CN101815770A - Adhesive set and bonding method using the same - Google Patents
Adhesive set and bonding method using the same Download PDFInfo
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- CN101815770A CN101815770A CN200880109669A CN200880109669A CN101815770A CN 101815770 A CN101815770 A CN 101815770A CN 200880109669 A CN200880109669 A CN 200880109669A CN 200880109669 A CN200880109669 A CN 200880109669A CN 101815770 A CN101815770 A CN 101815770A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Abstract
Disclosed is an adhesive set composed of a liquid A containing a first polymer having an alkyldialkoxysilyl group represented by the general formula (I) below at an end of a molecule, and a liquid B containing a second polymer having a trialkoxysilyl group represented by the general formula (II) below at an end of a molecule. This adhesive set is used by mixing the liquid A and the liquid B at such a ratio that the second polymer is not less than 0.07 part by weight relative to 100 parts by weight of the first polymer. -SiR2(OR1)2 (I) (In the formula (I), R1 represents an alkyl group having 1-6 carbon atoms, and R2 represents an optionally substituted alkyl group having 1-20 carbon atoms.) -Si(OR3)3 (II). In the formula (II), R3 represents an alkyl group having 1-6 carbon atoms.
Description
Technical field
The present invention relates to use the binding agent combination that binding agent, sealing material, coating-forming agent and coating etc. make and use this combination to carry out the agglutinating method.
Background technology
Exist the polymkeric substance of water-disintegrable silyl to be widely used in as so-called modified organic silicone resin in the binding agent and sealing material of a liquid ingredient type or two liquid ingredient types in molecular end.One liquid ingredient type is to add curing catalysts and other additive in modified organic silicone resin, and sealing is preserved, during use and airborne reaction of moisture and solidifying.And two liquid ingredient types are made up of host that contains modified organic silicone resin and solidifying agent, and the host that will separately pack during use and solidifying agent mix and airborne reaction of moisture and solidifying.
For example, have been proposed in and use the modified organic silicone resin that contains trimethoxysilyl in the liquid ingredient type, guarantee curing speed and the room-temperature-curable composition in work-ing life (patent documentation 1) faster.In addition, have been proposed in the silicone based Encapulant composition (patent documentation 2) of use deep layer solidified nature (inside solidification) through improving in the two liquid ingredient types.
[patent documentation 1] TOHKEMY 2006-63335 communique
[patent documentation 2] TOHKEMY 2001-172610 communique
Summary of the invention
Problem to be solved
Yet the work-ing life of an existing liquid ingredient type binding agent is still undesirable, also has difficulties aspect stability in storage.And with regard to two liquid ingredient types, though stability in storage is better than a liquid ingredient type, curing speed is slow, and inside solidification is undesirable.
Generally speaking, when using modified organic silicone resin, for promoting solidified nature such as curing speed and deep layer solidified nature, can increase the amount of solidifying catalytic materials, but cause operability bad, and owing to the existence of excessive curing catalytic materials causes weather resistance and weathering resistance (ageing resistance) to reduce owing to shortening work-ing life.In addition, for improving solidified nature, might sneak into moisture therein, or be mixed into hydrous matter, but can not fully solidify.This is to cause solidifying heterogeneity because moisture can not disperse fully in modified organic silicone resin, and this is to give that composition and moisture react and the interpolation of cohesiveness inequality, moisture causes reason such as curing catalysts inactivation to cause owing to bonding.
So present present situation is in the binding agent that has used modified organic silicone resin, no matter is a liquid ingredient type or two liquid ingredient types, all can not obtain curing speed is fast, have excellence inside solidification and the also excellent binding agent of stability in storage.
And the objective of the invention is to solve above-mentioned problem, provide curing speed fast, have the also excellent binding agent combination of excellent inside solidification and stability in storage and use this combination to carry out the agglutinating method.
Solve the method for problem
For solving above-mentioned problem, binding agent combined feature of the present invention is: by contain molecular end have the represented alkyl dialkoxy silyl of following general formula (I) the 1st polymkeric substance A liquid and contain the B liquid that molecular end has the 2nd polymkeric substance of the represented trialkoxysilyl of following general formula (II) and form, with following ratio A liquid and B liquid are mixed: with respect to the 1st polymkeric substance 100 weight parts, the 2nd polymkeric substance is more than 0.07 weight part.
-SiR
2(OR
1)
2 (I)
(wherein, R
1The expression carbonatoms is 1～6 alkyl, R
2It is 1～20 alkyl that expression can have substituent carbonatoms.)
-Si(OR
3)
3 (II)
(wherein, R
3The expression carbonatoms is 1～6 alkyl.)
In the present invention, all can contain colloid lime carbonate and water-ground limestone in A liquid and the B liquid as weighting agent.And in the mixed solution of A liquid and B liquid, the ratio of mixture of colloid lime carbonate and water-ground limestone (weight ratio) can be colloidal-carbon acid calcium/water-ground limestone=100～0.01.
