JP2001114963A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in water permeability, weatherability, and alkali resistance and is suitable for sealants, reactive hot-melts, various adhesives, etc. SOLUTION: A two-component curable resin composition is provided which comprises (A) a halogenation product of a copolymer of a p-alkylstyrene and a 4-8C isomonoolefin which is liquid at normal temperature and (B) a compound having at least two groups selected from among prim-amino, see-amino, thiol, acid anhydride, and carboxyl groups in the molecule. Moreover, a one-component curable resin composition is provided which contains (A) a halogenation product of a copolymer of a p-alkylstyrene and a 4-8C isomonoolefin which is liquid at normal temperature and (B) a hydrolyzable latent curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition.
The present invention relates to a curable resin composition suitable for a sealant, a reactive hot melt, various adhesives, etc. having excellent weather resistance and alkali resistance.

[0002]

BACKGROUND OF THE INVENTION Organic polymers such as polyisobutylene having a reactive allyl group or a silyl group having a saturated hydrocarbon as a main chain structure are disclosed in, for example, JP-A-63-6041.
JP-A-1-167371 or JP-A-7-53
No. 882, this organic polymer includes EPION (trade name) manufactured by Kaneka Chemical Industry Co., Ltd.
It has excellent properties such as moisture permeability, weather resistance and heat resistance, and is used in various applications such as sealing agents, coating agents and sealants.

As described above, other organic polymers having a polyisobutylene skeleton are disclosed in European Patent Application No. 893053.
No. 95.9 (Publication No. 0344021 published on November 29, 1989) discloses that isomonoolefins and p
-Halogenated copolymers with alkylstyrenes are disclosed. This polymer has excellent moisture permeation resistance and weather resistance similarly to the above-mentioned polyisobutylene having a reactive allyl group or a silyl group, and is superior to the above-mentioned polyisobutylene in alkali resistance. The application of this polymer as a rubber material mainly for tires has been studied, but there has been no attempt to use it for various adhesives, sealants and the like. There is also a problem that the applicability is narrow because this copolymer is a solid resin.

On the other hand, as the above-mentioned adhesive or sealant, a one-component technique using a latent curing agent which is activated by moisture such as atmospheric moisture and functions as a curing agent is known. For example, JP-A-2-88625 discloses that
A technique using an epoxy resin and a ketimine-based curing agent in combination is disclosed, and further disclosed in European Patent Application No. 98990683.8 (publication No. 089 published on January 13, 1999).
No. 0594) proposes a technique in which the use of a sterically hindered ketone as the ketimine can improve the balance between storage stability and curing speed. However, when an organic polymer having a main chain structure of a saturated hydrocarbon such as isobutylene as described above is applied as a one-component curable resin, the resin composition has low moisture permeability, so that deep curability and curing are performed. There was a problem with speed.

On the other hand, in recent years, a polymer compound having a property of reversibly changing its behavior with respect to water depending on temperature has been known as a thermosensitive agent, a thermosensitive thickener, an anti-staining agent, a marine anti-staining material, an artificial muscle, a drug delivery system. It is attracting attention as a system material. For example, it is known that an aqueous solution of an N-substituted acrylamide derivative has a property of exhibiting water absorption below a certain temperature and releasing water at a higher temperature. Japanese Patent Application Laid-Open No. 9-221645 proposes a temperature-sensitive gelling resin latex-based adhesive and a rubber latex-based adhesive which take advantage of this property and rapidly thicken and gel by heating during heating and drying. I have.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a two-part or one-part type which is excellent in moisture permeation resistance, weather resistance and alkali resistance using a halogenated copolymer of isomonoolefin and p-alkylstyrene. An object is to provide a curable resin composition. Another object is to provide a method for applying or curing the one-part curable resin composition.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, have found that the halogenated copolymer of isomonoolefin and p-alkylstyrene can be cured by two-part curing. The present invention was found to be applicable as a water-soluble resin composition and a one-pack type curable resin composition, and was further excellent in deep permeability, curing speed and storage stability.

A first aspect of the present invention is a two-part curable resin composition containing the following (a) and (b). (A) is a liquid at room temperature, the copolymer halides of isomonoolefin and p- alkylstyrene C ₄ -C _8, and (b) 1 primary amine in a molecule, a secondary amine, a thiol group, A compound having at least two groups selected from the group consisting of an acid anhydride group and a carboxyl group.

A second aspect of the present invention is a one-part curable resin composition containing the following (a) and (c). (A) is a liquid at room temperature, halide, and (c) hydrolysis of the latent curing agent of copolymer of isomonoolefin and p- alkylstyrene C ₄ -C _8.

[0010] The hydrolyzable latent curing agent (c) comprises:
It is preferably at least one selected from the group consisting of ketimine, aldimine, enamine and oxazolidine, and is synthesized from a ketone represented by the following formula (1) and a compound having two or more primary amino groups in the molecule. More preferably, it is ketimine.

