JP2000072973A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide curable compositions low in soiling the stones around the compositions applied and quickly curable with water in the air at normal temperature or the like to provide a cured product having an improvement in non-tackiness of its surface and low in dust adhesion. SOLUTION: Curable resin compositions comprise (1) a saturated hydrocarbon polymer having an hydroxyl group or a hydrolyzable group which is bonded to a silicon atom and at least one silicon-containing group which is crosslinkable by forming a siloxane bond and, based on 100 pts.wt. saturated hydrocarbon polymer, (2) 0.1-30 pts.wt epoxy resin, (3) 0.01-20 pts.wt. photocurable resin, and (4) 0.01-30 pts.wt. ketimine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel curable composition. For details, useful as a sealing material, etc.
The present invention relates to a curable composition having low contamination around stones, and having excellent curability and dust resistance.

[0002]

2. Description of the Related Art Conventionally, polyisobutylene (PIB) having a hydrolyzable silyl group has been used as an elastic sealing material for buildings.
However, the cured product of this polymer is
There is a problem that the surface of the cured product is contaminated by dust or the like depending on the composition, curing conditions, and the like, thereby deteriorating the appearance. In order to solve this problem, an invention has been proposed in which an oxygen-curable resin or a photo-curable resin, or a mixture of both, is blended with a PIB polymer to improve dust adhesion (Japanese Patent Laid-Open No. 8-41138). No., JP-A-8-41
No. 356, JP-A-8-41357). However, these compositions also do not sufficiently improve dust adhesion.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the contamination around stones, and to quickly cure at room temperature with moisture in the air to improve the surface of the cured product to be non-adhesive.
An object of the present invention is to provide a curable composition having low dust adhesion.

[0004]

That is, the present invention provides:
(1) a saturated hydrocarbon polymer having at least one silicon-containing group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond; (2) the above saturated hydrocarbon polymer 0.1 to 30 parts by weight of an epoxy resin based on 100 parts by weight of the polymer; and (3) 0.01 to 2 parts by weight based on 100 parts by weight of the saturated hydrocarbon polymer.
The present invention provides a curable composition containing 0 parts by weight of a photocurable resin, and (4) 0.01 to 30 parts by weight of ketimine based on 100 parts by weight of the saturated hydrocarbon polymer.

Further, it is preferable that the ketimine is a ketone derivative having photosensitivity.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The curable composition of the present invention (hereinafter, referred to as the composition of the present invention) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and has at least one silicon-containing group capable of crosslinking by forming a siloxane bond. It is a composition containing a photocurable resin, an epoxy resin, and ketimine in a saturated hydrocarbon-based polymer (hereinafter, referred to as polymer (A)).

[1] The polymer (A) contained in the composition of the present invention has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, having a saturated hydrocarbon group as a main chain, and forms a siloxane bond. It is a polymer having at least one silicon-containing group that can be crosslinked by the method. The main chain of the polymer (A) is
A saturated hydrocarbon polymer refers to a polymer that does not substantially contain unsaturated bonds between carbons other than aromatic hydrocarbons. As the main chain of such a polymer (A), for example, a polymer obtained by polymerizing an olefinic hydrocarbon having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene as a main monomer; butadiene, isoprene And the like, and those obtained by copolymerizing the above-mentioned olefin-based hydrocarbon and diene-based hydrocarbon and further hydrogenating them. Among these polymers, an isobutylene-based polymer and a hydrogenated polybutadiene-based polymer are preferable from the viewpoint that a functional group can be easily introduced into a terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be easily increased.

The isobutylene-based polymer may contain, as another monomer, a monomer copolymerizable with isobutylene, preferably at most 50% by weight, more preferably at most 30% by weight, particularly preferably at most 10% by weight of the isobutylene-based polymer. Weight% or less,
It may be contained. Such monomers include, for example, olefinic hydrocarbons having 4 to 12 carbon atoms, vinyl ether hydrocarbons, vinyl silanes, and allyl silanes.

[0009] The hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers also contain the above-mentioned monomer in addition to the main component monomer, as in the case of the isobutylene-based polymer. Is also good.

[0010] The polymer (A) may contain a monomer, such as a polyene compound such as butadiene or isoprene, having a double bond remaining after polymerization, preferably not more than 10% by weight, within a range not to impair the object of the present invention. , More preferably 5% by weight or less,
Particularly preferably, it may be contained in an amount of 1% by weight or less.

The polymer (A) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and has at least one silicon-containing group (hereinafter referred to as a reactive silicon group) which can be crosslinked by forming a siloxane bond. Have As the reactive silicon group used in the present invention, for example, the following formula (1):

Embedded image (Wherein, R ¹ and R ² are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms)
Aralkyl group or —OSi (R ⁻ ) ₃ (R
^- represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ^-
May be the same or different), and when there are two or more R ¹ and R ² , they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when there are two or more, they may be the same or different. p is an integer of 0-3, q is an integer of 0-2, and r is an integer of 0-19. Where p
+ Rq ≧ 1. r

Embedded image May be the same or different. )).