In addition, use the adhesive method of binding agent combination of the present invention to be characterised in that: before being about to coating, to contain molecular end have the represented alkyl dialkoxy silyl of general formula (I) the 1st polymkeric substance A liquid and contain the following mixing of B liquid that molecular end has the 2nd polymkeric substance of the represented trialkoxysilyl of following general formula (II) and use: with respect to the 1st polymkeric substance 100 weight parts, making the 2nd polymkeric substance is more than 0.07 weight part.
The invention effect
Binding agent combination of the present invention is made up of with the B liquid that contains the 2nd polymkeric substance of trialkoxysilyl the A liquid of the 1st polymkeric substance that contains alkyl dialkoxy silyl, solidify by this A liquid and B liquid were mixed before being about to use, these are different with an existing liquid ingredient type and two liquid ingredient types.Can seek inside solidification speed according to the present invention and significantly improve, and curing speed improves and cause the time of occurrence of cohesive strength significantly to shorten, and further can guarantee the stability in storage of no problem in practicality.And, according to the present invention, can make the ratio of mixture of A liquid and B liquid adopt very wide scope compared with the past, so needn't strictly observe ratio of mixture, operability is largely increased.According to the present invention, only, just can reach performance (hardness, intensity, unit elongation, curing speed etc.), therefore as the final cured article of target by changing the composition (ratio) of B liquid, as long as the polymkeric substance with alkyl dialkoxy silyl is arranged, the composition of A liquid just is not particularly limited.It should be noted that in the present invention, except special instruction is arranged, blended " preceding " is meant before being about to use, A liquid and B liquid mix the time range that the back can be coated with or use as binding agent.
The best mode that carries out an invention
Binding agent combination of the present invention is made up of with the B liquid that contains the 2nd polymkeric substance of trialkoxysilyl the A liquid of the 1st polymkeric substance that contains alkyl dialkoxy silyl.
A liquid contains the 1st polymkeric substance that molecular end has the represented alkyl dialkoxy silyl of following general formula (I).
-SiR
2(OR
1)
2 (I)
Herein, R
1The expression carbonatoms is 1～6 alkyl, R
2It is 1～20 alkyl that expression can have substituent carbonatoms.Preferred alkyl dialkoxy silyl is methyl dimethoxy oxygen base silyl, methyl diethoxy silyl, more preferably methyl dimethoxy oxygen base silyl.
In addition, can use polyoxyalkylene and vinylic polymers in the main chain of the 1st polymkeric substance.With regard to polyoxyalkylene, can use by being selected from-CH
2CH
2O-,-CH
2CH (CH
3) O-,-CH
2CH (C
2H
5) O-,-CH (CH
3) CH
2O-,-CH (C
2H
5) CH
2O-,-CH
2CH
2CH
2O-reaches-CH
2CH
2CH
2CH
2The material that the repeating unit more than a kind of O-is formed.Preferably-CH
2CH (CH
3) O-.In addition, with regard to vinylic polymers, any two or more co-polymers as composition that can enumerate polyethylene, polypropylene, polyisobutene, poly-(methyl) acrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyhutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral acetal and contain these polymkeric substance etc.Wherein, preferred poly-(methyl) acrylate.The number-average molecular weight of preferred the 1st polymkeric substance is 1000～3000.
As the specific examples of the 1st polymkeric substance, can enumerate MS Polymer-S203, MSPolymer-S303, Sairil SAT350, Sairil SAT400 (above is the production of Kaneka Co., Ltd.), Excestar S2410, Excestar S2420, Excestar S3630 (above is Asahi Glass Co., Ltd's production) etc.
In A liquid, in order to promote the curing with moisture, but the blending curing catalysts.As curing catalysts, can be extensive use of existing known silanol condensation catalyst.As its specific examples, but titanate esters such as illustration tetrabutyl titanate, metatitanic acid orthocarbonate; Alkanoic acid tin classes such as dibutyl tin laurate, toxilic acid dibutyl tin, dibutyltin diacetate, stannous octoate, naphthenic acid tin, tin laurate, Off エ Le ザ チ Star Network acid ス ズ; The reactant of Dibutyltin oxide and phthalic ester; Dibutyl tin diacetyl acetonate; Organo-aluminium compound classes such as praseodynium aluminium, triethyl aluminium acetylacetonate, dipropoxy ethylacetoacetone(EAA,HEAA) aluminium; Inner complex classes such as tetrem acyl acetone zirconium, four titanium acetylacetones; Lead octoate 36; Iron naphthenate; The metal species catalyzer of bismuth compounds such as three neodecanoic acid bismuths, three (2 ethyl hexanoic acid) bismuth and so on.These metal species catalyzer can use separately, also can share two or more.In addition, also can use known amines catalysts such as lauryl amine.
