mixed at the compounding ratios shown in Tables 1 and 2, A composition was prepared by mixing with the various components shown in Table 1. Next, each of the obtained compositions was formed into a sheet having a thickness of 2 mm, and then left in an atmosphere of 20 ° C. and 60% RH. twenty four
After a time, the physical properties of the obtained cured product, that is, hardness, tensile strength and elongation were measured in accordance with JIS-K-6301. The hardness was measured using a spring type hardness tester type A. Tables 1 and 2 show the obtained results. The deep curability was evaluated by placing the composition in a plastic container having a depth of 10 mm and measuring the deep cured thickness (thickness from the surface of the cured layer) after 2 hours.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

The composition of the present invention is excellent in fast-curing property and deep-curing property, and is also excellent in rubber properties of a cured product obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5:07 5:17 5:56) (72) Inventor Masatoshi Arai 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Shinetsu Chemical (56) References JP-A-2-145675 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 63/00-63/10 C08L 71/02 C08G 59/50

Claims (4)

(57) [Claims] (A) an alkylene oxide polymer having a molecular chain terminal blocked with a hydrolyzable silyl group, (B) an epoxy compound, (C) a ketone , (D) an organic compound having a primary amino group, and Ri Na contain a curing catalyst of component (E) (a), a ketone and component (D) of the component (C)
Deep curing due to reaction with organic compound having primary amino group
A room temperature-curable alkylene oxide polymer composition, which produces water acting as an agent . 2. The composition according to claim 1, wherein the hydrolyzable silyl group of the component (A) forms a ketone by hydrolysis. 3. The composition according to claim 1, wherein the organic compound having a primary amino group of the component (D) is an organosilicon compound having two or more primary amino groups in one molecule. . 4. A cured product obtained by curing the composition according to claim 1.