The hydrolyzable group X in the formula (1) is a hydrogen atom; an alkoxy group such as a methoxy group or an ethoxy group; an alkenyloxy group such as a vinyloxy group or a propenyloxy group; an acyloxy group such as an acetoxy group or a benzoyloxy group. Groups; ketoximate groups such as dimethylketoxime group and cyclohexylketoxime group; amino groups; amide groups such as acetamide; aminooxy groups; mercapto groups. Among these, an alkoxy group is preferable because of its mild hydrolytic property and easy handling.

The above-mentioned hydrolyzable groups and hydroxyl groups can be bonded to one to three silicon atoms. (P + rq)
Is 1 or more, preferably 1 to 5. When two or more hydroxyl groups or hydrolyzable groups are bonded to the reactive silicon group, they may be the same or different.
The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms connected by a siloxane bond, the number is preferably 20 or less. In particular, the formula:

Embedded image (Wherein R ² , X, and p are R in formula (1)
Synonymous with ² , X and p. The reactive silicon group represented by ()) is preferable because it is easily available.

The number of reactive silicon groups in the molecule of the polymer (A) is preferably at least one, preferably 1.1 to 5. If the number is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be bonded to the molecular terminal of the polymer (A), may be present internally, or may be present on both. In particular, when it is bonded to a molecular end, the amount of the effective network chain of the polymer (A) component contained in the finally formed cured product increases, so that a rubbery cured product excellent in strength and elongation is obtained. It is preferable in that it can be easily obtained. These polymers (A) having a reactive silicon group may be used alone or in combination of two or more.

The molecular weight of the polymer (A), particularly the number average molecular weight of the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer, is preferably about 500 to 100,000,
Particularly, those having a liquid or fluidity of about 1,000 to 30,000 are preferable from the viewpoint of handling workability.

The method for producing the polymer (A) is described in JP-A-8-4.
It is described in detail in Japanese Patent Publication No. 1356. As such a polymer (A), a commercially available product can also be used. For example, EPION EP505 manufactured by Kanegafuchi Chemical Industry Co., Ltd.
S (molecular weight: about 20,000) and the like can be used.

[2] The epoxy resin contained in the composition of the present invention is not particularly limited, and any known epoxy resin such as a bisphenol epoxy resin and a novolak epoxy resin can be used. One or more resins may be used in combination. As such an epoxy resin, a commercially available product can be used,
For example, Epicoat 828 manufactured by Yuka Shell Epoxy can be used. As the epoxy resin contained in the composition of the present invention, those having a liquid or fluidity are preferable, and those having reactivity at room temperature are preferable. The content of the epoxy resin contained in the composition of the present invention is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer (A). If the amount is less than 0.1 part by weight, the improvement in dust adhesion becomes insufficient, and if the amount is more than 30 parts by weight, the tensile properties and the like of the cured product are undesirably impaired. Examples of the method for producing the epoxy resin contained in the composition of the present invention include a known production method such as a method of reacting a phenol resin or a novolak resin with an epihalohydrin such as epichlorohydrin to glycidylate. Further, a catalyst or a metal dryer for accelerating the oxidative curing reaction may be used together with the epoxy resin. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, and amine compounds.

[3] The photocurable resin contained in the composition of the present invention is one in which the molecular structure is chemically changed in a short time by the action of light, and causes physical changes such as curing. As the photocurable resin, organic monomers, oligomers, resins, or compositions containing these are known, and specifically, unsaturated acrylic compounds, polyvinyl cinnamates,
Azide resins and the like.

The unsaturated acrylic compound is a monomer or oligomer having one or several acrylic or methacrylic unsaturated groups, or a mixture thereof, such as ethylene glycol (meth) acrylate and butylene glycol (meth). Monomers such as acrylate, propylene glycol (meth) acrylate, and neopentyl glycol di (meth) dimethacrylate or oligoesters having a molecular weight of 10,000 or less can be mentioned.

As the polyvinyl cinnamate, a photosensitive resin having a cinnamoyl group as a photosensitive group is known, and examples thereof include polyvinyl cinnamate derivatives such as cinnamate of polyvinyl alcohol.

As the azide resin, there is known a photosensitive resin having an azide group as a photosensitive group. Specific examples thereof include a rubber photosensitive liquid containing a diazide compound as a photosensitive agent, and a photosensitive resin. (Published March 17, 1972, published by the Printing Society of Japan, pp. 93-106, pp. 117-117)
Page-) for a detailed illustration. These photocurable resins are
They can be used alone or as a mixture of two or more.