In A liquid, can the agent of blending cohesiveness, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxy oxygen base silicomethane, γ-aminopropyl trimethoxy silicomethane, gamma-aminopropyl triethoxy silane, vinyl trimethoxy silicomethane, γ-glycidoxy propyl trimethoxy silicomethane, N-(β-aminoethyl)-γ-silane coupling agents such as aminopropyl trimethoxy silicomethane.Wherein preferred N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicomethane.
In A liquid, can use water-disintegrable silicon compounds such as methyl trimethoxy oxygen base silicomethane, vinyl methoxy methyl silane, tetramethoxy-silicane, tetraethoxy-silicane as dewatering agent.Preferred vinyl methoxy methyl silane.
In A liquid, be the raising mechanical characteristics, but the blending weighting agent.As packing material, can be extensive use of known in the past packing material, specifically can enumerate packing materials such as vapor deposition silicon-dioxide, precipitated silica, silicic anhydride, moisture silicic acid and carbon black, packing materials such as lime carbonate, magnesiumcarbonate, diatomite, chainotte, clay, talcum powder, titanium oxide, wilkinite, organobentonite, ferric oxide, zinc oxide, active zinc flower, hydrogenated castor oil and granulated glass sphere, and fibrous packing materials such as asbestos, glass fibre and long filament etc.
Preferred lime carbonate.Even a spot of lime carbonate can both promote viscosity.As lime carbonate, preferably combination is used colloid lime carbonate and water-ground limestone.Colloid lime carbonate can increase breaking tenacity, and water-ground limestone can increase by 50% modulus (50% モ ジ ユ ラ ス 50%modulus).Therefore, both share may increase breaking tenacity and 50% modulus simultaneously.It should be noted that, in B liquid, also can be added into weighting agent.That is, at least in a side of A liquid or B liquid absorb fillers get final product.Therefore, with regard to the ratio of mixture (mass ratio) of colloid lime carbonate and water-ground limestone, preferably in the mixed solution of A liquid and B liquid, add, make colloid lime carbonate/water-ground limestone=100～0.01, more preferably 10～0.1.
The median size of colloid lime carbonate is the particulate of submicron order, the water absorbability height, and compare with water-ground limestone and to be not easy dehydration.Therefore, the moisture that contains on producing of known colloid lime carbonate is more.So, even share the liquid ingredient type curable resin composition that the 1st polymkeric substance of alkyl dialkoxy silyl and the 2nd polymkeric substance that molecular end contains trialkoxysilyl prepare further use colloid lime carbonate that has used in the present invention, also cause stability in storage relatively poor, and can not use colloid lime carbonate because dehydration is insufficient.But, can pack respectively in the present invention, be A liquid with the 1st polymer packaging, be B liquid with the 2nd polymer packaging, even in weighting agent, use colloid lime carbonate thus, also can guarantee good preservation stability.
And, if necessary, can be in (A) of the present invention liquid suitably blending Resins, epoxy and solidifying agent, plasticizer, viscous modifier, other additive etc.
As Resins, epoxy, can be extensive use of known in the past material, for example can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, nonflammable Resins, epoxy such as the glycidyl ether of tetrabromo-bisphenol, phenol aldehyde type epoxy resin, the hydrogenation bisphenol A type epoxy resin, the Racemic glycidol ether type epoxy of bisphenol-A epoxy propane additive, Racemic glycidol-p-oxybenzene formic acid, o-phthalic acid diglycidyl ester, the tetrahydrophthalic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester based epoxy resins such as hexahydrophthalic acid 2-glycidyl ester, m-aminophenols Resins, epoxy, the diaminodiphenylmethane based epoxy resin, urethane-modified Resins, epoxy, various alicyclic ring based epoxy resins, N, the N-diglycidylaniline, N, N-diglycidyl-o-Tolylamine, isocyanuric acid three-glycidyl ester, the polyalkylene glycol diglycidylether, the diglycidylether of the polyvalent alcohol of glycerine etc., glycolylurea type Resins, epoxy, the epoxide of unsaturated polymers such as petroleum resin etc.In these Resins, epoxy,, reactive height and cured article easily generate aspect considerations such as tridimensional network during from curing, contain the Resins, epoxy of 2 epoxy group(ing) in the preferred molecule at least.As preferred Resins, epoxy, but illustration bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin and o-phthalic acid diglycidyl ester type Resins, epoxy.
