CN103694712A - Curable composition and cured product of same - Google Patents

Curable composition and cured product of same Download PDF

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Publication number
CN103694712A
CN103694712A CN201310562135.2A CN201310562135A CN103694712A CN 103694712 A CN103694712 A CN 103694712A CN 201310562135 A CN201310562135 A CN 201310562135A CN 103694712 A CN103694712 A CN 103694712A
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composition
solidification compound
group
weight parts
weight
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CN103694712B (en
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川上敦史
笠井充弘
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

A curable composition which contains (A) a branched polyoxyalkylene polymer having a reactive silicon group, (C) calcium carbonate and (D) carbon black, and which is characterized in that the reactive silicon group is represented by general formula (1). -SiXnR3-n (1) (In the formula, X represents a hydroxyl group or a hydrolyzable group; R represents an optionally substituted monovalent organic group having 1-20 carbon atoms (excluding a hydrolyzable group); and n represents 1, 2 or 3. In cases where there are a plurality of X moieties, the X moieties may be the same as or different from each other. In cases where there are a plurality of R moieties, the R moieties may be the same as or different from each other.).

Description

Solidification compound and cured article thereof
Technical field
The present invention relates to contain solidification compound and the cured article thereof of the polyoxyalkylene polymers with reactive silicon group.
Background technology
Even if there is the polyoxyalkylene polymers of reactive silicon group for being at room temperature also solidified into elastomeric polymkeric substance with airborne reaction of moisture, in industrial production, be widely used in the purposes of sealing material, caking agent etc.
In addition, as the similar polymkeric substance of the polyoxyalkylene polymers with having reactive silicon group, also known have as having imported the polymkeric substance of reactive silicon group, so-called silylated polyurethane to carbamate prepolymer.
In thering is the polyoxyalkylene polymers of reactive silicon group, added the solidification compound of softening agent, weighting agent, stablizer, curing catalysts etc. such as being disclosed in patent documentation 1, patent documentation 2, patent documentation 3 etc.The solidification compound of these patent documentations can be applicable to sealing material purposes.
Prior art document
Patent documentation
Patent documentation 1CN1995140A communique
Patent documentation 2CN102086366A communique
Patent documentation 3CN102994034A communique
Summary of the invention
Invent problem to be solved
In the situation that the solidification compound that contains the polyoxyalkylene polymers with reactive silicon group is used in caking agent purposes, the excellences such as the physical property that need to stretch (tensile stress, tensile break strength, tension fracture elongation rate), bonding strength, need tensile break strength high especially.Yet in the situation that the solidification compound of recording in above-mentioned patent documentation is applied to caking agent purposes, tensile break strength etc. is insufficient sometimes.Therefore,, in order to be applied to caking agent purposes, expectation has the solidification compound of higher tensile break strength.
The object of the invention is to, the rising that the excellent and then tensile shear strength of tensile break strength is provided is the excellent solidification compound that can be applicable to industrial sealing material, industrial caking agent also.
For solving the means of problem
The inventor etc., in order to solve above-mentioned problem, concentrate on studies, found that, by use, contain chain polyoxyalkylene polymers that (A) have reactive silicon group, straight chain shape polyoxyalkylene polymers that (B) has reactive silicon group, (C) calcium carbonate and (D) solidification compound of carbon black, can solve above-mentioned problem, so that completed the present invention.
That is, the present invention relates to:
(1). a kind of solidification compound, it is characterized in that, it has a chain polyoxyalkylene polymers, (C) calcium carbonate of reactive silicon group and (D) solidification compound of carbon black for containing (A),
Reactive silicon group is represented by following general formula (1).
-SiX nR 3-n...(1)
(in formula, X represents hydroxyl or hydrolization group, and R represents to have the organic group (wherein, not comprising hydrolization group) of 1 valency of substituent carbon number 1～20.N represents 1,2 or 3.When X is a plurality of, X can be identical or different mutually.When R is a plurality of, R can be identical or different mutually.)
(2). the solidification compound as described in (1), it also contains the straight chain shape polyoxyalkylene polymers that (B) has the reactive silicon group being represented by above-mentioned general formula (1).
(3). the solidification compound as described in (1) or (2), it is characterized in that, (A) composition and (B) mixture ratio of composition with weight ratio, count 100/0～5/95.
(4). the solidification compound as described in any one of (1)～(3), it is characterized in that, (A) composition and (B) mixture ratio of composition with weight ratio, count 100/0～60/40.
(5). the solidification compound as described in any one of (1)～(4), it is characterized in that, (D) oil number of composition is more than 50ml/100g.
(6). the solidification compound as described in any one of (2)～(5), it is characterized in that, (A) composition and/or (B) number-average molecular weight of composition be respectively 15,000～50,000 and/or (A) composition and (B) number-average molecular weight of the mixture of composition be 15,000～50,000.
(7). the solidification compound as described in any one of (1)～(6), it is characterized in that, (C) composition be selected from water-ground limestone, precipitated chalk and by these calcium carbonate carried out in surface-treated calcium carbonate more than at least a kind.
(8). the solidification compound as described in any one of (1)～(7), it is characterized in that, (C) composition is the calcene below median size 1 μ m.
(9). the solidification compound as described in any one of (1)～(8), it is characterized in that, with respect to (A) composition and (B) total 100 weight parts of composition, contain (C) composition 60～200 weight parts, (D) composition 20～50 weight parts.
(10). a kind of cured article, it is solidification compound described in any one of (1)～(9) to be solidified form.
The effect of invention
The tensile break strength of the cured article of solidification compound of the present invention is excellent, and then the rising of tensile shear strength is also excellent.In addition, can be applicable to caking agent purposes.
Embodiment
Below, the present invention is at length described.
The solidification compound the present invention relates to, is characterized in that, contains chain polyoxyalkylene polymers that (A) have reactive silicon group, (C) calcium carbonate and (D) carbon black.
Solidification compound also can also contain the straight chain shape polyoxyalkylene polymers that (B) has reactive silicon group.
(A) there is a chain polyoxyalkylene polymers of reactive silicon group and (B) there is the reactive silicon group that the straight chain shape polyoxyalkylene polymers of reactive silicon group has, by following general formula (1), being represented.
-SiX nR 3-n...(1)
In formula (1), X represents hydroxyl or hydrolization group, and R represents to have the organic group (wherein, not comprising hydrolization group) of 1 valency of substituent carbonatoms 1～20.N represents 1,2 or 3.When X is a plurality of, X can be identical or different mutually.When R is a plurality of, R can be identical or different mutually.
As R, preferably the alkyl of carbon number 1～20 is, the aralkyl of the aryl of carbon number 6～20, carbon number 7～20, the particularly preferably alkyl of carbon number 1～20.As the concrete example of R, can enumerate methyl, ethyl, cyclohexyl, phenyl, benzyl, methoxymethyl, chloromethyl, R ' for the R ' of methyl, phenyl etc. 3three organic siloxyies shown in SiO-etc.Wherein, more preferably methyl, ethyl.
As hydrolization group, such as enumerating halogen atom, alkoxyl group, acyloxy, alkene oxygen base etc.As the concrete example of hydrolization group, can enumerate methoxyl group, oxyethyl group, isopropoxy, methoxymethyl, chloromethyl etc.Wherein, more preferably methoxyl group, oxyethyl group.