As such a photocurable resin, a commercially available product can be used, for example, Aronix M-309 manufactured by Toa Gosei Chemical Co., Ltd.

The content of the photocurable resin contained in the composition of the present invention is based on 100 parts by weight of the polymer (A).
It is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight. If the amount is less than 0.01 part by weight, the effect of photocuring is small, and if it exceeds 20 parts by weight, the surface of the cured product is undesirably cracked or adversely affected in physical properties.

[4] The ketimine contained in the composition of the present invention refers to a compound in which oxygen of a carbonyl group of a ketone is substituted with an imino group, CRR '= NR''. As the ketimine used in the present invention, ketimine, which is a ketone derivative having photosensitivity, is preferable. Such a ketimine is obtained by a dehydration condensation reaction between a ketone having photosensitization and an amine. Ketone having photosensitivity is
It is a ketone that is excited by light and generates a free radical by a hydrogen abstraction reaction. Examples of such ketones include ketones such as benzophenone, acetophenone, and thioxanthone derivatives. As the ketimine contained in the composition of the present invention, among these ketones having photosensitivity, ketimine which is a derivative of benzophenone (shown by the following formula (2)) is particularly preferable.

Embedded image In the formula, Y represents an alkyloxy group such as a hydroxyl group, a methoxy group or an ethoxy group, a halogen group such as a chloro group, or a nitro group. Examples of amines which are dehydrated and condensed with ketones to form ketimines include aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and laurylamine; isophoronediamine, mensendiamine, bis (4-amino-3-methyl). Known amine compounds used as curing agents for epoxy resins such as alicyclic amines such as cyclohexyl) methane and norbornane diamine compounds; aromatic amines such as meta-xylylenediamine; and the above-mentioned polymer ( It can be appropriately selected and used depending on the structure of A). Among these, a norbornane diamine compound is preferable because of its excellent curability. Such ketimine contained in the composition of the present invention is converted into a ketone and an amine by hydrolyzing in the composition, and the amine is a photosensitizing agent for the ketone as a curing agent for the epoxy resin. When the compound has the formula (1), it absorbs light to efficiently generate free radicals and reacts with a monomer in the composition to act as a substance that initiates chain polymerization. The photosensitizing ketone is preferable when it coexists with an aliphatic or aromatic amine, because the above-described working efficiency of the photosensitizing ketone is improved by the electron transfer and proton transfer mechanisms. These ketimines can be used alone or as a mixture of two or more.

The content of ketimine contained in the composition of the present invention is 0.0 to 100 parts by weight of the polymer (A).
It is 1 to 30 parts by weight, preferably 0.1 to 20 parts by weight. If the amount is less than 0.01 part by weight, the effect of photocuring is small, and if it is more than 30 parts by weight, the physical properties of the cured product are undesirably deteriorated.

The composition of the present invention may contain a curing catalyst, a filler, a plasticizer, a solvent, a colorant, and the like, if necessary, in order to adjust viscosity, physical properties, etc., in addition to the above essential components. Good.

As the curing catalyst, for example, tin octylate, dibutyltin dilaurate, dibutyltin maleate,
Metal salts of carboxylic acids such as dibutyltin phthalate; reaction products of organic tin oxides and esters; tetrabutyl titanate;
Organic titanates such as organosiloxytitanium; amines; amine salts; quaternary ammonium salts; granidine compounds and the like. These catalysts may be used alone or in combination of two or more. These curing catalysts are added in an amount of 0.1 to 100 parts by weight of the polymer (A).
It is preferably from 10 to 10 parts by weight from the viewpoint of the curing speed.

The plasticizer is not particularly limited as long as it is a process oil or another hydrocarbon that is compatible with the polymer, and various known plasticizers can be used. For example, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; paraffin chlorides;
Alkyl diphenyl; hydrocarbon oils such as partially hydrogenated terphenyl; process oils; alkyl benzenes and the like. Among them, the use of process oils is preferred from the viewpoint of good compatibility with the polymer. The amount of the plasticizer is 50 to 20 parts by weight based on 100 parts by weight of the polymer (A).
0 parts by weight is preferable because the viscosity becomes suitable for workability.

Examples of the filler include ordinary calcium carbonate, kaolin, clay, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, and the like.
And carbon black. These can be used alone or in combination. The addition amount of the filler is preferably from 10 to 300 parts by weight based on 100 parts by weight of the polymer (A) from the viewpoint of the physical properties of the composition of the present invention to be obtained.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, petroleum solvents from gasoline to kerosene fraction, acetone, methyl ethyl ketone, methyl isobutyl ketone And ether esters such as cellosolve acetate and butyl cellosolve acetate. The addition amount of the solvent is preferably 0 to 50 parts by weight based on 100 parts by weight of the polymer (A) from the viewpoint of workability and volume shrinkage. Examples of the coloring agent include inorganic pigments such as titanium oxide, red iron oxide, and chromium oxide, and organic pigments such as copper phthalocyanine blue.