As curing agent for epoxy resin, can be extensive use of known in the past hardener for epoxy resin, for example, Triethylenetetramine (TETA), tetren, diethyl amino propylamine, the N-aminoethyl piperazine, the m-dimethylphenylene diamine, the m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS), isophorone diamine, 2,4, the amine of 6-three (dimethylamino methyl) phenol etc., the tertiary amine salt, polyamide resin lipid, kitimine, the aldimine class, latent curing agents such as eneamines, imidazoles, the Dyhard RU 100 class, the boron trifluoride complex class, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, the tetrahydrochysene phthalate anhydride, endo-methylene group tetrahydrochysene phthalate anhydride (acid of エ Application De メ チ レ Application テ ロ ラ ヒ ド ロ No water Off タ Le), dodecenylsuccinic anhydride, the pyromellitic acid acid anhydride, carboxyanhydrides such as hexachloroendomethylene-tetrahvdrophthalic anhydride, alcohols, phenol, carboxylic-acid etc.
As plasticizer, can be extensive use of known in the past plasticizer, specifically can use following a kind or use following mixture more than 2 kinds separately: phthalates such as dioctyl phthalate (DOP), dibutyl phthalate, butyl benzyl phthalate; Alphatic carboxylic acid esters such as Octyl adipate, succsinic acid isodecyl ester, Uniflex DBS, butyl oleate; Glycol ester classes such as pentaerythritol ester; Phosphoric acid ester such as trioctyl phosphate, Tritolyl Phosphate; Epoxy plasticizers such as epoxidised soybean oil, epoxystearic acid benzyl ester; Clorafin etc.Can also use terminal-modified things such as polyoxygenated propylidene monohydroxy-alcohol, polyoxygenated propylidene dibasic alcohol etc.Terminal-modified thing can be enumerated and terminal hydroxyl is modified as the compound of alkoxyl group, alkene oxygen base and via amino-formate bond, ester bond, urea bond or the carbonic acid ester bond compound by alkyl sealing etc.
As viscous modifier, can enumerate jelling agents such as dibenzylidene sorbitol, tribenzylidene sorbitol, the cured lipid acid amination thing that waits of amine.
As other additive, for example can enumerate pigment, various antiaging agent, UV light absorber etc.
In addition,, also can use Sharpie ヘ Application セ イ SiliconM, Sharpie ヘ Application セ イ SiliconLM, binding agent and sealing materials such as Sharpie ダ Application セ イ ボ Application De MS+ (more than be シ ヤ one プ chemical industry Co., Ltd. produce) as A liquid.
The mixing proportion of each composition is as follows in the A liquid, per 100 weight parts the 1st polymkeric substance, blending curing catalysts 0.1～10 weight part, preferred 0.5～5 weight part, more preferably 1～3 weight part, dewatering agent 0.1～15 weight part, preferred 0.5～10 weight part, more preferably 1～5 weight part, bonding imparting agent 0.1～15 weight part, preferred 0.5～10 weight part, more preferably 1～7 weight part, packing material 0.1～300 weight part, plasticizer 1～150 weight part, viscous modifier 0.1～20 weight part.If necessary, blending Resins, epoxy 1～100 weight part, preferred 10～50 weight parts, per 100 weight part Resins, epoxy blending curing agent for epoxy resin, 1～200 weight part, preferred 10～100 weight parts.And the concentration of the 1st polymkeric substance in the A liquid is 10～50 weight %, preferred 20～40 weight %.
B liquid comprises molecular end and has the 2nd silica-based polymkeric substance of the represented tri-alkoxy of following general formula (II).
-Si(OR
3)
3 (II)
Herein, R
3It for carbonatoms 1～6 alkyl.The silica-based preferred use trimethoxy of tri-alkoxy is silica-based.
It should be noted that, on the main chain of the 2nd polymkeric substance, can use polyoxyalkylene.With regard to polyoxyalkylene, can use by being selected from-CH
2CH
2O-,-CH
2CH (CH
3) O-,-CH
2CH (C
2H
5) O-,-CH (CH
3) CH
2O-,-CH (C
2H
5) CH
2O-,-CH
2CH
2CH
2O-reaches-CH
2CH
2CH
2CH
2The material that the repeating unit more than a kind of O-is formed.Wherein, preferred-CH
2CH (CH
3) O-.
In the 2nd polymkeric substance, preferred trialkoxysilyl is a trimethoxysilyl, and the formation unit of polyoxyalkylene is the resin of oxypropylene group.Like this, intermiscibility, rapidly-curable and the transparency of resin with other is excellent.And number-average molecular weight is 500～30000, preferred 5000～20000.The specific examples of the 2nd polymkeric substance is Excestar-AX2551, Excestar-AX2851 (above produce for Asahi Glass Co., Ltd).
In order to adjust and the blending dispersion of A liquid and the flowability of mixture, the above-mentioned dewatering agent that in A liquid, uses, bonding imparting agent, weighting agent, plasticizer, weighting agent, viscous modifier, other additive, but for example pigment, various antiaging agent, UV light absorber etc. also blending in B liquid.