As the concrete example of reactive silicon group, can enumerate dimethoxy-methyl silyl, diethoxymethyl silyl, diisopropoxy methyl-silicane base, (chloromethyl) dimethoxy silyl, (methoxymethyl) dimethoxy silyl, trimethoxysilyl, triethoxysilyl etc.Wherein, because dimethoxy-methyl silyl, diethoxymethyl silyl can obtain having the cured article of good mechanical properties, therefore preferably, dimethoxy-methyl silyl particularly preferably.
(A) composition and (B) main chain backbone of composition, preferably by the repeating unit shown in general formula (2).
-R 1-O-...(2)
In its Chinese style, R 1the straight chain shape or the chain alkylidene group that represent carbonatoms 1～14.
As general formula (2), for example, can enumerate-CH 2o-,-CH 2cH 2o-,-CH 2cH (CH 3) O-,-CH 2cH (C 2h 5) O-,-CH 2c (CH 3) 2o-,-CH 2cH 2cH 2cH 2o-etc.
The in the situation that at (A) composition and (B) composition being used in sealing agent or caking agent purposes, as main chain backbone, preferably have more than 80 % by weight by-CH 2cH (CH 3) propylene oxide units shown in O-, more than more preferably containing 90 % by weight.
In the situation that manufacture conduct (A) composition and (B) polyoxyalkylene polymers of the main chain backbone of composition, from the viewpoint of obtaining the polymkeric substance of narrow molecular weight distribution, preferably under the existence of composition metal cyanide complex catalyst, make the polymerization process of epoxy alkane and initiator for reaction.
As composition metal cyanide complex catalyst, can enumerate by Zn 3[Co (CN) 6] 2six shown cyano group cobalt acid zinc complexes etc.The catalyzer that in addition, also can use at least a kind of compound in ether compounds such as alkylol cpds such as being selected from the trimethyl carbinol, glycol dimethyl ether, diglyme, triglyme etc. to form as coordinations such as organic ligand and six cyano group cobalts acid zinc complexes.
The compound preferably for the synthesis of the initiator of (A) composition with 3～6 active hydrogens, more preferably has the compound of 3～4 active hydrogens, particularly preferably has the compound of 3 active hydrogens.As the functional group with active hydrogen, particularly preferably hydroxyl.
As the concrete example of the initiator for the synthesis of (A) composition, can enumerate the polyvalent alcohols such as glycerine, TriMethylolPropane(TMP), tetramethylolmethane, glucose, Sorbitol Powder.In addition, also can use with the molecular weight of (A) composition and be in a ratio of polyoxy alkylidene triol of lower molecular weight and number-average molecular weight 500～20,000 etc.
The compound preferably for the synthesis of the initiator of (B) composition with 2 active hydrogens.As the functional group with active hydrogen, particularly preferably hydroxyl.
As the concrete example of the initiator for the synthesis of (B) composition, can enumerate the dibasic alcohol of ethylene glycol, glycol ether, propylene glycol etc.In addition, also can use with the number-average molecular weight of (B) composition and be in a ratio of polyether polyols of lower molecular weight and number-average molecular weight 500～20,000 etc.
As the concrete example of epoxy alkane, can enumerate oxyethane, propylene oxide, epoxy Trimethylmethane etc.
The method that to (A) composition and (B) main chain backbone of composition imports reactive silicon group for example can be undertaken by known method shown below.
(i) terminal hydroxyl of polyoxyalkylene polymers refined and after form-OM (M is basic metal), it reacted with the halohydrocarbon that contains unsaturated group (chlorallylene and/or methallyl chloride) and manufacture unsaturated group end polyoxyalkylene polymers.Then, make this unsaturated group with by HSiX nr 3-n(X, R, n are identical with X, R, the n of above-mentioned general formula (1).) shown in organoalkoxysilane effect and carry out hydrosilylation, import thus the method for reactive silicon group.
(ii) method that the unsaturated group of the polyoxyalkylene polymers of the unsaturated group end that similarly obtains with (i) is reacted with hydrosulphonyl silane compound.
(iii) method that the terminal hydroxyl of polyoxyalkylene polymers is reacted with isocynate silane compound.
(iv) make the terminal hydroxyl of polyoxyalkylene polymers react with polyisocyanate compound and terminal hydroxyl is become after isocyanate group, the method that this isocyanate group is reacted with isocynate silane compound and/or amino silane compounds.
Wherein, (ii) method exists the stink based on hydrosulphonyl silane compound to become the situation of problem, (iii) there is the situation that viscosity uprises, workability becomes problem of the polymkeric substance obtaining in method and (iv), in addition, exists stability in storage to become the situation of problem.Therefore, in these methods, the method for (i) particularly preferably.
(A) composition and (B) number-average molecular weight of composition in GPC conversion molecular weight, respectively preferably 15,000～50,000, more preferably 17,000～45,000, further preferably 18,000～40,000, particularly preferably 19,000～35,000, most preferably 21,000～35,000.Number-average molecular weight is lower than 15,000 o'clock, has the tension fracture elongation rate of the cured article the obtaining inadequate tendency that becomes.Number-average molecular weight surpasses at 50,000 o'clock, because reduction, the viscosity of the curing speed of solidification compound uprises, therefore, the tendency in workability variation.
(A) composition and (B) number-average molecular weight of the mixture of composition in GPC conversion molecular weight, preferably 15,000～50,000, more preferably 17,000～45,000, further preferably 18,000～40,000, particularly preferably 19,000～35,000, most preferably 21,000～35,000.Lower than 15,000 o'clock, there is the inadequate tendency of tension fracture elongation rate of the cured article obtaining in number-average molecular weight.Number-average molecular weight surpasses at 50,000 o'clock, because the curing speed of solidification compound reduces and viscosity uprises, therefore, the tendency in workability variation.
(A) composition and (B) number-average molecular weight of composition can be used as be equivalent to by import the measuring method of hydroxyl value based on JIS K1557 of polymer precursor utilization before reactive silicon group and the iodine number of JIS K0070 measuring method titrimetry and the molecular weight (terminal group molecular weight) of the number-average molecular weight obtained is obtained.
In addition, also can be used as by (A) composition and (B) components utilising GPC measure and the polystyrene conversion molecular weight (GPC conversion molecular weight) obtained is obtained.
(A) the reactive silicon group number of composition, preferred 1.5～3 of average out in 1 Molecularly Imprinted Polymer, more preferably average out to is 1.7～3, further preferred 1.8～2.8 of average out to, particularly preferably average out to is 1.9～2.7, and most preferably average out to is 2.0～2.5.During on average lower than 1.5, there is the tensile break strength of the cured article inadequate tendency that becomes.On the other hand, while on average surpassing 3, there is the tension fracture elongation rate of the cured article inadequate tendency that becomes.
(B) preferred 1.1～2 of the average out in 1 Molecularly Imprinted Polymer of the reactive silicon group number of composition, more preferably average out to is 1.2～1.9, further preferred 1.3～1.8 of average out to, particularly preferably average out to is 1.4～1.7.During on average lower than 1.1, the curing of solidification compound becomes insufficient sometimes.In addition, there is the tensile break strength of the cured article inadequate tendency that becomes.On the other hand, while on average surpassing 2, there is the tension fracture elongation rate of the cured article inadequate tendency that becomes.