[0011]

Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group R ⁴ : hydrogen atom and 1 to 6 carbon atoms Any one selected from the group consisting of 6 alkyl groups R ⁵ : hydrogen atom, methyl group or ethyl group R ⁶ : hydrogen atom, methyl group or ethyl group

A third aspect of the present invention is a one-part curable resin composition containing the above (a) and (c) and the following (d). (D) a mixture of a polyacrylamide derivative and water.

[0013] A fourth aspect of the present invention is the above (a),
In the third aspect, which is a one-part curable resin composition containing (c) and (d), a mixture (d) of the polyacrylamide derivative and water is subjected to a surface treatment with an inorganic filler. .

In a fifth aspect of the present invention, the one-pack type curable resin composition containing the mixture (d) of the polyacrylamide derivative and water is heated during or after coating. This is a method of applying or curing a mold-curable resin composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each embodiment of the present invention will be described in detail. 1. Two-component curable resin composition In the first embodiment of the present invention, the following components (a) and (b) are used as a main component and a two-component curing agent, respectively. It causes a reaction.

(A) A halide of a copolymer of a C ₄ -C ₈ isomonoolefin and a p-alkylstyrene, which is liquid at ordinary temperature. C ₄ -C ₈ which is liquid at ordinary temperature used in the present invention. those isomonoolefin and p- alkylstyrene, copolymers halide of (a) is a liquid at a halide of a copolymer of isomonoolefin and p- alkylstyrene C ₄ -C _8, Alternatively, it is made into a liquid by blending a solvent or a liquid material with it.

Examples of the above C ₄ -C ₈ isomonoolefin include isobutylene, isopentene, isooctene and the like, and preferably isobutylene. Examples of the p-alkylstyrene include C
₁ is an alkyl group having -C ₅ are styrene illustrated having in the para position, preferably, p- methyl styrene, p- ethyl styrene. The p-alkylstyrene content is
The content of the copolymer having a p-alkylstyrene skeleton, including the alkyl halide of p-alkylstyrene described below, is 5 to 25% by weight, preferably 5 to 10% by weight in the copolymer component. If the content is less than 5% by weight, the desired content of the below-mentioned alkyl halide of p-alkylstyrene does not reach the desired content, and the crosslink density is low, so that the moisture permeation resistance is insufficient. On the other hand, if it exceeds 25% by weight, the glass transition temperature of the polymer becomes high, and the polymer becomes brittle at a low temperature, which is not preferable.

Such isomonoolefin and p-al
Examples of halides of copolymers with alkylstyrene include
The para-substituent of the p-alkylstyrene possessed is C₁
~ C _FiveAnd the first and second alkyl groups
Consisting of what is a 2-alkyl halide
Any of these can be used.

Examples of the halogen include bromine and chlorine, preferably bromine. The halogen content is
1.0% by weight or more, preferably 1.
0 to 3.0% by weight. Within this range, the crosslink density becomes appropriate and the desired properties are sufficiently obtained.

In the polymerization reaction of the above copolymer, for example, an isomonoolefin and p-alkylstyrene are mixed and polymerized in a copolymerization reaction vessel in the presence of a catalyst such as a Lewis acid catalyst and a diluent. be able to. Examples of the polymerization method include a slurry polymerization method, a solution polymerization method, and a cement suspension polymerization method. In the solution polymerization method and the cement suspension polymerization method, the polymerization temperature may be from −35 to −100 ° C., depending on the catalyst system and copolymer molecular weight used. The overall residence time depends on the activity and concentration of the catalyst, the monomer concentration, the reaction temperature, etc., but generally ranges from about 1 minute to 5 hours,
Preferably, it is about 10 to 60 minutes. Introduction of a functional group such as halogenation may be performed by a known method such as radical halogenation of a copolymer of polymerized isomonoolefin and p-alkylstyrene. Examples of the initiator used for radical halogenation include azobisisobutylnitrile.

As the above-mentioned copolymer, commercially available products can also be used. For example, EXX manufactured by Exxon Chemical Co., Ltd.
PRO (grades such as MDX90-10).

In the present invention, in order to use a liquid in the above-mentioned copolymer, or to convert it into a liquid when it is in a solid state, the copolymer is dissolved in a solvent to be in a liquid state. Either use a liquid that can be mixed with the copolymer to make the entire mixture liquid, or both. The solvent or liquid is not particularly limited as long as it is a substance which easily dissolves the copolymer and is inert to the copolymer.

Specifically, the solvent includes aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic hydrocarbons such as n-hexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate and ethyl acetate. And ethers such as diethyl ether, tetrahydrofuran and dioxane.

Examples of the liquid material include various oils such as liquid polybutene, liquid polyisoprene, and paraffin oil. Preferably, liquid polybutene is used because it has good compatibility and does not deteriorate air permeability resistance. .

In the present invention, the term "liquid" means that the viscosity of the composition is reduced by containing the above-mentioned solvent, liquid substance, or both, and the viscosity of the whole composition at 38 ° C. is 1 to 10, 000 Poise. Within this range, the concentration can be adjusted to a suitable level as a sealant, a reactive hot melt, or various adhesives.