The method for producing the composition of the present invention is not particularly limited. Preferably, the above-mentioned components are sufficiently kneaded using a stirring device such as a mixing mixer, and uniformly dispersed to obtain a composition. .

The composition of the present invention obtained as described above has the following characteristics. In the composition of the present invention, the silyl group of the polymer (A) contained therein is surrounded by the hydrophobic group and is further polymerized, so that the contamination around the stone is low. In addition, the composition of the present invention is characterized in that the reactive silicon group of the polymer (A) is hydrolyzed at room temperature by moisture or the like in the air to cause a cross-linking reaction, and the photo-curable resin contained therein is also exposed to light. Since the epoxy resin causes a curing reaction due to oxygen in the air and further contains ketimine in the composition, it exhibits excellent curability as a whole, and the tackiness on the surface of the cured product is remarkably reduced. Therefore, dust adhesion on the cured product surface of the composition of the present invention is low. Further, a composition containing a ketone derivative such as benzophenone having photosensitizing properties as a ketimine contained in the composition of the present invention exhibits particularly excellent curability and exhibits dust resistance.

[0034]

The present invention will be specifically described below with reference to examples. (Examples 1-2, Comparative Examples 1-2) The following compounds were blended in the blending amounts shown in Table 1, and stirred and mixed using a 5 L planetary (universal stirrer) to obtain a curable composition. .

The properties of the compositions obtained in Examples and Comparative Examples were measured and evaluated by the following methods. 1) Contamination around stones After the composition was manufactured, it was applied between stones and cured at 20 ° C. for 7 days. After that, it was exposed outdoors for one month, and the stones around the composition were observed for contamination.
No pollution had occurred. 2) Surface tackiness After the composition was manufactured and cured at 20 ° C. for one week,
Polyethylene terephthalate was pressed on the surface of the cured product.
In the table, ○ indicates that there was no adhesion of the cured product and no residual tack, and X indicates that there was. 3) Dust adhesion After the composition was manufactured, it was cured outdoors, and one month later, it was observed and evaluated whether dust had adhered to the surface of the cured product. In the table,
は indicates that no dust had adhered, △ indicates that dust had been adhered, and x indicates that contamination of the cured product surface with dust was significant. Table 1 shows the results.

[0036] In the table, the unit of the compound is part by weight. In addition, EPION
50 parts by weight of the 150 parts by weight are process oil.

The compounds used in the preparation of the compositions shown in the table are as follows. Polymer (A): EPION (EP505S) (PIB oligomer; manufactured by Kaneka Chemical Co., Ltd .; chemical structure is represented by the following formula)

Embedded image Epoxy resin: Epicoat 828 (manufactured by Yuka Shell Epoxy) Photocurable resin: ARONIX M-309 (manufactured by Toa Gosei Chemical Co., Ltd., chemical structure is represented by the following formula)

Embedded image Ketimine: benzophenone derivative ketimine, chemical structure is shown by the following formula)

Embedded image Colloidal calcium carbonate: Calfine 200 (manufactured by Maruo Calcium Co., Ltd.) Heavy calcium carbonate: Softon 3200 (manufactured by Bihoku Kagaku Co., Ltd.) Process oil: PAO5004 (manufactured by Idemitsu Petrochemical Co., Ltd.) Tin octylate: Neostan U-28 (Nitto Kasei Co., Ltd.) Laurylamine: Farmin 20D (Kao Corporation) Titanium oxide: Thai Bake R-820 (Ishihara Sangyo Co., Ltd.)

[0038]

Industrial Applicability The composition of the present invention does not show any contamination around stones, has excellent curability, reduces surface tack quickly, and has low dust adhesion. Therefore, the composition of the present invention is useful as a sealing material and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA073 AC111 BB201 BE023 BG043 BG053 CD062 CP171 EH077 ER006 ES006 FD010 FD020 FD143 FD146 FD147 FD150 FD156 GJ02

Claims (2)

[Claims] 1. A saturated hydrocarbon polymer having at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, 0.1 to 30 parts by weight of an epoxy resin with respect to 100 parts by weight of the saturated hydrocarbon polymer, and (3) 0.01 to 20 parts by weight of photocuring with respect to 100 parts by weight of the saturated hydrocarbon polymer. (4) A curable composition containing: 0.01 to 30 parts by weight of ketimine based on 100 parts by weight of the saturated hydrocarbon polymer. 2. The curable composition according to claim 1, wherein the ketimine is a ketone derivative having photosensitization.