As B liquid, can only use the 2nd polymkeric substance, or use the material that in the 2nd polymkeric substance, adds various additives.When adding additive, the mixing proportion of various compositions is as follows in the B liquid, in per 100 weight parts the 2nd polymkeric substance, dewatering agent is 0～15 weight part, preferred 0.5～10 weight part, more preferably 1～5 weight part, the bonding imparting agent is 0～15 weight part, preferred 0.5～10 weight part, more preferably 1～7 weight part, packing material is 0～600 weight part, and plasticizer is 1～300 weight part, and viscous modifier is 0.1～20 weight part.In addition, the concentration of the 2nd polymkeric substance in the B liquid is 10～100 weight %, preferred 20～40 weight %.
In the present invention, the ratio of mixture of A liquid and B liquid need not strict regulation, can guarantee sufficient curing speed in the scope of wide ratio of mixture.With regard to A liquid and B liquid, preferably mix with the weight ratio of the 1st polymkeric substance and the 2nd polymkeric substance, make that the 2nd polymkeric substance is more than 0.07 weight part with respect to 100 parts of weight of the 1st polymkeric substance.If at this more than ratio, and only use A liquid as binding agent or only use B liquid to compare as the situation of binding agent, can significantly reduce surface drying time (ベ タ Star Network Off リ one タ イ system).More preferably with respect to the 1st polymkeric substance 100 weight parts, the 2nd polymkeric substance is more than 0.7 weight part, below 500 weight parts, more than further preferred 7 weight parts, below 100 weight parts.As be lower than 0.07 weight part, and then effect is insufficient, as adding more than 500 weight parts, accelerates though solidify, and curing reaction will begin rapidly and finish when two fluid components mix, so cohesive strength is prone to heterogeneity.Therefore, when this binding agent that uses interpolation more than 500 parts makes up, need special vent pipe and container.In addition, not only by changing the ratio of mixture of the 1st polymkeric substance and the 2nd polymkeric substance, also can reach the performance (hardness, intensity, unit elongation, curing speed etc.) of acquisition by changing the kind and the content of plasticizer and weighting agent as the final cured article of purpose.
Blending means as A liquid and B liquid, can enumerate (1) and use the method for the mouth of pipe blended automatization pipe of the special-purpose vent pipe that uses respectively at A liquid and B liquid, (2) in the special container that the static type nozzle is installed while extruding the blended method, (3) A liquid and B liquid are transferred in the proper container, use spatula etc. carries out the blended method, (4) directly on coated thing, smear A liquid and B liquid, carry out blended method etc. with spatula etc.In order to be easy to confirm that A liquid and B liquid are mixed fully, can be mutual distinct colors by for example adjusting A liquid and B liquid, by visual resolution admixture.
In addition, if the example to adhesive method carries out specific description, then can bond by the following method: before being about to use, A liquid and B liquid are mixed, make with respect to the 1st polymkeric substance 100 weight parts, the 2nd polymkeric substance is more than 0.07 weight part, to being coated with, each coated thing is pressed together by at least one side of the coated thing of being fitted.Or A liquid is coated with completely coated thing, and on coated thing, smear B liquid, make that the 2nd polymkeric substance is more than 0.07 weight part, each coated thing is pressed together bond with respect to the 1st polymkeric substance 100 weight parts.In above-mentioned arbitrary method, all need not strictly observe the blending ratio of A liquid and B liquid, so just can shorten working hours.
Embodiment 1
Use embodiment that the present invention is had been described in detail below, but the present invention is not limited to following embodiment.It should be noted that, " part " among the following embodiment, if no special instructions, expression be " weight part ".
(preparation of A liquid and B liquid)
A liquid: form shown in table 1-1, add 30 parts of MS Polymer S303 (or SairilSAT400 or ExcestarS420) and as 15 parts of the DOP of plasticizer, as weighting agent through 15 parts of 37 parts in the dewatered colloid lime carbonate of heat drying and water-ground limestones, use planetary stirrer (production of Kurabo company) to stir, mix.The mixture that obtains is cooled to room temperature, then add 1 part of vinyl trimethoxy silicomethane, add together as amino silicomethane N-(2-aminoethyl)-1.5 parts of the 3-aminopropyl trimethoxy silicomethanes of bonding imparting agent, as the reactant of the Dibutyltin oxide of curing catalysts and phthalic ester and stir, mix, obtain various A liquid as dewatering agent.Below, the modified organic silicone resin that uses in the A liquid is called the 1st modified organic silicone resin.
B liquid: form shown in table 1-1 and 1-2, add ExcestarAX2551 and as the DOP of plasticizer, as weighting agent through dewatered colloid lime carbonate of heat drying and water-ground limestone, use planetary stirrer to stir, mix.The mixture that obtains is cooled to room temperature, then adds, after stirring, mixing, obtain B liquid as 1 part of the vinyl trimethoxy silicomethane of dewatering agent.Below, the modified organic silicone resin that uses in the B liquid is called the 2nd modified organic silicone resin.