(B) a primary amine, a secondary amine,
Compounds having two or more thiol groups, acid anhydride groups, and carboxyl groups A primary amine, a secondary amine,
The compound (b) having at least two groups selected from the group consisting of a thiol group, an acid anhydride group, and a carboxyl group functions as a curing agent for the two-part curable resin composition of the present invention. Specific examples of the above (b) include an amine-based curing agent, an acid or acid anhydride-based curing agent, a basic active hydrogen compound, and a polythiol-based curing agent.

Examples of the amine curing agent include ethylenediamine, propylenediamine, butylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, DuPont MPM manufactured by Japan
D, aliphatic polyamines such as meta-xylylenediamine; diamines having a polyether skeleton represented by Jeffamine EDR148 manufactured by San Techno Chemical Co .; isophorone diamine, 1,3-bisaminomethylcyclohexane, 1
Alicyclic polyamines such as -cyclohexylamino-3-aminopropane and 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine; NB manufactured by Mitsui Chemicals, Inc.
A diamine having a norbornane skeleton represented by DA; a polyamidoamine having an amino group at a molecular terminal of the polyamide;
2,5-dimethyl-2,5-hexamethylenediamine,
Examples thereof include Jeffamine D230 and Jeffamine D400 manufactured by Sun Techno Chemical Co., Ltd. having a skeleton of mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and polypropylene glycol (PPG).

Examples of the acid or acid anhydride-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid, pyromellitic anhydride, 3,3 ′, 4,4 ′.
-Aromatic acid anhydrides such as benzophenonetetracarboxylic anhydride, cycloaliphatic acid anhydrides such as methylcyclohexenetetracarboxylic anhydride, poly (phenylhexadecandioic acid) anhydride, polyadipic anhydride, polyazeleic anhydride , Polysebacic anhydride, and aliphatic acid anhydrides such as poly (ethyloctadecanedioic anhydride).

The polythiol-based curing agent is, for example, 2,
Esters of thioglycolic acid such as partial epoxy adduct of 2'-bisthiolethyl ether, pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane trithioglycolate, and polysulfides having a thiol group at the terminal Compounds containing two or more thiol groups, such as rubber, are exemplified.

Of these, amine compounds are preferred, and in particular, 1,3-bisaminomethylcyclohexane,
Norbornanediamine, metaxylylenediamine, and polyamidoamine are particularly preferably used because they have excellent storage stability and are particularly excellent in curability.

The first embodiment of the present invention may contain the following optional components, which may be contained on the main agent side or on the hardener side, respectively. As optional components, for example, fillers, plasticizers, thixotropic agents, pigments, dyes,
An antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent, and the like can be added.

As the filler, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, Barium oxide, maglesium oxide; calcium carbonate, magnesium carbonate,
Organic carbonates and inorganic fillers such as zinc carbonate; limestone clay, kaolin clay and calcined clay; carbon black; and fatty acid, resin acid and fatty acid ester-treated products thereof.

As a plasticizer, dioctyl phthalate (D
OP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, adipic acid Butylene glycol polyester and the like.

Examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparone (manufactured by Kusumoto Kasei Co., Ltd.), calcium carbonate, Teflon, and the like. Examples include quaternary ammonium salts and hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

In the first embodiment of the present invention, for example, the above-mentioned essential components (a) and (b) are mixed in a separate container, if necessary, by adding an additive as needed, and mixing under a reduced pressure. The mixture may be sufficiently kneaded using a stirrer or the like, uniformly dispersed and stored, and used by mixing at the time of use.

The compounding amount of the compound (b) when mixing the two components is 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer halide (a). Is preferred. Within this range, sufficient curability can be obtained.

The two-part curable resin composition thus obtained is excellent in moisture permeation resistance, weather resistance and alkali resistance, and is suitable for various adhesives, pressure-sensitive adhesives, paints, sealing agents for double-glazing. And the like, a waterproofing agent, a spraying agent, a molding material, a sealant, a hot melt, a direct glazing material and the like.

[0038] 2. One-component curable resin composition A second aspect of the present invention is a composition containing the above (a) and the following (c). The composition is sealed and stored when not in use, and is opened and air when used. It is a composition in which the latent curing agent acts as a curing agent due to the moisture therein and undergoes crosslinking and curing. The component (a) is as described above. Hereinafter, (c) will be described.

(C) Hydrolyzable Latent Curing Agent The hydrolyzable latent curing agent (c) used in the present invention is present in the one-part curable resin composition of the second embodiment of the present invention. It is activated by the water released or the water released by a mixture (d) of a polyacrylamide derivative and water described below, and can function as a curing agent for the one-part curable resin composition.

As such a hydrolyzable latent curing agent (c), preferably, ketimine, aldimine,
It is preferably at least one selected from the group consisting of enamine and oxazolidine.