(A) composition and (B) mean number of the reactive silicon group of composition, can be used as to utilize the proton on the carbon of reactive silicon group Direct Bonding used to high de-agglomeration energy 1h-NMR equipment carries out quantitative method and obtains mean number and obtain.
In the calculating of the mean number of the reactive silicon group in polymkeric substance in the present invention, when importing reactive silicon group to precursor polymer, the polymkeric substance that does not import the precursor polymer of reactive silicon group and obtained by side reaction is also regarded a part for the polyoxyalkylene polymers with reactive silicon group with identical backbone structure as, in the population parameter (female number) (molecule number) while being included in the mean number in 1 molecule that calculates reactive silicon group, calculates.
(A) composition and/or (B) reactive silicon group of composition, can be present in the inside of molecular chain with the form of side chain, also may reside in the end of molecular chain.For sealing agent, caking agent purposes etc. in the situation that, from the viewpoint of stretching physical property, cementability, more preferably reactive silicon group is present in the end of molecular chain.
From the viewpoint of reducing the viscosity of the solidification compound obtain, (A) composition and/or (B) molecular weight distribution of composition (Mw/Mn) is preferably narrower, preferably below 1.6, more preferably below 1.5, particularly preferably below 1.4.
(A) composition and (B) composition, can distinguish separately and use, and also two or more kinds may be used.
(A) composition and (B) mixture ratio of composition (A/B), preferably count 100/0～5/95 with weight ratio.
From the viewpoint of the rising of tensile break strength or tensile shear strength, (A) composition and (B) preferred lower limit of the scope of the mixture ratio of composition, for A/B >=40/60, more preferably A/B >=50/50, more preferably A/B >=60/40, be particularly preferably A/B >=70/30, most preferably be A/B >=85/15.From the viewpoint of tensile break strength, be limited to 80/20 >=A/B, 100/0 >=A/B more preferably on preferred, from the viewpoint of the rising of tensile shear strength, be limited to 100/0 >=A/B on preferably.(A), when composition is lower than 40 % by weight of polyalcohol integral, sometimes cannot obtain the rising of sufficient tensile shear strength.
In addition, from the viewpoint of tension fracture elongation rate, (A) composition and (B) mixture ratio of composition (A/B), in weight ratio, preferably 95/5～5/95.Under the scope of mixture ratio preferred, be limited to A/B >=10/90, more preferably A/B >=15/85, be particularly preferably A/B >=25/75, most preferably be A/B >=40/60, be limited on preferred 90/10 >=A/B, more preferably 85/15 >=A/B, be particularly preferably 75/25 >=A/B, most preferably be 60/40 >=A/B.By (A) composition and (B) mixing of composition use, can obtain stretching physics value than distinguish independent use (A) composition and (B) composition and the stretching physics value simple average that obtains and tensile break strength and the tension fracture elongation rate of the value excellence obtained.
(A) composition and (B) mixture of composition, by synthesizing respectively (A) composition and (B) mixing to obtain after composition.In addition, also can by first will the initiator of (A) composition and (B) initiator of composition with the ratio of expectation, mix, the material obtaining is used as to initiator and synthesizes to obtain mixture.It should be noted that, in the present invention, used the initiator of mixing (A) composition and (B) initiator of the initiator of composition and the polyoxyalkylene polymers that there is reactive silicon group, comprises branched structure and linear chain structure of having synthesized as (A) composition and (B) mixture of composition process.
In the present invention, as weighting agent, coordinate (C) calcium carbonate.Calcium carbonate can use be selected from water-ground limestone, precipitated chalk and by these calcium carbonate carried out in surface-treated calcium carbonate more than at least a kind.
Precipitated chalk is categorized as light calcium carbonate and the calcene below median size 1 μ m more than major diameter 1 μ m, but can use calcium carbonate arbitrarily.Wherein, from the viewpoint of obtaining good mechanics physical property, preferably use calcene.
Also can use and carry out surface-treated calcene in addition.As surface treatment agent, resinous acid, paraffin, polyethylene wax, the positively charged ion that can enumerate the lipid acid, fatty acid ester, modified fat acid, rosin etc. of stearic acid etc. are tensio-active agent etc.
Wherein preferably carry out surface-treated calcene, particularly preferably carried out the acid-treated calcene of fatty acid treatment or resin.
As the median size of calcene, more preferably below 0.5 μ m, further preferably below 0.2 μ m, 0.02～0.1 μ m particularly preferably.
Calcene, such as can be with the form acquisition of the commercially available product of calcene CCR, calcene CC, calcene O, Calmos, Vigot10 (being Bai Shi カ Le シ ウ system (strain) system), Neolight SP (the former chemical industry of bamboo (strain) system) etc.
The median size of water-ground limestone is 0.3～10 μ m preferably, more preferably 0.7～7 μ m, particularly preferably 0.7～5 μ m, most preferably 1.1～4 μ m.During lower than 0.3 μ m, the viscosity in solidification compound uprises, the tendency of workability variation.While surpassing 10 μ m, in obtaining the tendency of sufficient cementability.
In addition, also can use and carry out surface-treated water-ground limestone.As surface treatment agent, lipid acid, fatty acid ester, modified fat acid, paraffin, polyethylene wax, the positively charged ion that can enumerate stearic acid etc. are tensio-active agent etc.
Water-ground limestone, such as obtaining with the form of the commercially available product of SS-88, NS-100, NS-400, NS-600, NS-1000, NS-2300, NS-2500, NCC-110, NCC-410, NCC-610, NCC-1010, NCC-2510, NEW-F, NCC-P (being FORMOSA PLASTICS CORPORATION system) etc.
(C) composition can be used separately, and also two or more kinds may be used.
(C) usage quantity of composition preferably with respect to (A) composition and (B) total 100 weight parts of composition be 60～200 weight parts, more preferably 100～180 weight parts, further preferably 120～180 weight parts, particularly preferably 130～170 weight parts.
It should be noted that, although the use of water-ground limestone in the present invention has the effect of the viscosity that reduces solidification compound, sometimes cannot improve fully the tensile break strength of cured article.Therefore the usage quantity of water-ground limestone is preferably few than precipitated chalk, more preferably with respect to (A) composition and (B) total 100 weight parts of composition lower than 10 weight parts, in the present invention, particularly preferably do not use.
In the present invention, in order to obtain the rising of tensile break strength and tensile shear strength, need to coordinate (D) carbon black.
(D) composition can be used the material obtaining by known method for making.For example can enumerate the furnace black that obtains by Audit For Process or steam stove method, dim, channel black, channel black, pyrolytic carbon black, acetylene black.From the viewpoint of acquired, the carbon black that preferably oven process of the main flow by the method for making as present obtains.
(D) oil number of composition (value of being measured by the absorbed dose of dibutyl phthalate (DBP) according to JIS K6217 (ISO4656)) is preferably more than 50ml/100g, more preferably 50～150ml/100g, further preferred 50～130ml/100g, further more preferably 70～120ml/100g, particularly preferably 90～120ml/100g.During lower than 50ml/100g, in obtaining the tendency of sufficient tensile break strength.While surpassing 150ml/100g, the viscosity in solidification compound uprises, the tendency of workability variation.