[table 1-1]
[table 1-2]
(evaluation of the tackify rate of A liquid and B liquid)
A liquid and B liquid are all measured viscosity the next day after preparation, as initial stage viscosity.Same blend was placed 7 down at 70 ℃, further measured viscosity after placing 1 down, and calculate the tackify rate according to following formula (I) at 23 ℃.
Several 1
The tackify rate=((70 ℃ of viscosity-initial stage viscosity of placing after 7 days)/initial stage viscosity) * 100 (%) (I)
Stability in storage is estimated following carrying out.
Zero: tackify rate less than 50%.
△: the tackify rate surpasses 50%.
*: be not easy to take out from container.
As show shown in the comparative example 1-3 of 1-1, the tackify rate of A liquid is 6～20%, surface drying time is 30～45 minutes.And for B liquid, shown in comparative example 8～10, the B-12 of not blending dewatering agent～14 are tackify after 70 ℃ of heating to can not viscometric degree, and solidify.In contrast, by blending dewatering agent, in B-1～10, though the 2nd modified organic silicone resin concentration more than 40%, do not reach yet can not viscometric degree high viscosity, and in container, do not solidify yet.And the surface drying time of B liquid is all more than 24 hours.Even add the bonding imparting agent in B liquid, shown in B-11, surface drying time is also all more than 24 hours.
In addition, also studied the 1st modified organic silicone resin and the 2nd modified organic silicone resin have been share comparative example 5～7 as a liquid ingredient type.The surface drying time of comparative example 5～7 is fast, be in 15 minutes, the blending ratio of the 1st modified organic silicone resin/the 2nd modified organic silicone resin is up to 9 degree, if do not reduce the ratio of the 2nd modified organic silicone resin, then tackify and solidifies to can not viscometric degree after 70 ℃ of heating.
According to The above results as can be known, can guarantee that by the blending dewatering agent A liquid and B liquid have sufficient stability in storage.
(inside solidification evaluation)
With the disposable beaker of PP measure A-1 as A liquid, as the B-1 of B liquid, making its weight ratio is 1: 1, use spatula to stir rapidly, mix, be packed into the junction of wide 10mm, high 10mm, every through specific time, use cutting knife to cut off the junction, measure cured thickness (mm) when observing the section state.
The result is as shown in table 2.According to following standard evaluation inside solidification.
◎: by solidifying more than the 10mm to 24 hours.
△: more than the 1-4 day after fixing 10mm.
*: solidifying 10mm needs more than 5 days.
It should be noted that, " curing " in the table 2 refers to the elastomeric state that is solidified into, and " pasty state " refers to the state of mixed liquid object just, and " tackify " refers to the intermediateness of " curing " and " pasty state ", completely solidified not, but obviously neither just mixed state.In the table, mixed with resin is meant the ratio of mixture (A)/(B) (weight ratio) of the modified organic silicon (B) of the modified organic silicon (A) of alkyl dialkoxy silyl end and trialkoxysilyl end than (A)/(B).
In comparative example 1～3 as the cured article that A liquid is only arranged, by solid state needs 96～120 hours to reaching completely, and in contrast, the cured article 12 hours of embodiment 1～3 of sneaking into B liquid in A liquid is with regard to completely solidified, compare with the situation of independent use A liquid, inside solidification raises greatly.
It should be noted that what comparative example 4 was represented is the example that adds the bonding imparting agent in comparative example 3.With the surface drying time of comparative example 3 is that 50 minutes surface drying time is compared, and the surface drying time of comparative example 4 significantly increases to 480 minutes.This shows that the imparting agent that bonds does not influence greatly inner solidified nature generation when A liquid is solidified separately, but effective on the minimizing surface drying time.On the other hand, embodiment 4 is the situation that A liquid and B liquid all do not add the bonding imparting agent.In this case, by A liquid and B liquid are mixed, can reduce surface drying time.That is, this shows in A liquid and B liquid blended the present patent application, though do not add the bonding imparting agent or addition few, can both reduce surface drying time.
[table 2]
(the ratio of mixture evaluation of A liquid and B liquid)
With the disposable beaker amount of PP according to weight ratio as shown in table 3 get A-3 as A liquid, as the B-1 of B liquid, use spatula to stir rapidly, mix, be packed into the junction of wide 10mm, high 10mm, every through specific time, use cutting knife to cut off the junction, when observing the section state, measure cured thickness.Measure surface drying time simultaneously.In addition, the mixture of each ratio is made the thick flat board of 3mm, after 7 days, measure dumbbell rerum natura (ダ Application ベ Le rerum natura) in 23 ℃ of slakings (Raising gives birth to curing).The result is as shown in table 3.
