JP2010248307A - Two-pack curable joint composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-pack curable joint composition, which is used as a joint material for an agricultural water passage and so forth formed with a concrete or the like and is sometimes exposed to the outdoors, excellent in the storage stability and curability and also good in water resistance. <P>SOLUTION: The two-pack type curable joint composition includes an agent A which contains a reactive silicon group-containing organic polymer and an epoxy group-containing compound, and an agent B which contains an amine compound and a curing catalyst for the reactive silicon group-containing organic polymer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

 The present invention relates to a two-component curable joint composition which is used as a joint material for agricultural waterways formed of concrete or the like and may be exposed outdoors.

  Conventionally, room temperature curable compositions using reactive silicon group-containing polyoxyalkylene polymers as joint materials for construction, civil engineering, and industrial applications are easy to handle and have stable rubber elasticity. A two-component curable composition has been proposed that is widely used in the art and has excellent internal curability and good storage stability (Patent Document 1).

  Such a curable composition is obtained by blending an A compound containing an organic polymer having a reactive silicon group with a silane coupling agent and an amine compound, which is included because the amine compound is hydrophilic. The moisture adsorbed on the inorganic filler when mixing inorganic filler such as calcium carbonate for practical use may be dehydrated with a silane coupling agent, and the organic polymer having a reactive silicon group It is considered that the storage stability is improved.

  However, if the amount of the silane coupling agent is too small or contains too much water, the organic polymer having a reactive silicon group may gradually react to increase the viscosity and decrease the storage stability. In order to improve this, an amine compound or an organic compound having an amine compound and a reactive silicon group is heated under reduced pressure to usually have a water content of 500 ppm or less, and then a silane coupling material is added. There has been a problem that a so-called dehydration treatment step is required to stabilize the moisture state of the agent A. Such a dehydration process requires time and energy, and the inorganic filler to be blended for practical use may require a heat treatment to reduce the adsorbed moisture in advance, which is a major manufacturing issue. It was.

  Further, when the adherend is a porous substrate, a curable composition has been proposed that can suppress a decrease in adhesiveness even if water permeates through the pores (Patent Document). 2).

  The curable composition contains (A) a crosslinkable silyl group-containing organic polymer, (B) a glycidyl ether having a polyalkylene glycol skeleton, and (C) a silicon compound having a functional group capable of reacting with an epoxy group. However, in order to use the curable composition for practical use, it is necessary to add a water absorbent (vinyl methoxysilane in the examples in the document) separately.

  The effect of vinyl methoxysilane varies depending on the amount of water contained in the composition before blending when the amount of the compound is a certain amount, and storage stability of the crosslinkable silyl group-containing organic polymer when the amount of water is large. When the property is lowered and the water content is small, the curing time of the curable composition is delayed or the deep part curability is poor. When used as a joint material, if the expansion and contraction of the joint due to temperature change or the like when the deep curability is not sufficient, the curable composition that is the joint material cracks and a problem arises in that the waterproof property is defective. . In addition, there is a problem that the water resistance of the cured product is lowered when the amount of water is small and curing is not completed sufficiently.

WO 2006/006512 JP 2004-107652 A

The problem of the present invention is that there is no delay in curing time, there is no need to add vinyl methoxysilane or the like as a dehydrating agent in order to improve storage stability, and further, the reduced pressure that has been carried out as necessary in the past. Another object of the present invention is to provide a two-component curable joint composition that does not require heat dehydration and has good water resistance.

The inventors of the present invention diligently studied the above problems, and the invention according to claim 1 is directed to an agent A containing an organic polymer having a reactive silicon group and an epoxy group-containing compound, an amine compound, and the reactive silicon. A two-part curable joint composition comprising a curing agent for an organic polymer having a group, and having a good storage stability and having a reactive silicon group The present invention provides a two-component curable joint composition that does not require a heat treatment under reduced pressure for dehydration of the A agent containing, does not delay the curing time, and has good water resistance.

The invention according to claim 2 is characterized in that the amine compound according to claim 1 is an amine compound which does not have a cyclic moiety or has no cyclic bond even if it has a cyclic moiety. Liquid type curable joint composition, good storage stability, no need for heat treatment under reduced pressure for dehydration of agent A containing organic polymer having reactive silicon group, and curing time is delayed Furthermore, the present invention provides a two-component curable joint composition that does not cause yellowing even when used outdoors, in addition to having good water resistance.