(D) concrete example of composition can obtain with the form of the commercially available product of HIBLACK30, HIBLACK10, HIBLACK5L, HIBLACK20L, HIBLACK30L (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system) etc.
(D) composition can be used separately, and also two or more kinds may be used.
(D) usage quantity of composition preferably with respect to (A) composition and (B) total 100 weight parts of composition be 5～50 weight parts, more preferably 10～50 weight parts, further preferably 20～50 weight parts, particularly preferably 20～45 weight parts.During lower than 5 weight part, in obtaining the tendency of sufficient tensile break strength.While surpassing 50 weight part, in following tendency: because viscosity uprises, so workability variation maybe cannot be made solidification compound.
In solidification compound of the present invention, also can be at other the weighting agent of range fit that does not damage the physical property of cured article.As other weighting agent, can enumerate aerosil, the bat wool of the toner of the enhancement filler of precipitated silica, crystallinity silicon-dioxide, fused silica, calcined clay, clay and kaolin etc., rhombspar, anhydrous silicic acid, moisture silicic acid, magnesiumcarbonate, diatomite, talcum, titanium oxide, wilkinite, organobentonite, ferric oxide, aluminium micropowder, zinc oxide, active zinc white, PVC powder and PMMA powder etc., glass fibre etc. etc.
In solidification compound of the present invention, in order to promote (A) composition and/or (B) solidifying of composition, can coordinate curing catalysts.As curing catalysts, can enumerate organo-tin compound, carboxylic acid, carboxylic metallic salt, amine compound etc.
Organo-tin compound, can enumerate dibutyl tin laurate, toxilic acid dibutyl tin, phthalic acid dibutyl tin, two sad dibutyl tins, two (2 ethyl hexanoic acid) dibutyl tin, two (methyl-maleic acid) dibutyl tin, two (ethyl toxilic acid) dibutyl tin, two (butyl toxilic acid) dibutyl tin, two (octyl group toxilic acid) dibutyl tin, two (tridecyl toxilic acid) dibutyl tin, two (benzyl toxilic acid) dibutyl tin, dibutyltin diacetate, two (ethyl toxilic acid) dioctyl tin, two (octyl group toxilic acid) dioctyl tin, dibutyl dimethoxy tin (ジ Block チ Le WU ジ メ ト キ サ イ De), two (Nonylphenoxy) tin (ジ Block チ Le WU PVC ス (ノ ニ Le Off エ ノ キ サ イ De)) of dibutyl, oxidation dibutene base tin, dibutyltin oxide, two (acetyl acetone) dibutyl tin, two (ethylacetoacetone(EAA,HEAA) closes) dibutyl tin, the reactant of dibutyltin oxide and silicate ester compound or silicate compound, the reactant of dibutyltin oxide and phthalic ester, dioctyl dimethoxy tin (ジ オ Network チ Le WU ジ メ ト キ サ イ De), di-n-octyltin oxide, two (acetyl acetone) dioctyl tin, the reactant of di-n-octyltin oxide and silicate ester compound or silicate compound, the reactant of di-n-octyltin oxide and phthalic ester etc.
Carboxylic acid can be enumerated neodecanoic acid, tertiary monocarboxylic acid, 2, and 2-dimethyl is sad, 2-ethyl-2,5-dimethyl caproic acid etc.
Carboxylic metallic salt can be enumerated carboxylic acid tin, carboxylic acids of lead, bismuth carboxylate, carboxylic acid potassium, calcium carboxylates, carboxylic acid barium, carboxylic acid titanium, carboxylic acid zirconium, carboxylic acid hafnium, carboxylic acid vanadium, manganese carboxylate, ferric carboxylate, carboxylic acid cobalt, nickel carboxylate, carboxylic acid cerium etc.
Amine compound can be enumerated lauryl amine, diethylamino propyl group amine, guanidine, diphenylguanidine, 1,8-diazabicyclo (5,4,0) undecylene-7 (DBU) etc.
In above-mentioned, dibutyl tin compound, dioctyl tin compound are owing to can showing soon intensity, therefore preferably.
The usage quantity of curing catalysts, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.05～20 weight part, more preferably 0.1～15 weight part, further preferred 0.5～10 weight part, particularly preferably 1～7 weight part, most preferably 1.5～5 weight parts.If lower than 0.05 weight part, in the slack-off tendency of curing speed.On the other hand, if surpass 20 weight parts, because curing speed became slow, therefore, cannot obtain good cured article.
In solidification compound of the present invention, can add softening agent.By the interpolation of softening agent, can adjust the viscosity, slump of solidification compound and solidification compound be solidified and the mechanical characteristics of the tensile strength of the cured article that obtains, elongation etc.As the example of softening agent, can enumerate the phthalate of dibutyl phthalate, diheptyl phthalate, phthalic acid two (2-ethylhexyl) ester, butyl benzyl phthalate etc.; The non-aromatic diester class of Octyl adipate, dioctyl sebacate, Uniflex DBS, succsinic acid two isodecyl esters etc.; The aliphatic ester of butyl oleate, methyl acetylricinolate etc.; The phosphoric acid ester of Tritolyl Phosphate, tributyl phosphate etc.; Trimellitate class; Clorafin class; The hydrocarbon system oil of alkyl biphenyl, partially hydrogenated terphenyl etc.; Operation oils; The epoxy plasticizer class of epoxidised soybean oil, epoxystearic acid benzyl ester etc. etc.In addition, also can use the compound that phthalic ester is carried out to hydrogenation and obtain.This compound by BASF AG with trade(brand)name: the form of Hexamoll DINCH, in industrial manufactured sale, also easily obtains.
In addition, can use polymeric plasticizer.While using polymeric plasticizer, the softening agent that does not contain component of polymer with use in molecule is that the situation of simple plasticizer is compared, the physical property at long term maintenance initial stage.As polymeric plasticizer, can enumerate the vinyl based polymer that ethene base system monomer is ined all sorts of ways and carries out polymerization and obtain; The ester class of the polyalkylene glycol of diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester etc.; The polyester being obtained by dibasic alcohol such as the diprotic acid of sebacic acid, hexanodioic acid, nonane diacid, phthalic acid etc. and ethylene glycol, glycol ether, triethylene glycol, propylene glycol, dipropylene glycols is softening agent; The polyether glycol of the polyoxyethylene glycol by molecular weight more than 500 and then more than 1000, polypropylene glycol, polytetramethylene glycol etc. or the hydroxyl of these polyether glycols become the polyethers such as derivative of ester group, ethyl etc.; The polystyrene type such as polystyrene, Poly-alpha-methylstyrene; Polyhutadiene, polybutene, poly-isobutyl diene, butadiene-acrylonitrile, sovprene etc.
Wherein, good from the viewpoint of the deep solidified nature of solidification compound, more preferably polyether plasticizer.The number-average molecular weight of polyether plasticizer, preferably 500～15,000, more preferably 800～10,000, particularly preferably 1,000～5,000.If molecular weight, softening agent flows out, and cannot maintain good physical property.In addition, if molecular weight is excessive, viscosity uprises, workability variation.Polyethers is the molecular weight distribution preferred narrow of softening agent, preferably lower than 1.8, more preferably below 1.6, particularly preferably below 1.4.It should be noted that, polyether plasticizer also can have reactive silicon group.Now, composition is little, reactive silicon group number is also few than (A) composition and (B) for preferred number average molecular weight.