Ketimine is a compound obtained by reacting a polyamine with a ketone. For example, polyamines such as ethylenediamine, propylenediamine butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), methyl isopropyl ketone, propiophenone, It is obtained by reacting with a ketone such as benzophenone.

Aldimine is a compound obtained by reacting a polyamine with an aldehyde. Examples of the polyamine include those similar to the above-described polyamine. Examples of the aldehyde include aliphatic aldehydes such as acetaldehyde, 2-methylbutyraldehyde, propionaldehyde, and n-butyraldehyde; and aromatic aldehydes such as benzaldehyde, trimethylbenzaldehyde, and methoxybenzaldehyde.

The enamine is an aldehyde or ketone,
It is a compound obtained by reacting with a secondary amine. Examples of the aldehyde or ketone include those similar to the aldehyde or ketone described above.

As the secondary amine, dimethylamine,
Examples include diethylamine, di-n-propylamine, diallylamine, diisopropylamine, diisobutylamine, and diphenylamine.

Oxazolidine is a compound obtained by a condensation reaction between an aldehyde or ketone and an alkanolamine. Oxazolidine hydrolyzes with water to form a secondary amine and functions as a curing agent. Examples of the aldehyde or ketone include those similar to the aldehyde or ketone described above.

As the alkanolamine, aminoethylethanolamine, diethylethanolamine, (2
-Hydroxyethyl) amine and N-2- (hydroxyethyl) -N- (2-hydroxypropyl) amine, and the like, such as bis-N-2-hydroxyethylamine and bis-N-2-hydroxypropylamine. Is preferred in terms of price.

These may be used alone or in combination of two or more. Among them, ketimines having relatively mild reactivity are preferable, and particularly, steric hindrance represented by the following formula (1) is preferable. And a compound having two or more primary amino groups in the molecule.

[0048]

Embedded image

R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl or ethyl group R ³ : hydrogen atom, methyl or ethyl group R ⁴ : hydrogen atom and carbon Any one selected from the group consisting of alkyl groups of formulas 1 to 6 R ⁵ : hydrogen atom, methyl group or ethyl group R ⁶ : hydrogen atom, methyl group or ethyl group

As the ketone having a large steric hindrance represented by the formula (1), specifically, methyl isopropyl ketone, methyl t-butyl ketone, diisopropyl ketone and the like are preferably exemplified.

Compounds having two or more primary amino groups in the molecule include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, and trimethylhexamethylenediamine. , N-aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, diamine having a polyether skeleton represented by Jeffamine EDR148 manufactured by San Techno Chemical Co., 1,3-bisaminomethyl Cyclohexane, 1-cyclohexylamino-3-
Aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, N manufactured by Mitsui Chemicals, Inc.
Diamines having a norbornane skeleton represented by BDA; meta-xylylenediamine; polyamide amines having an amino group at the molecular terminal of polyamide;

Each of the above polyamines and methyl t-
Butyl ketone, ketimines obtained by combining with each ketone such as methyl isopropyl ketone, especially ketimines synthesized from Jeffamine series and methyl t-butyl ketone or methyl isopropyl ketone,
Since it has particularly excellent storage stability and good curability, it is suitably used as a latent curing agent of the two-part curable resin composition of the present invention.

Specifically, Jeffamine D230 and methyl isopropyl ketone or methyl tert-butyl ketone, Jeffamine D400 and methyl isopropyl ketone or methyl tert-butyl ketone, 2,5-dimethyl-
Ketimines synthesized from 2,5-hexamethylenediamine and methyl isopropyl ketone or methyl t-butyl ketone are preferably used.

The above-mentioned ketimine can be obtained by reacting the above-mentioned ketone and polyamine by heating to reflux without solvent or in the presence of a solvent such as benzene, toluene or xylene, and removing elimination water by azeotropic distillation. .

The ketimine thus obtained has a bulky substituent near the double bond of the ketimine group, so that the nitrogen atom of the ketimine is protected and its basicity is greatly reduced. As a result, the storage stability of the resin composition of the present invention can be prevented from lowering, and at the same time, the curability becomes good. In the one-component curable resin composition of the present invention, the hydrolyzable latent curing agent (c) can be used in combination with a conventionally known curing agent, if necessary.

The second embodiment of the present invention may contain optional components in addition to the above essential components. Examples of the optional component include those similar to those exemplified in the first embodiment.

The production method according to the second aspect of the present invention includes:
It is obtained by sufficiently kneading each essential component and various optional components in a container using a stirring device such as a mixing mixer under reduced pressure, and dispersing them uniformly.

The thus obtained second embodiment of the present invention is excellent in moisture permeation resistance, weather resistance and alkali resistance. Furthermore, by using a ketimine compound having a large steric hindrance as a latent curing agent, it is possible to improve the curing speed while maintaining storage stability.
Therefore, it is suitably used for various uses similar to the first embodiment, and has an advantage of excellent workability.