The two-component curable joint composition of the present invention includes an agent A containing an organic polymer having a reactive silicon group and an epoxy group-containing compound, an amine compound, and curing of the organic polymer having the reactive silicon group. A two-component curable joint composition comprising a B agent containing a catalyst, having good storage stability, and for dehydrating the A agent containing an organic polymer having a reactive silicon group There is no need to perform a heat treatment under reduced pressure, the curing time is not delayed, and the water resistance is good.

Hereinafter, the present invention will be described in detail.
The two-part curable joint composition of the present invention has an agent A containing an organic polymer having a reactive silicon group and an epoxy group-containing compound, an amine compound, or has no cyclic part or has a cyclic part. Is a two-component curable joint composition comprising: an amine compound having no unsaturated bond in the cyclic portion; and a B agent containing a curing catalyst for the organic polymer having the reactive silicon group. If necessary, a diluent, a pigment, a filler, and an antioxidant are blended.

  The organic polymer having a reactive silicon group of the present invention is one in which the organic polymer is cured by a polymerization reaction with moisture in the air or moisture adsorbed on the filler, and at least in one molecule. It is a so-called modified silicone compound having one reactive silicon group. The main chain that is the skeleton of the organic polymer having a reactive silicon group is a polyether obtained by polymerization of a cyclic ether such as propylene oxide, ethylene oxide, or tetrahydrofuran, or a condensation of a dibasic acid such as adipic acid and a glycol or a lactone. And polyethers obtained by ring-opening polymerization.

  The reactive silicon group is a functional group that contains a hydrolyzable group or a silicon atom to which a hydroxyl group is bonded, and undergoes condensation polymerization with moisture by a silanol condensation reaction. Specific examples include a halogenated silyl group, an alkoxysilyl group, an acyloxysilyl group, an aminosilyl group, an alkenyloxysilyl group, an oximesilyl group, an amidosilyl group, and a mercapto group. Is preferred. Such an organic polymer having a reactive silicon group, which is a modified silicone compound, is commercially available from Kaneka Chemical Industry Co., Ltd. as MS polymer, silyl, or epion (trade name).

  The number average molecular weight of the organic polymer having a reactive silicon group used in the present invention is preferably 500 to 100,000 in terms of polystyrene in GPC. 1000 to 70000 is suitable from the viewpoint of easy handling.

  Epoxy group-containing compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol type epoxy resin, bisphenol A propylene oxide addition Examples of such glycidyl ether type epoxy resins are not limited thereto, and generally used epoxy resins can be used. In particular, those containing two epoxy groups in the molecule are preferred because of their high curability.

  The weight blending part of the epoxy group-containing compound is 2 to 50% by weight, preferably 5 to 35% by weight, based on 100 parts by weight of the organic polymer having a reactive silicon group. If it is less than 2% by weight, the water resistance is poor, and if it exceeds 50% by weight, the elongation becomes small and it is not suitable for a stretch joint. If it is less than 5% by weight, the adhesion to concrete tends to decrease, and if it exceeds 35% by weight, the elongation tends to decrease.

  As the amine compound, a generally used curing agent for epoxy resin is used. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris ( Examples include, but are not limited to, amines such as (dimethylaminomethyl) phenol, tertiary amines, polyamide amines, and ketimines.

  An amine compound having no cyclic part or having no cyclic bond even if it has a cyclic part is the above-mentioned triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine. In addition, alicyclic polyamines such as norbornene diamine, polyoxypropylene diamine, polyoxypropylene triamine, 1.3 bisaminomethylsiloxane, bis (4-aminocyclohexyl) methane, and lalomine, and polyether polyamines are exemplified. However, it is not limited to these.

  The compounding amount of the amine compound or the amine compound having no cyclic part or having no cyclic bond even if it has a cyclic part is the epoxy group equivalent of the epoxy group-containing compound and the active hydrogen equivalent of the amine compound. The equivalence ratio is 0.6 to 1.4. If it is less than 0.6, the adhesiveness and water resistance are lowered, and if it exceeds 1.4, excessive amine bleeds on the surface of the cured product and causes soiling.

  The curing catalyst for the organic polymer having a reactive silicon group is a catalyst that promotes the silanol condensation reaction, specifically, titanate esters such as tetrabutyl titanate and tetrapropyl titanate, dibutyltin dilaurate, and dibutyltin. Maleate, dibutyltin diacetate, tin carboxylates such as tin octylate and tin naphthenate, organoaluminum compounds, chelate compounds, lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanol Amine compounds such as ethanolamine and diethylenetriamine, low molecular weight polyamide resin obtained from excess polyamine and polybasic acid, polyamine compounds obtained by reaction of excess polyamine and epoxy compound, Silanol catalyst such as a silane coupling agent having an amino group can be mentioned. These catalysts may be used alone or in combination of two or more.