Softening agent can be used separately, and also two or more kinds may be used.
The usage quantity of softening agent, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 5～150 weight parts, more preferably 10～120 weight parts, particularly preferably 20～100 weight parts.During lower than 5 weight part, cannot show the effect as softening agent, if surpass 150 weight parts, the physical strength of cured article is not enough.
In solidification compound of the present invention, can coordinate tackifier.Tackifier can be enumerated gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, gamma-amino propyl group dimethoxy-methyl silane, gamma-amino propyl group diethoxymethyl silane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, N-(beta-aminoethyl)-gamma-amino propyl group dimethoxy-methyl silane, N-(beta-aminoethyl)-γ aminopropyltriethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl group diethoxymethyl silane etc. containing amino silane compounds, containing isocyanato silanes compound, containing hydrosulphonyl silane compound, containing epoxy radicals silicone hydride compound, contain (methyl) acryl silane compound etc.Wherein, from the viewpoint of cementability, more preferably containing amino silane compounds.
The usage quantity of tackifier, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～20 weight part, 0.5～10 weight part particularly preferably.
In addition, from the viewpoint of the cementability with ceramic coating glass, preferably with respect to composition in its entirety (100 % by weight), coordinate the amino silane compounds that contains of 1.0～6.0 % by weight, more preferably coordinate 1.2～6.0 % by weight, further preferably coordinate 1.2～5.0 % by weight, particularly preferably coordinate 1.3～4.0 % by weight.
In solidification compound of the present invention, for the object that improves the surperficial weathering resistance of cured article, can combined with ultraviolet radiation absorption agent.As UV light absorber, can illustration benzophenone series, benzotriazole system, salicylate system, replace toluene base system and metallo-chelate based compound etc., but benzotriazole system particularly preferably.Benzotriazole system can obtain with the form of the commercially available product of Tinuvin P, Tinuvin1130, Tinuvin99-2, Tinuvin928, Tinuvin326, Tinuvin329 (BASF AG's system) etc.
The usage quantity of UV light absorber, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～10 weight part, more preferably 0.2～5 weight part.
In solidification compound of the present invention, for the object that prevents the photo-oxidative degradation of cured article, can coordinate photostabilizer.As photostabilizer, can illustration benzotriazole system, hindered amine system, benzoic ether based compound etc., but hindered amine system particularly preferably.Hindered amine system, can obtain with the form of the commercially available product of Tinuvin770, Tinuvin770DF, Tinuvin292, Tinuvin5050, Tinuvin5151, Tinuvin5060 (BASF AG's system) etc.
The usage quantity of photostabilizer, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～10 weight part, 0.2～5 weight part particularly preferably.
In solidification compound of the present invention, the object for preventing the oxidative degradation that cured article causes because of heat, can coordinate thermo-stabilizer.As thermo-stabilizer, can enumerate hindered phenol system, single phenol system, bis-phenol system, polyphenol system, but particularly preferably hindered phenol is.Hindered phenol system can obtain with the form of the commercially available product of IRGANOX1010, IRGANOX1035 (BASF AG's system) etc.
The usage quantity of thermo-stabilizer, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～10 weight part, more preferably 0.2～5 weight part.
In solidification compound of the present invention, the object for improving stability in storage, can coordinate dewatering agent.As dewatering agent, such as the alkoxysilane compound containing trialkylsilyl group in molecular structure that can enumerate vinyltrimethoxy silane, vinyl methyl dimethoxysilane etc.
The usage quantity of dewatering agent, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～20 weight part, more preferably 0.5～10 weight part.
In solidification compound of the present invention, in order to improve workability, can coordinate thixotropic agent.As thixotropic agent, can enumerate polyamide wax, hydrogenated castor oil, metallic soap etc.
The usage quantity of thixotropic agent, preferably with respect to (A) composition and (B) total 100 weight parts of composition be 0.1～20 weight part.
In solidification compound of the present invention, for the object of each physical property of the cured article that improves solidification compound or obtain, can further coordinate as required tackifying resin, physical property conditioning agent, photocurable compound, oxygen solidified nature compound, epoxy compounds, particle-like substance, fire retardant, solidified nature conditioning agent, free radical inhibitors, metal passivator, ozone deterioration preventing agent, phosphorus is peroxide decomposer, lubricant, pigment, whipping agent, solvent, mould inhibitor etc.
Solidification compound of the present invention, can mix and the batch production mode of making, to the forcing machine of screw-type extruder etc., successively add Synergist S-421 95, mix and the method arbitrarily of the continuous mode of production of making etc. is made with the mixing roll of whole Synergist S-421 95s being put into mixing machine etc.
Solidification compound of the present invention, also can be pre-mixed, seal preservation by whole gradation compositions, is prepared into the 1 one-tenth somatotype solidification compound being cured by airborne moisture when construction.In addition, the solidifying agent that also can be divided into the host that contains polymkeric substance etc. and contain curing catalysts etc., is prepared into 2 one-tenth somatotype solidification compounds that mix when construction and use.
Solidification compound of the present invention, the sealing agent that can be used as buildings, boats and ships, automobile, railway, road etc. is used.In addition, the sealing agent, the caking agent that can be used as healant, motorbus or the truck of automobile are used.And then, also can be used as separately or sealing compositions and bonding composition that can be closely sealed with the base material of wide scope as glass, chinaware, timber, metal, resin forming article etc. by primer coating be used.As caking agent, except common caking agent, also can be used as contact caking agent and use.
By being solidified, solidification compound of the present invention can obtain cured article of the present invention.
Embodiment
Below the present invention is being described particularly, but the present invention is not limited to these embodiment.
(synthesis example 1)
With molecular weight approximately 3,000 polyoxypropylene triol is as initiator, with six cyano group cobalts acid zinc glycol dimethyl ether complex compound catalysts by Polymerization of Propylene Oxide, obtain the number-average molecular weight of GPC under converting and be approximately 26,000 C-terminal polyoxypropylene triol (Shi Yong East ソ mono-(strain) HLC-8120GPC processed (post: East ソ mono-(strain) TSK-GEL H processed type, solvent: the polystyrene conversion molecular weight of THF) measuring as liquor charging system).
With respect to the hydroxyl of the C-terminal polyoxypropylene triol obtaining, add 1.2 times of equivalents NaOMe methanol solution and hydroxyl is converted into after NaO base, further make it react with chlorallylene, use normal hexane and water to refine, by approximately 97% of end, be converted into allyl group thus, obtain the number-average molecular weight of GPC under converting and be approximately 26,000 allyl group end polyoxypropylene polymer.
With respect to the allyl group end polyoxypropylene polymer obtaining, the aqueous isopropanol of platinum content 3wt% of platinum vinylsiloxane complex compound of take is catalyzer, make itself and dimethoxy-methyl silane reaction, obtain having in molecular end a chain polyoxypropylene polymer (polymer A-1) of dimethoxy-methyl silyl.Use 1hNMR (is used NEC (strain) JNM-LA400 processed at CDCl 3in solvent, measure) mensuration, dimethoxy-methyl silyl 2.4 of average out in every 1 molecule.In addition, the number-average molecular weight under GPC conversion is 26,000.