[0059] 3. Mixing polyacrylamide derivative with water
One-component curable resin composition containing compound The third aspect of the present invention relates to a one-component curable resin composition containing the above (a) and (c) and a composition further containing the following (d): There is a composition in which the latent curing agent can function effectively due to the presence of the component (d) capable of releasing the moisture retained by heating. The components (a) and (c) are as described above. Hereinafter, the mixture (d) of the polyacrylamide derivative and water will be described.

(D) Mixture of Polyacrylamide Derivative and Water A mixture (d) of a polyacrylamide derivative and water (hereinafter referred to as a mixture (d)) is prepared by mixing a mixture of water with water.
It is a mixture of polyacrylamide and water having a lower critical solution temperature and having a phase transition temperature of 0 ° C or more and less than 100 ° C.

The lower critical solution temperature generally refers to a transition temperature at which a transition from a homogeneous system to a two-phase system occurs in a phase diagram of a mixed system of a liquid and a polymer, and the transition temperature varies with the composition of the system. A certain composition has a lower critical solution temperature. Having a lower critical solution temperature means that at a temperature higher than the transition temperature, the two components contained in the mixed system can be separated, and at a temperature lower than the transition temperature, the two components can be combined.

Specifically, in the mixture (d), the transition temperature is a temperature at which water molecules can be held between molecules of the polyacrylamide derivative by the polarity of the molecules or a hydrogen bond with a functional group in the molecule. This is a temperature that gives a critical point to the temperature at which water is released without being discharged.

In the mixture (d), below the transition temperature, the two components are in the above-mentioned bond (not a strong bond such as a chemical bond) to form a homogeneous phase. In the present invention, it is called a mixture.

The polyacrylamide derivative having the above properties contained in the mixture (d) exhibits a phase transition reversibly at the transition temperature, and if the temperature is lower than the phase transition temperature, it releases water more spontaneously than between molecules. Shows hydrophobicity. Therefore, in the present invention, utilizing this property, the mixture (d) is used as a moisture carrier of a so-called moisture-curable resin composition.

That is, in the one-pack type curable resin composition containing the hydrolyzable latent curing agent (c) of the present invention, a polyacrylamide derivative in a state of retaining water is added and dispersed. After this is applied to the adherend or immediately before the application, the polyacrylamide derivative is subjected to a short-time heat treatment so as to have a transition temperature or higher, thereby releasing water from the polyacrylamide derivative, and hydrolyzing contained in the resin composition. The latent curing agent is hydrolyzed to activate the latent curing agent, thereby curing the deep portion of the resin composition and increasing the curing speed. The heat treatment method is not particularly limited as long as the polyacrylamide derivative can be heated to a transition temperature or higher. Specifically, the fifth embodiment will be described in detail.

The transition temperature can be determined by giving a heat treatment to an aqueous solution or gel liquid of the polyacrylamide derivative for a short time and gradually heating the solution, and measuring the temperature at which the aqueous solution starts to become cloudy. Is preferably 30 to 90 ° C. At this time, it is preferable that the mixing ratio of the polyacrylamide derivative and water is a ratio actually used.

The polyacrylamide derivative used in the present invention is a compound represented by the following formula (2).

[0068]

Embedded image (Wherein, R ⁷ and R ⁸ represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group,
It represents tert- butyl group, cyclobutyl group, cyclopropylmethyl group, a methylcyclopropyl group, R ^7, R
⁸ may be cyclized to form a 5- or 6-membered ring containing a nitrogen atom to which R ⁷ and R ⁸ are bonded. n represents the degree of polymerization and is an integer. )

Specifically, poly N-isopropylacrylamide (p-NIPAM, transition temperature 31 ° C.), poly N
-Methyl-N-ethylacrylamide (p-MEAM,
Transition temperature 56-57 ° C.), poly N-methyl-N-n-propyl acrylamide, poly N-methyl-N-isopropyl acrylamide, poly N, N-diethyl acrylamide, poly N-acryloyl pyrrolidine, poly N-acryloyl piperidine, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, poly N-isopropylacrylamide (p-NIPAM, transition temperature 31 ° C.) which transitions at a relatively low temperature, poly N
-Methyl-N-ethylacrylamide (p-MEAM,
Transition temperature 56-57 ° C.) is preferred.

The weight average molecular weight of the polyacrylamide derivative is preferably from 1,000 to 5,000,000, more preferably from 10,000 to 2,000,000. The weight ratio of the polyacrylamide derivative to water in the mixture (d) is 95/5 to 30/7 at a temperature lower than the transition temperature of the polyacrylamide derivative.
0 is preferred. Within this range, the deep curability of the resin composition of the present invention is excellent, and the curing speed is high,
Further, the storage stability is also good.

The method of absorbing water into the polyacrylamide derivative is not particularly limited. For example, water is sprayed on the polyacrylamide derivative by spraying, or the polyacrylamide derivative is held in a container with high humidity.
Alternatively, a method such as mixing in the coexistence with water may be mentioned.