  The amount of the curing catalyst for the organic polymer having a reactive silicon group is 0.2 to 3% by weight, preferably 0.5 to 2% by weight based on 100 parts by weight of the organic polymer having a reactive silicon group. %. If it is less than 0.2% by weight, curing is remarkably slow, and the joint composition may break due to joint expansion and contraction during curing. If it exceeds 3% by weight, the curing time is remarkably shortened and the workability to the joint is lowered. If it is less than 0.5% by weight, curing tends to be delayed, and if it is 2% by weight, curing tends to be accelerated.

  Diluents include, for example, phthalic acid esters such as DOP, DBP, DINP (diisononyl phthalate), dioctyl adipate, isodecyl succinate, dibasic acid esters such as dibutyl sebacate, glycol esters such as diethylene glycol dibenzoate, Aliphatic esters such as butyl oleate, phosphate esters such as tricresyl phosphate, epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil, polyethers such as polypropylene glycol and derivatives thereof, and polyoxyalkylene ether , Chlorinated paraffins, alkylbenzene plasticizers and the like can be arbitrarily used alone or in the form of a mixture of two or more. A combination of those having good compatibility is preferable. The weight blending part of the diluent is 20 to 100% by weight, preferably 30 to 75% by weight, based on 100 parts by weight of the organic polymer having a reactive silicon group. If it is less than 20% by weight, the viscosity of the joint composition is increased and workability is lowered. If it exceeds 100% by weight, the strength of the cured product decreases, and breakage tends to occur due to expansion and contraction of joints. If it is less than 30% by weight, the viscosity of the joint composition tends to increase, and if it exceeds 75% by weight, the strength of the cured product tends to decrease.

  As the pigment, titanium oxide is mainly used, and other carbon black, iron oxide and the like can be used. The weight blending part of the pigment is 0.1 to 30% by weight, preferably 1 to 25% by weight based on 100 parts by weight of the organic polymer having a reactive silicon group. If it is less than 0.1% by weight, the concealability is insufficient, and if it exceeds 30% by weight, the viscosity of the composition becomes too high, resulting in poor workability. If it is less than 1% by weight, the concealability tends to decrease, and if it exceeds 25% by weight, the viscosity tends to increase.

  As the filler, calcium carbonate having an average particle diameter of 0.2 μm or less is used as primary particles. By using the calcium carbonate, no sagging or the like occurs in the curable joint composition during construction work. The average particle size is preferably from 0.01 to 0.15 μm, and calcium carbonate surface-treated with organic substances such as fatty acids, resin acids, lignins, and particularly fatty acids is preferred. The surface-treated calcium carbonate is commercially available under the names of white gloss flower O, gelton 50, white gloss flower CC, white gloss flower CCR, and Calfine 200M.

  The weight blending part of the filler is 50 to 200% by weight, preferably 70 to 170% by weight, based on 100 parts by weight of the organic polymer having a reactive silicon group. If it is less than 50% by weight, sagging occurs when filling a joint on a vertical surface, and if it exceeds 200% by weight, the workability of construction on the joint is lowered. If it is less than 70% by weight, sagging tends to occur, and if it exceeds 170% by weight, the workability on the joint tends to be lowered.

  Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols.

  In addition to the above ingredients, the compatibility between the polymer obtained by condensation polymerization of the organic polymer having a reactive silicon group and the cured epoxy resin is improved, and the cured epoxy resin is added to the so-called “sea” where the polymer is. In order for the “islands” to form a substantially uniform sea-island structure, alkoxysilane can be added to the B agent. As the alkoxysilane, for example, γ-aminopropyltrimethoxylane, γ-aminopropylmethyldimethoxysilane and the like can be used. Moreover, the weight compounding part of alkoxysilane is 0.5-5 weight% with respect to 100 weight part of organic polymers which have a reactive silicon group, Preferably it is 0.8-3 weight%. If it is less than 0.5% by weight, the tensile strength and elongation are lowered, and if it exceeds 5% by weight, the water resistance is lowered. If it is less than 0.8% by weight, the tensile strength and elongation tend to decrease, and if it exceeds 3% by weight, the water resistance tends to decrease.

Hereinafter, it demonstrates concretely in an Example and a comparative example.