It should be noted that the evaluation of surface drying time is as described below.
◎: compare with the independent surface drying time of A liquid that uses, acknowledging time shortens more than 50%.
△: compare with the independent surface drying time of A liquid that uses, acknowledging time shortens less than 50%.
*: compare with the independent surface drying time of A liquid that uses, the time unconfirmed shortens.
[table 3-1]
[table 3-2]
(1) inside solidification
Completely solidified needs 120 hours when separately using A liquid, but shown in embodiment 5～7, if mix B liquid more than 7.5 parts with respect to 10 parts of A liquid, and completely solidified in 24 hours then.A liquid uses after 12 hours separately, only solidifies 1mm, and in contrast, shown in embodiment 13, even only mix 0.01 part of B liquid with respect to 10 parts of A liquid, promptly mixed with resin is 100 weight parts/0.07 weight part than (A)/(B), still can promote to be cured to 3.5mm.
(2) surface drying time
Surface drying time was 30～45 minutes when A liquid used separately, in contrast, as long as mix B liquid, all can shorten surface drying time.Particularly in embodiment 13, confirm the free effect that shortens.
(3) rerum natura of cured article
Compare with the independent cured article of A liquid, mix the cured article that obtains by A liquid and B liquid and all have high strength and high rigidity.Even mix B liquid below 10 parts with respect to 10 parts of A liquid, its elongation at break also is more than 400%, compares also not inferior performance even obtain with the independent cured article of A liquid.
According to above result as can be known, even do not strictly observe the ratio of mixture of A liquid and B liquid, also can give its rapidly-curable, hence one can see that, when giving rapidly-curable, can also in wide region, change the ratio of mixture of A liquid and B liquid, that is to say,, can not damage the performance of the cured article that obtains by A liquid and control inside solidification by changing the composition of B liquid.(effect of colloid lime carbonate)
With the disposable beaker of PP measure A-3 as A liquid, as the B-1 or the B-2 of B liquid, making its weight ratio is 10: 7.5, use spatula to stir rapidly, mix, be packed into the junction of wide 10mm, high 10mm, every through specific time, use cutting knife to cut off the junction, when observing the section state, measure cured thickness.Measure surface drying time simultaneously.The result is as shown in table 4.
[table 4]
The 2nd modified organic silicone resin amount in the B liquid of embodiment 14 and embodiment 15 is identical, the weight ratio (amount of the amount/water-ground limestone of colloid lime carbonate) of mixed colloid lime carbonate of A liquid and B liquid and water-ground limestone, being 60/38 in embodiment 14, is 37/60 among the embodiment 15.The embodiment 15 few with the amount of colloid lime carbonate compares, and the inside solidification of the embodiment 14 that the amount of colloid lime carbonate is many is better.Therefore, make the 2nd modified organic silicone resin amount in the B liquid identical, by changing the amount of colloid lime carbonate, may command inside solidification.(evaluation of the surface drying time when commercially available product and B liquid mix)
Use a commercially available liquid ingredient type binding agent and sealing agent as A liquid, use B-1 as B liquid, measure with the disposable beaker of PP, making its weight ratio is 10: 10, uses spatula to stir rapidly, mix, and measures surface drying time.The result is as shown in table 5.Employed commercially available product all is principal constituent with the modified organic silicone resin among the embodiment 16,17,19,20,21,22.In addition, the commercially available product of using among the embodiment 18 and 23 is principal constituent with organosilicon epoxy resin.
[table 5]
Shown in embodiment 16～23,,, also can significantly shorten surface drying time by mixing B liquid even A liquid uses commercially available product as long as contain modified organic silicone resin.
Utilize possibility on the industry
The novel binders combination of the problem that can solve existing two liquid component types and a liquid component type can be provided by the present invention. In the two liquid component types, as not strictly observing the mixing ratio of producer's appointment, solidfied material softness will occur, not solidify or opposite problem really up to the mark, and adopts the present invention just can not produce such problem. And can significantly promote storage stability as the problem of a liquid component type. In addition, in the building site, the working site such as civil engineering scene and factory's streamline, even strictly do not set mixing ratio, also can obtain required inside solidification and solidfied material rerum natura, can improve operability.
Claims (4)
1. binding agent combination, it is characterized in that, by contain molecular end have the represented alkyl dialkoxy silyl of following general formula (I) the 1st polymkeric substance A liquid and contain the B liquid that molecular end has the 2nd polymkeric substance of the represented trialkoxysilyl of following general formula (II) and form, with following ratio A liquid and B liquid are mixed: with respect to the 1st polymkeric substance 100 weight parts, the 2nd polymkeric substance is more than 0.07 weight part
-SiR
2(OR
1)
2 (I)
Wherein, R
1The expression carbonatoms is 1～6 alkyl, R
2It is 1～20 alkyl that expression can have substituent carbonatoms,
-Si(OR
3)
3 (II)
Wherein, R
3The expression carbonatoms is 1～6 alkyl.