(synthesis example 2)
By molecular weight approximately 3,000 polyoxypropylene triol molecular weight and approximately 2,1/1 (weight ratio) mixture of 000 polyoxypropylene diols is used in initiator, in addition, carry out the operation same with synthesis example 1, obtain the number-average molecular weight of GPC under converting and be 19,700, in molecular end, there is the dimethoxy-methyl silyl of 1.7 of average out in every 1 molecule, the polyoxypropylene polymer (polymer A B-1) that contains branched structure and linear chain structure with the ratio of 1/1 (weight ratio).
(synthesis example 3)
By molecular weight approximately 3,000 polyoxypropylene diols is used in initiator, in addition, carry out the operation same with synthesis example 1, obtain the number-average molecular weight of GPC under converting and be 25,500, in molecular end, there is the straight chain shape polyoxypropylene polymer (polymer B-1) of the dimethoxy-methyl silyl of 1.4 of average out in every 1 molecule.
(embodiment 1)
100 weight parts with respect to polymer A-1 obtaining in synthesis example 1, weighing is as polypropylene glycol (Mitsui Chemicals (strain) system of polyether plasticizer, trade(brand)name: ア Network ト コ mono-Le P-23) 50 weight parts, surface treatment calcium carbonate (the former chemical industry of bamboo (strain) system, trade(brand)name: Neolight SP, with lipid acid, carried out surface-treated calcene, median size: 0.08 μ m) 140 weight parts, carbon black (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, trade(brand)name: HIBLACK10, oil number: 97ml/100g, median size: 30nm) 40 weight parts, thermo-stabilizer (BASF AG's system, trade(brand)name: IRGANOX1010) 1 weight part, UV light absorber (BASF AG's system, trade(brand)name: Tinuvin326) 1 weight part, photostabilizer (BASF AG's system, trade(brand)name: Tinuvin770) 1 weight part, after mixing, use 3 paint rollers that it is fully disperseed.Then, interpolation as the vinyltrimethoxy silane of dewatering agent (Momentive company system, trade(brand)name: A-171) 0.5 weight part, as N-(the beta-aminoethyl)-gamma-amino propyl trimethoxy silicane of tackifier (Momentive company system, trade(brand)name: A-1120) 5 weight parts and (day east changes into (strain) system, trade(brand)name: ネ オ ス タ Application U-220H) 2 weight parts and fully mixing, obtain solidification compound thus as two (acetyl acetone) dibutyl tins of condensation catalyst.
(embodiment 2～6, comparative example 1)
By the method identical with embodiment 1, according to Synergist S-421 95 and the usage quantity (parts by weight) recorded in table 1, modulate, obtain solidification compound.
Figure BSA0000097570590000171
For at solidification compound obtained above, by following method, carry out physical property measurement.
(stretching physical property)
Under 23 ℃, the atmosphere of relative humidity 50%, not enter the mode of bubble, solidification compound is filled in to the molding box of the polyethylene system of thickness 3mm.Then, 23 ℃, relative humidity 50% time aging 3 days and then at 50 ℃ aging 4 days, obtain thus cured article.From the cured article obtaining, according to die-cut No. 3 dumbbells of JIS K6251, carry out tension test (draw speed 200mm/ minute, 23 ℃, relative humidity 50%), measure 50% tensile stress (M50), 100% tensile stress (M100), tensile break strength (TB), tension fracture elongation rate (EB).Measurement result is shown in to table 1.
(rising of tensile shear strength)
The mode of bond area 25mm * 12.5mm, thickness 1mm of usining under 23 ℃, the atmosphere of relative humidity 50% is coated with solidification compound and pastes as the stainless steel of adherend each other, makes thus test body.Using while pasting as the time opening, then, under 23 ℃, the atmosphere of relative humidity 50%, after 1 hour, after 2 hours and after 3 hours, carrying out tensile shear(ing) test (draw speed 50mm/ minute), carry out the mensuration of tensile shear strength.In addition by visual observation collapse state.It should be noted that, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 1.
From table 1 clearly, with weight ratio 100/0～50/50, mix (A) composition and (B) composition and the solidification compound (embodiment 1～6) that uses, compare with only having used the solidification compound (comparative example 1) of (B) composition, there is the rising of excellent tensile shear strength.
(embodiment 7)
100 weight parts with respect to polymer A-1 obtaining in synthesis example 1, weighing is as polypropylene glycol (Mitsui Chemicals (strain) system of polyether plasticizer, trade(brand)name: ア Network ト コ mono-Le P-23) 50 weight parts, surface treatment calcium carbonate (the former chemical industry of bamboo (strain) system, trade(brand)name: Neolight SP, with lipid acid, carried out surface-treated calcene, median size: 0.08 μ m) 130 weight parts, carbon black (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, trade(brand)name: HIBLACK10, oil number: 97ml/100g, median size: 30nm) 50 weight parts, thermo-stabilizer (BASF AG's system, trade(brand)name: IRGANOX1010) 1 weight part, UV light absorber (BASF AG's system, trade(brand)name: Tinuvin326) 1 weight part, photostabilizer (BASF AG's system, trade(brand)name: Tinuvin770) 1 weight part, after mixing, use 3 paint rollers that it is fully disperseed.Then, at 120 ℃, carry out 2 hours drying under reduced pressure, after below being cooled to 50 ℃, interpolation as the vinyltrimethoxy silane of dewatering agent (Momentive company system, trade(brand)name: A-171) 4 weight parts, as N-(the beta-aminoethyl)-gamma-amino propyl trimethoxy silicane of tackifier (Momentive company system, trade(brand)name: A-1120) 5 weight parts and (day east changes into (strain) system, trade(brand)name: ネ オ ス タ Application U-220H) 2 weight parts and fully mixing, obtain solidification compound thus as two (acetyl acetone) dibutyl tins of condensation catalyst.The solidification compound obtaining is filled in to the container of moisture resistance, carries out airtightly, obtain thus 1 liquid type solidification compound.
(embodiment 8～10)
By the method identical with embodiment 7, according to Synergist S-421 95 and the usage quantity (parts by weight) recorded in table 2, adjust, obtain 1 liquid type solidification compound.
Figure BSA0000097570590000201
For at 1 liquid type solidification compound obtained above, by following method, carry out physical property measurement.
(stretching physical property)
Under 23 ℃, the atmosphere of relative humidity 50%, not enter the mode of bubble, solidification compound is filled in to the molding box of the polyethylene system of thickness 3mm.Then, 23 ℃, relative humidity 50% time aging 3 days, and then at 50 ℃ aging 4 days, obtain thus cured article.From the cured article obtaining, according to die-cut No. 3 dumbbells of JIS K6251, carry out tension test (draw speed 200mm/ minute, 23 ℃, relative humidity 50%), measure 50% tensile stress (M50), 100% tensile stress (M100), tensile break strength (TB), tension fracture elongation rate (EB).Measurement result is shown in to table 2.