Preparation of Sample According to Table 1, A agent and B agent of the two-component curable joint compositions of Example 1, Example 2, and Comparative Examples 1 to 3 were prepared. In Table 1, Kanekasilyl EST270 (viscosity 15 Pa · s / 23 ° C., B-type viscometer, trade name, manufactured by Kaneka Corporation) is used as the organic polymer having a reactive silicon group, and jER828 is used as the epoxy group-containing compound. (Bisphenol A type epoxy resin, epoxy equivalent 190, Japan Epoxy Resin Co., Ltd., trade name), Adeka Polyether P3000 (average molecular weight 3000, number of functional groups 2, viscosity 450 mPas / 25 ° C., ADEKA Co., Ltd.) Manufactured under the trade name), and the antioxidant, IRGANOX1010 (pentaerythritol tetrakis (3- (3.5-di-t-butyl-4-hydroxyphenyl) propionate)), Ciba Japan ( Co., Ltd., trade name), and the pigment is Taipure R-960 (titanium oxide, DuPont ( Co., Ltd., trade name), Calfine 200M (surface fatty acid-treated calcium carbonate, Maruo Calcium Co., Ltd., trade name) as filler, and Z-6300 (vinyl trimethoxysilane, Toray Dow Corning) as vinyl silane. (Trade name) manufactured by Co., Ltd., Ancamine K54 (tris (dimethylaminomethyl) phenol, manufactured by Air Products Japan Co., Ltd., trade name) is used for amine compound 1, and 1.3 BAC (1. 3bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Inc.), SH-620 (aminoethylaminopropyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd., trade name) as the alkoxysilane, and reactive silicon group Neostan U-130 (1,1,3,3-tetrabutyl-1,3-dila as a curing catalyst for organic polymers having Uroyloxy distannoxane, manufactured by Nitto Kasei Co., Ltd., trade name), each of which is mixed with a filler for each of the A agent or B agent, after mixing with a disper, in three rolls Evenly dispersed. Those with no filler were mixed uniformly with a high-speed disper.

Evaluation methods

Storage stability 500 g of agent A or agent B is put in an iron can container and sealed. This is left in a 50 ° C. constant temperature bath for 4 weeks, then cooled to 23 ° C., and the initial viscosity is compared. The viscometer used was a BH type rotational viscometer. Those that remained within 60% to 140% of the initial production viscosity were marked with ◯, and others were marked with x.

Curing time After preparation of the sample, the agent A and the agent B which were allowed to stand at 23 ° C. for 2 days were respectively stirred and mixed according to Table 1, and the width of 20 mm formed by holding two mortar plates 10 mm wide 40 mm long 40 mm at intervals of 20 mm Fill a joint with a length of 40 mm and a depth of 10 mm. The joint surface was smoothed with a spatula. Then, after curing for 15 hours at 23 ° C., the joints are bent by folding two mortar plates with the joints at the center, and the state of destruction of the cured product at that time is visually observed. When there were no abnormalities such as cracks and fractures, it was marked as ◯, and when abnormalities were found, it was marked as x.

Water resistance Agent A and Agent B, which were allowed to stand at 23 ° C. for 2 days after sample preparation, were respectively stirred and mixed according to Table 1, and cured into a sheet having a thickness of 4 mm. After curing at 23 ° C. for 14 days, the sample is cut into a length of 50 mm and a width of 50 mm, immersed in 50 ° C. warm water for 7 days, then immersed in 23 ° C. water and immediately taken out. Thereafter, the moisture adhering to the surface is wiped off with a waste cloth and the weight is measured. Compared with the weight before immersion in 50 ° C. warm water, the weight change rate is obtained. When the weight change rate was 10% or less, ◯ was marked, and over 10% was marked x.

Yellowing resistance After preparation of the sample, the agent A and the agent B, which were allowed to stand at 23 ° C. for 2 days, were respectively stirred and mixed according to Table 1, and cured into a sheet having a thickness of 4 mm. After curing at 23 ° C. for 14 days, cut into 50 mm length and 50 mm width, and expose to the south surface outdoors for 6 months at 45 ° angle. Then, visually compare the color tone with the cured pieces sealed and stored indoors in a cool and dark place. A sample in which yellowing was not observed was rated as ◯, and a sample in which yellowing was observed was marked as ×.

Evaluation results The evaluation results are shown in Table 1.

Claims (2)

  It comprises an organic polymer having a reactive silicon group, an agent A containing an epoxy group-containing compound, an amine compound, and an agent B containing a curing catalyst for the organic polymer having a reactive silicon group. A two-component curable joint composition. A two-component curable joint composition, wherein the amine compound is an amine compound having no cyclic portion or having no cyclic bond even if it has a cyclic portion.