2. the curable resin composition of claim 1 is characterized in that, A liquid and at least one side of B liquid are contained colloid lime carbonate and the water-ground limestone as weighting agent.
3. the curable resin composition of claim 2 is characterized in that, the colloid lime carbonate in the mixed solution of A liquid and B liquid and the ratio of mixture of water-ground limestone are colloid lime carbonate/water-ground limestone=100～0.01, and described ratio of mixture is a weight ratio.
4. adhesive method, it is characterized in that, before being about to coating, to contain molecular end have the represented alkyl dialkoxy silyl of following general formula (I) the 1st polymkeric substance A liquid and contain the following mixing of B liquid that molecular end has the 2nd polymkeric substance of the represented trialkoxysilyl of following general formula (II) and use: with respect to the 1st polymkeric substance 100 weight parts, making the 2nd polymkeric substance is more than 0.07 weight part
-SiR
2(OR
1)
2 (I)
Wherein, R
1The expression carbonatoms is 1～6 alkyl, R
2It is 1～20 alkyl that expression can have the substituting group carbonatoms,
-Si(OR
3)
3 (II)
Wherein, R
3The expression carbonatoms is 1～6 alkyl.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007254614A JP5178116B2 (en) | 2007-09-28 | 2007-09-28 | Adhesive set and bonding method using the same |
| JP2007-254614 | 2007-09-28 | ||
| PCT/JP2008/067379 WO2009041550A1 (en) | 2007-09-28 | 2008-09-26 | Adhesive set and bonding method using the same |
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| CN101815770A true CN101815770A (en) | 2010-08-25 |
| CN101815770B CN101815770B (en) | 2013-03-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102140268A (en) * | 2011-05-17 | 2011-08-03 | 欧美龙（南通）重防腐涂料有限公司 | Ship ballast tank anticorrosion solventless epoxy coating modifying additive and modified epoxy coating |
| CN104409549A (en) * | 2014-11-18 | 2015-03-11 | 苏州福斯特新材料有限公司 | High-efficiency black solar cell backplane and preparation method thereof |
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| JP5335507B2 (en) * | 2009-03-24 | 2013-11-06 | シャープ化学工業株式会社 | Bonding method |
| JP5599670B2 (en) * | 2010-07-27 | 2014-10-01 | シャープ化学工業株式会社 | Masking material and masking method using the same |
| CN113242897A (en) * | 2018-10-31 | 2021-08-10 | 美国陶氏有机硅公司 | Adhesive agent |
| JP7325077B2 (en) * | 2018-11-21 | 2023-08-14 | 積水フーラー株式会社 | Curable composition |
| CN109796927B (en) * | 2019-01-25 | 2021-10-19 | 杭州福斯特应用材料股份有限公司 | Quick-curing silicone structural adhesive and application thereof |
| WO2023127443A1 (en) * | 2021-12-27 | 2023-07-06 | 株式会社カネカ | Curable composition and cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3413453B2 (en) * | 1997-03-03 | 2003-06-03 | コニシ株式会社 | Silicone resin composition |
| JP3286749B2 (en) * | 1997-03-07 | 2002-05-27 | コニシ株式会社 | Silicone resin composition |
| EP0918062B1 (en) * | 1997-04-21 | 2004-02-18 | Asahi Glass Company Ltd. | Room temperature setting compositions |
| JP4493136B2 (en) * | 2000-01-21 | 2010-06-30 | コニシ株式会社 | Silicone contact adhesive |
| JP3464972B2 (en) * | 2000-08-31 | 2003-11-10 | コニシ株式会社 | Curable resin composition |
| CN1233771C (en) * | 2003-04-29 | 2005-12-28 | 中国印钞造币总公司 | Adhesive compound |
| WO2007094274A1 (en) * | 2006-02-16 | 2007-08-23 | Kaneka Corporation | Curable composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140268A (en) * | 2011-05-17 | 2011-08-03 | 欧美龙（南通）重防腐涂料有限公司 | Ship ballast tank anticorrosion solventless epoxy coating modifying additive and modified epoxy coating |
| CN102140268B (en) * | 2011-05-17 | 2013-04-10 | 欧美龙（南通）重防腐涂料有限公司 | Ship ballast tank anticorrosion solventless epoxy coating modifying additive and modified epoxy coating |
| CN104409549A (en) * | 2014-11-18 | 2015-03-11 | 苏州福斯特新材料有限公司 | High-efficiency black solar cell backplane and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| JP2009084386A (en) | 2009-04-23 |
| CN101815770B (en) | 2013-03-27 |
| WO2009041550A1 (en) | 2009-04-02 |
| JP5178116B2 (en) | 2013-04-10 |
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