The third embodiment of the present invention may contain optional components in addition to the above essential components. Examples of the optional component include those similar to those exemplified in the first embodiment. Further, similarly to the second embodiment, in addition to the latent curing agent, an ordinary curing agent can be used in combination. The third aspect of the present invention is obtained by a manufacturing method similar to that of the second aspect.

The third aspect of the present invention is that the one-part curable resin composition of the second aspect having the above-mentioned excellent properties further comprises a mixture of a polyacrylamide derivative and water, whereby the atmosphere is improved. Moisture can be imparted also to a deep part where it is difficult for moisture or the like to reach inside, and the problems of the deep part curability and the curing speed, which have been problems to date, can be overcome.

[0074] 4. Polyak surface-treated with inorganic filler
One-part curable tree containing a mixture of a rilamide derivative and water
Fat composition According to a fourth aspect of the present invention, in the one-pack type curable resin composition containing the above (a), (c) and (d), the following component (d) is surface-treated with an inorganic filler. Is a composition that is The components (a), (c) and (d) are as described above. Hereinafter, the mixture (d) of the polyacrylamide derivative surface-treated with the inorganic filler and water will be described.

Mixture of Polyacrylamide Derivative Surface-treated with Inorganic Filler and Water (d) In the fourth embodiment, instead of directly blending the above mixture (d) into the resin composition of the present invention, an inorganic filler is used. The mixture (d) is surface-treated with the agent and blended into the resin composition. The mixture (d) is surface-treated with an inorganic filler and held on the surface of the inorganic filler, whereby the mixture (d) is a copolymer (a) or a hydrolyzable latent curing agent (c). Even when it is difficult to dissolve in the resin composition, it can be easily dispersed in the resin composition.

Examples of the inorganic filler include calcium carbonate, titanium oxide, aluminum oxide, hydrous silicic acid, silicic anhydride, calcium silicate, aluminum silicate, magnesium silicate, sodium aluminosilicate, magnesium aluminosilicate, carbon black and the like. And calcium carbonate is preferably used.

The method of surface-treating the mixture (d) with the inorganic filler is not particularly limited. As a general method, a mixture of a polyacrylamide derivative and water is mixed with a suitable solvent (for example, acetone, methanol, ethanol, ME
K), if necessary, a compatibilizing agent such as a surfactant is added, and the inorganic filler is immersed or coated at room temperature in this solution and dried at room temperature. Alternatively, the inorganic filler may be immersed in a solvent for the polyacrylamide derivative, and then the solvent may be evaporated, and then water may be sprayed to cause the polyacrylamide derivative to absorb water.

In the present invention, when the surface treatment of the inorganic filler with the mixture (d) is carried out,
0.1 parts by weight of the polyacrylamide derivative is 0.1 to
20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable. If the amount is less than this range, the desired effect cannot be obtained. If the amount is too large, the mixture which does not bond to the inorganic filler increases, and the dispersion of the mixture is not always good.

The fourth embodiment of the present invention may contain optional components in addition to the above-mentioned essential components. As the optional components, those similar to those exemplified in the above-mentioned first embodiment can be used. No. Also here, in addition to the latent curing agent, an ordinary curing agent can be used in combination. The manufacturing method according to the fourth aspect of the present invention is the same as that described in the second aspect.

As described above, in the fourth embodiment of the present invention, the mixture (d) of the third embodiment having the above-mentioned excellent properties is subjected to the surface treatment of the inorganic filler, whereby the mixture is adhered to the surface of the inorganic filler. Mixture (d) as a water carrier
Can be easily dispersed in the composition. Therefore,
This is particularly effective when the mixture (d) has poor compatibility with other essential components.

[0081] 5. Coating or curing method A fifth aspect of the present invention is a one-pack type containing a mixture (d) of the above polyacrylamide derivative and water or a mixture (d) of water and a polyacrylamide derivative surface-treated with an inorganic filler. A one-pack type curable resin composition is applied or cured by heating the curable resin composition during or after the application.

A one-component curable resin composition containing the mixture (d) of the polyacrylamide derivative and water (third embodiment) and a mixture (d) of a polyacrylamide derivative surface-treated with an inorganic filler and water ) Is applied to an adherend by a commonly used application method such as dip coating, spray coating, knife coating, brush coating or the like, or at the time of curing after application. For a short time, preferably 1 second to 2
Heat for 0 minutes at a temperature higher than the temperature at which the polyacrylamide derivative in the mixture (d) changes from hydrophilic to hydrophobic (transition temperature). Heating at the time of application may be performed by heating the composition immediately before application, or the object to be coated may be heated. By doing so, the mixture (d) in the composition can release moisture effectively during application.

As described above, as a specific example of the coating or curing method having at least one heating step at a temperature higher than the transition temperature of the polyacrylamide derivative, the resin composition is coated and then kept at a temperature higher than the transition temperature of the polyacrylamide derivative. Hold in the oven for a predetermined time or heat and dry with a dryer, etc., heat the application surface of the adherend just before applying the resin composition, or squirt the composition when applying the resin composition For example, a method of applying a resin composition by applying heat to a jetting port to be applied is exemplified.