(tensile shear strength)
The mode of bond area 25mm * 12.5mm, thickness 3mm of usining under 23 ℃, the atmosphere of relative humidity 50% is coated with solidification compound and pastes as the stainless steel of adherend each other.Then, under 23 ℃, the atmosphere of relative humidity 50% aging 7 days, 14 days and 21 days and 23 ℃ aging 7 days, and then at 50 ℃ aging 4 days, make thus test body.The test body that use obtains carries out the mensuration that tensile shear strength is carried out in tensile shear(ing) test (draw speed 50mm/ minute).In addition, by visual observation collapse state.It should be noted that, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 2." C50A50 " meaning is for condensing destruction 50%, interfacial failure 50%, and " C40A60 " meaning is cohesion destruction 40%, interfacial failure 60%.
From table 2 clearly, if the usage quantity of carbon black with respect to (A) composition 100 weight parts in the scope of 5～50 weight parts, can obtain excellent tensile shear strength.
(embodiment 11)
100 weight parts with respect to the polymer A B-1 obtaining in synthesis example 2, weighing is as polypropylene glycol (Mitsui Chemicals (strain) system of polyether plasticizer, trade(brand)name: ア Network ト コ mono-Le P-23) 50 weight parts, surface treatment calcium carbonate (the former chemical industry of bamboo (strain) system, trade(brand)name: Neolight SP, with lipid acid, carried out surface-treated calcene, median size: 0.08 μ m) 140 weight parts, carbon black (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, trade(brand)name: HIBLACK10, oil number: 97ml/100g, median size: 30nm) 40 weight parts, thermo-stabilizer (BASF AG's system, trade(brand)name: IRGANOX1010) 1 weight part, UV light absorber (BASF AG's system, trade(brand)name: Tinuvin326) 1 weight part, photostabilizer (BASF AG's system, trade(brand)name: Tinuvin770) 1 weight part, after mixing, use 3 paint rollers that it is fully disperseed.Then, interpolation as the vinyltrimethoxy silane of dewatering agent (Momentive company system, trade(brand)name: A-171) 0.5 weight part, as N-(the beta-aminoethyl)-gamma-amino propyl trimethoxy silicane of tackifier (Momentive company system, trade(brand)name: A-1120) 5 weight parts and (day east changes into (strain) system, trade(brand)name: ネ オ ス タ Application U-220H) 2 weight parts and fully mixing, obtain solidification compound thus as two (acetyl acetone) dibutyl tins of condensation catalyst.
(embodiment 12～14)
By the method identical with embodiment 11, according to Synergist S-421 95 and the usage quantity (parts by weight) recorded in table 3, modulate, obtain solidification compound.
It should be noted that, the median size of HIBLACK10,30,5L, 20L is respectively 30nm, 23nm, 35nm, 28nm.
Figure BSA0000097570590000231
For at solidification compound obtained above, by following method, carry out physical property measurement.
(stretching physical property)
Under 23 ℃, the atmosphere of relative humidity 50%, not enter the mode of bubble, solidification compound is filled in to the molding box of the polyethylene system of thickness 3mm.Then, 23 ℃, relative humidity 50% time aging 3 days and then at 50 ℃ aging 4 days, obtain thus cured article.From the cured article obtaining, according to die-cut No. 3 dumbbells of JISK6251, carry out tension test (draw speed 200mm/ minute, 23 ℃, relative humidity 50%), measure 50% tensile stress (M50), 100% tensile stress (M100), tensile break strength (TB), tension fracture elongation rate (EB).Measurement result is shown in to table 3.
(rising of tensile shear strength)
The mode of bond area 25mm * 12.5mm, thickness 1mm of usining under 23 ℃, the atmosphere of relative humidity 50% is coated with solidification compound and pastes as the stainless steel of adherend each other, makes thus test body.Using while pasting as the time opening, then, under 23 ℃, the atmosphere of relative humidity 50%, after 1 hour, after 2 hours and after 3 hours, carry out tensile shear(ing) test (draw speed 50mm/ minute), carrying out the mensuration of tensile shear strength.In addition, by visual observation collapse state.It should be noted that, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 3.
From table 3 clearly, the cooperation of embodiment 11～14 solidification compound of carbon black all there is the rising of excellent tensile shear strength.
(embodiment 15)
100 weight parts with respect to polymer A-1 obtaining in synthesis example 1.Weighing is as polypropylene glycol (Mitsui Chemicals (strain) system of polyether plasticizer, trade(brand)name: ア Network ト コ mono-Le P-23) 50 weight parts, surface treatment calcium carbonate (the former chemical industry of bamboo (strain) system, trade(brand)name: Neolight SP, with lipid acid, carried out surface-treated calcene, median size: 0.08 μ m) 140 weight parts, carbon black (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, trade(brand)name: HIBLACK10, oil number: 97ml/100g, median size: 30nm) 40 weight parts, thermo-stabilizer (BASF AG's system, trade(brand)name: IRGANOX1010) 1 weight part, UV light absorber (BASF AG's system, trade(brand)name: Tinuvin326) 1 weight part, photostabilizer (BASF AG's system, trade(brand)name: Tinuvin770) 1 weight part, after mixing, use 3 paint rollers that it is fully disperseed.Then, at 120 ℃, carry out 2 hours drying under reduced pressure, after below being cooled to 50 ℃, interpolation as the vinyltrimethoxy silane of dewatering agent (Momentive company system, trade(brand)name: A-171) 4 weight parts, as N-(the beta-aminoethyl)-gamma-amino propyl trimethoxy silicane of tackifier (Momentive company system, trade(brand)name: A-1120) 5 weight parts and (day east changes into (strain) system, trade(brand)name: ネ オ ス タ Application U-220H) 2 weight parts and fully mixing, obtain solidification compound thus as two (acetyl acetone) dibutyl tins of condensation catalyst.The solidification compound obtaining is filled in to the container of moisture resistance, carries out airtightly, obtain thus 1 liquid type solidification compound.
(embodiment 16)
By the method identical with embodiment 15, according to Synergist S-421 95 and the usage quantity (parts by weight) recorded in table 4, modulate, obtain 1 liquid type solidification compound.
Table 4
Figure BSA0000097570590000251
For at 1 liquid type solidification compound obtained above, by following method, carry out physical property measurement.
(stretching physical property)
Under 23 ℃, the atmosphere of relative humidity 50%, not enter the mode of bubble, solidification compound is filled in to the molding box of the polyethylene system of thickness 3mm.Then, 23 ℃, relative humidity 50% time aging 3 days, and then at 50 ℃ aging 4 days, obtain thus cured article.In the cured article obtaining, according to die-cut No. 3 dumbbells of JISK6251, carry out tension test (draw speed 200mm/ minute, 23 ℃, relative humidity 50%), measure 50% tensile stress (M50), 100% tensile stress (M100), tensile break strength (TB), tension fracture elongation rate (EB).Measurement result is shown in to table 4.
(tensile shear strength)
The mode of bond area 25mm * 12.5mm, thickness 3mm of usining under 23 ℃, the atmosphere of relative humidity 50% is coated with solidification compound and pastes as the stainless steel of adherend each other.Then, under 23 ℃, the atmosphere of relative humidity 50% aging 7 days and 14 days, make thus test body.The test body that use obtains carries out tensile shear(ing) test (draw speed 50mm/ minute), carries out the mensuration of tensile shear strength.In addition, by visual observation collapse state.In addition, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 4.