By doing so, the moisture retained in the mixture (d) is released, and as a result, the latent curing agent can be effectively activated even in a deep part where the moisture in the air is difficult to reach. The curing time can be shortened as compared with the case of simply applying. Therefore, the curability in the deep part can be improved, and the storage stability at room temperature is excellent. Therefore, according to the fifth aspect of the present invention, it is possible to exhibit excellent deep curability and curing speed even in a dry environment such as winter.

[0085]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of Ketimine 100 g of a diamine having a norbornane skeleton (NBDA; manufactured by Mitsui Chemicals, Inc.) and 200 of methyl isopropyl ketone
g and 200 g of toluene were placed in a flask, and the reaction was continued at a bath temperature of 150 ° C. for 20 hours while removing generated water by azeotropic distillation to obtain ketimine.

Example 1 A brominated product of a copolymer of polyisobutylene and p-methylstyrene and liquid polybutene were mixed in the composition shown in Table 1, kneaded uniformly, and norbornanediamine was added immediately before use. Thus, a two-part curable resin composition was obtained.

(Comparative Example 1) Instead of a bromide of a copolymer of polyisobutylene and p-methylstyrene and liquid polybutene, uniformly kneaded using an allyl group-modified polyisobutylene, and a curing agent ( SiH compound) was added at the composition shown in Table 1 to obtain a two-part curable resin composition.

(Example 2) Brominated copolymer of polyisobutylene and p-methylstyrene, liquid polybutene,
And a sterically hindered ketimine in a composition shown in Table 1,
The mixture was uniformly kneaded to obtain a one-part curable resin composition.

(Comparative Example 2) Instead of a bromide of a copolymer of polyisobutylene and p-methylstyrene and liquid polybutene, polypropylene glycol modified with a terminal silyl group and a condensation catalyst were blended in the composition shown in Table 1 and uniformly mixed. The mixture was kneaded to obtain a one-part curable resin composition.

Comparative Example 3 In place of the bromide of a copolymer of polyisobutylene and p-methylstyrene and liquid polybutene, a polyisobutylene modified with a terminal silyl group, and a condensation catalyst were blended in the composition shown in Table 1 and uniformly mixed. The mixture was kneaded to obtain a one-part curable resin composition.

Example 3 Poly (N-isopropylacrylamide) (p-NIPAM) Transition temperature 31
C.), water was sprayed onto the poly (N-isopropylacrylamide) to obtain a mixture of a polyacrylamide derivative and water. The weight ratio of poly (N-isopropylacrylamide) to water is as follows. p-NIPAM (produced by Kojin): water = 5: 2 One-part curable resin composition was prepared in the same manner as in Example 2 except that a mixture of the obtained polyacrylamide derivative and water was added. I got

Example 4 The procedure of Example 4 was repeated except that a mixture of a polyacrylamide derivative and water was surface-treated on calcium carbonate (hereinafter referred to as surface-treated calcium carbonate) and added as follows. In the same manner as in 3, a one-pack type curable resin composition was obtained. <Preparation of surface-treated calcium carbonate> Poly (N-isopropylacrylamide) (described as p-NIPAM; transition temperature: 31 ° C) was dissolved in methyl ethyl ketone (MEK) to prepare a solution. Soak calcium carbonate in this,
Next, the calcium carbonate was taken out and left to evaporate the MEK. Next, water was sprayed on this, and water was absorbed by poly (N-isopropylacrylamide). The weights of poly (N-isopropylacrylamide) and water retained in calcium carbonate are as shown below. Calcium carbonate (Calfine 200, manufactured by Maruo Calcium Co.) 100 parts by weight p-NIPAM (produced by Kojin) 1.7 parts by weight Water 0.051 part by weight

(Example 5) After coating Example 3, 80 ° C. ×
The procedure was performed in the same manner as in Example 3 except that heating was performed for 5 minutes. The tack-free time was 30% shorter than in Example 3. (Example 6) The procedure of Example 4 was repeated, except that the coating was applied and heated at 80 ° C for 5 minutes. The tack-free time was 30% shorter than in Example 4.

The resin compositions of Examples 1 to 4 and Comparative Examples 2 and 3 were subjected to the following tests. At this time, the storage stability test was not performed for Example 1 of the two-part curable resin composition, and for Comparative Example 1 of the thermosetting resin composition,
No tack-free, storage stability test was performed. The tensile test was performed by heating at 150 ° C. for 30 seconds to cure. 1. After each tack-free resin composition was prepared, it was cured at 20 ° C. under the condition of 60% relative humidity, and the time until tack disappeared (tack-free time) (Hrs) was measured according to JISA5758.

[0095] 2. Storage stability test Among the obtained resin compositions, the storage stability of Examples 1 to 4 and Comparative Examples 2 and 3, which are one-pack type curable resin compositions, was evaluated as follows. Immediately after the preparation, the viscosity (Pa · S) of the obtained composition was measured by rotating the rotor # 6 at 10 rpm using a BH type viscometer. On the other hand, the obtained resin composition was placed in a closed container and left at 70 ° C. for 24 hours. Similarly, the viscosity was measured, the rate of increase in the viscosity was calculated, and the storage stability was evaluated.

[0096] 3. Tensile test For the obtained resin composition, the breaking strength (T _B ) at normal state (25 ° C.) [MP] was measured in accordance with JIS K6251.
a] and elongation at break (E _B ) [%] were measured. When preparing the test pieces of Examples 3 and 4, a glass plate was used as an adherend, and a cured product was obtained by heating in an oven at 80 ° C. for 5 minutes.

[0097] 4. Weather resistance test A sunshine weathering test (SWOM) was performed at 20, 50 and 100 hours in accordance with JIS K6860. When one of the elongations was 90% or less, the evaluation was Δ, and when both of the elongations were 90% or less, the evaluation was ×. Table 1 shows the results.

[0098]

[Table 1]

Note: Brominated copolymer of polyisobutylene and p-methylstyrene: Exxon Chemical Co., Ltd., trade name: EXXPRO90-10 Liquid polybutene: Nippon Petrochemical Co., Ltd., trade name: HV-100 Terminal Silyl Group Polypropylene Glycol (PPG): Kanebuchi Chemical Industry Co., Ltd., Trade Name: MS Polymer S303 Terminal Allyl Group Modified Polyisobutylene: Kanebuchi Chemical Industry Co., Ltd., Trade Name: Epion 600A Terminal Silyl Group Modified Poly Isobutylene: manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name: Epion 505S norbornanediamine (diamine having a norbornane skeleton): manufactured by Mitsui Chemicals, Inc., trade name: NBDA Ketimine: compound obtained in Synthesis Example 1 SiH compound: bell Fuchi Chemical Industry Co., Ltd., trade name: CR100, condensation catalyst: dibutyltin laurate (reagent)

[0100]

Is a liquid of the present invention according to the present invention, C ₄ one-containing halogenated product of a copolymer of isomonoolefin and p- alkylstyrene -C ₈ and two-component curable resin composition, It has excellent moisture permeation resistance, weather resistance and alkali resistance, and can be suitably used for sealants, reactive hot melts and adhesives. Further, in the one-part curable resin composition, a one-part curable resin composition having excellent storage stability and curability by incorporating a sterically hindered ketimine as a hydrolyzable latent curing agent. Things are obtained. Furthermore, by using a mixture of water and a polyacrylamide derivative which releases water by heating as a water carrier, the deep part curability is also improved. Such curable resin compositions include various adhesives, pressure-sensitive adhesives, paints, sealant compositions such as double-layer glass sealing agents, waterproofing agents, spraying agents, materials for molding, sealants,
It can be widely applied to hot melts, direct glazing materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 33/26 C08L 33/26 F-term (Reference) 4J002 BB241 BG122 BG132 CL003 CN023 DA037 DE028 DE137 DE147 DE237 DJ007 DJ017 EF066 EF126 EL136 EN036 EN046 ER006 EU136 EU226 EV066 FB267 FD143 FD146 GJ01 GJ02 HA01

Claims (7)

[Claims] 1. A halogenated copolymer of a C ₄ -C ₈ isomonoolefin and a p-alkylstyrene which is liquid at normal temperature and (b) a primary amine or a secondary amine in the molecule. , A two-part curable resin composition comprising a compound having at least two groups selected from the group consisting of thiol groups, acid anhydride groups and carboxyl groups. Is wherein (a) liquid at room temperature, comprising a C ₄ -C ₈ isomonoolefin and p- halides alkylstyrene, copolymers and (c) hydrolysis of the latent curing agent One-part curable resin composition. 3. The method according to claim 1, wherein the latent curing agent (c) is
3. The at least one member selected from the group consisting of ketimine, aldimine, enamine and oxazolidine.
1. The one-part curable resin composition according to item 1. 4. The method according to claim 1, wherein the latent curing agent (c) is
The one-part curable resin composition according to claim 2 or 3, which is a ketimine synthesized from a ketone represented by the following formula (1) and a compound having two or more primary amino groups in a molecule. Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group R ⁴ : hydrogen atom and 1 to 6 carbon atoms Any one selected from the group consisting of 6 alkyl groups R ⁵ : hydrogen atom, methyl group or ethyl group R ⁶ : hydrogen atom, methyl group or ethyl group 5. The one-component curable resin composition according to claim 2, further comprising a mixture (d) of a polyacrylamide derivative and water. 6. The one-part curable resin composition according to claim 5, wherein the mixture (d) of the polyacrylamide derivative and water has been subjected to a surface treatment with an inorganic filler. 7. A method for applying or curing a one-part curable resin composition, comprising heating the one-part curable resin composition according to claim 5 during or after application.