(hand is peeled off cementability)
Under 23 ℃, the atmosphere of relative humidity 50% while making solidification compound and abundant closely sealed coating the in ceramic coating glass pearl ground as adherend.Then, 23 ℃, relative humidity 50% time aging 7 days and 14 days, make thus test body.Between adherend and cured article, with cutters, cut the indentation of about 1cm, by hand, peel off and carry out 90 ° of stripping tests, visual observation collapse state.It should be noted that, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 4." C40T40A20 " meaning is cohesion destruction 40%, thin layer destruction 40%, interfacial failure 20%.
From table 4 clearly, if increase the use level containing amino silane compounds as tackifier, can improve to the cementability of ceramic coating glass.
(embodiment 17)
100 weight parts with respect to polymer A-1 obtaining in synthesis example 1, weighing is as polypropylene glycol (Mitsui Chemicals (strain) system of polyether plasticizer, trade(brand)name: ア Network ト コ mono-Le P-23) 50 weight parts, surface treatment calcium carbonate (the former chemical industry of bamboo (strain) system, trade(brand)name: Neolight SP) 160 weight parts, carbon black (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, trade(brand)name: HIBLACK30, oil number: 110ml/100g, median size 23nm) 20 weight parts, UV light absorber (BASF AG's system, trade(brand)name: Tinuvin326) 1 weight part, photostabilizer (BASF AG's system, trade(brand)name: Tinuvin770) 1 weight part, after mixing, use 3 paint rollers that it is fully disperseed.Then, at 120 ℃, carry out 2 hours decompression dehydrations, be cooled to 50 ℃ following after, add vinyltrimethoxy silane as dewatering agent (Momentive company system, trade(brand)name: A-171) 3 weight parts and as N-(the beta-aminoethyl)-gamma-amino propyl trimethoxy silicane of tackifier (Momentive company system, trade(brand)name: A-1120) 5 weight parts mixing.And then (day east changes into (strain) system, trade(brand)name: ネ オ ス タ Application U-220H) 2 weight parts mixing, obtain solidification compound thus to add two (acetyl acetone) dibutyl tins as condensation catalyst.The solidification compound obtaining is filled in to the container of moisture resistance, carries out airtightly, obtain thus 1 liquid type solidification compound.
(embodiment 18～23, comparative example 2)
By the method identical with embodiment 1, according to Synergist S-421 95 and the usage quantity recorded in table 5, adjust, obtain 1 liquid type solidification compound.
Figure BSA0000097570590000281
For the Synergist S-421 95 using, be shown in following.
HIBLACK10 (オ リ オ Application エ Application ジ ニ ア De カ mono-ボ Application ズ (strain) system, oil number: 97ml/100g, median size: 30nm)
Monarch570 (CABOT company system, oil number: 115ml/100g, median size: 24nm)
For at solidification compound obtained above, by following method, carry out physical property measurement.
(stretching physical property)
Under 23 ℃, the atmosphere of relative humidity 50%, not enter the mode of bubble, solidification compound is filled in to the molding box of the polyethylene system of thickness 3mm.Then, aging 3 days of 23 ℃, relative humidity 50%, and then at 50 ℃ aging 4 days, obtain thus cured article.From the cured article obtaining, according to die-cut No. 3 dumbbells of JISK6251, carry out tension test (draw speed 200mm/ minute, 23 ℃, relative humidity 50%), measure 50% tensile stress (M50), 100% tensile stress (M100), breaking tenacity (TB), elongation at break (EB).Measurement result is shown in to table 5.
(tensile shear strength)
The mode that the bond area of usining under 23 ℃, the atmosphere of relative humidity 50% reaches 25mm * 12.5mm, thickness 0.2mm is coated with solidification compound and pastes as the aluminium of adherend each other.Then, 23 ℃, relative humidity 50% time aging 7 days, make thus test body.By the test film obtaining, carry out tensile shear(ing) test (draw speed 50mm/ minute), carry out the mensuration of tensile shear strength.In addition by visual observation collapse state.It should be noted that, collapse state is made as cohesion and destroys (CF), thin layer destruction (TF), interfacial failure (AF).Evaluation result is shown in to table 5.
From table 5 clearly, the solidification compound that contains (A) composition (embodiment 17～23) is compared with only having used the solidification compound (comparative example 2) of (B) composition, and tensile break strength and tensile shear strength are excellent.
In addition, known, particularly with 1/1 (weight ratio) by (A) composition and (B) composition mix and the solidification compound (embodiment 18～20) that uses, there is excellent tensile break strength and tension fracture elongation rate.This result shows than by having used separately the solidification compound (embodiment 17) of (A) composition and having used separately the simple average of solidification compound (comparative example 2) of (B) composition and the value excellence that derives.
Utilizability in industry
Solidification compound of the present invention, the sealing agent that can be used as buildings, boats and ships, automobile, railway, road etc. is used.In addition, the sealing agent, the caking agent that can be used as healant, motorbus or the truck of automobile are used.And then, also can be used as separately or sealing compositions and bonding composition that can be closely sealed with the base material of wide scope as glass, chinaware, timber, metal, resin forming article etc. by the coating of priming paint be used.As caking agent, except common caking agent, also can be used as contact caking agent and use.

Claims (10)

1. a solidification compound, is characterized in that, it has a chain polyoxyalkylene polymers, (C) calcium carbonate of reactive silicon group and (D) solidification compound of carbon black for containing (A),
Reactive silicon group represents by following general formula (1),
-SiX nR 3-n…(1)
In formula, X represents hydroxyl or hydrolization group, and R represents to have the organic group of 1 valency of substituent carbon number 1～20, wherein, does not comprise hydrolization group; N represents 1,2 or 3; When X is a plurality of, X can be identical or different mutually; When R is a plurality of, R can be identical or different mutually.
2. solidification compound as claimed in claim 1, it also contains the straight chain shape polyoxyalkylene polymers that (B) has the reactive silicon group being represented by above-mentioned general formula (1).
3. solidification compound as claimed in claim 1 or 2, is characterized in that, (A) composition and (B) mixture ratio of composition with weight ratio, count 100/0～5/95.
4. the solidification compound as described in any one of claim 1～3, is characterized in that, (A) composition and (B) mixture ratio of composition with weight ratio, count 100/0～60/40.
5. the solidification compound as described in any one of claim 1～4, is characterized in that, (D) oil number of composition is more than 50ml/100g.
6. the solidification compound as described in any one of claim 2～5, it is characterized in that, (A) composition and/or (B) number-average molecular weight of composition be respectively 15,000～50,000 and/or (A) composition and (B) number-average molecular weight of the mixture of composition be 15,000～50,000.
7. the solidification compound as described in any one of claim 1～6, is characterized in that, (C) composition be selected from water-ground limestone, precipitated chalk and by these calcium carbonate carry out surface treatment calcium carbonate in more than at least a kind.
8. the solidification compound as described in any one of claim 1～7, is characterized in that, (C) composition is the calcene below median size 1 μ m.
9. the solidification compound as described in any one of claim 1～8, is characterized in that, with respect to (A) composition and (B) total 100 weight parts of composition, contains 60～200 weight parts (C) composition, 20～50 weight parts (D) composition.
10. a cured article, it is to make the solidification compound described in any one of claim 1～9 solidify the cured article forming.
CN201310562135.2A 2012-11-09 2013-11-11 Solidification compound and solidfied material thereof Active CN103694712B (en)

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