JPH01188557A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, curable by, e.g., moisture, capable of giving cured products with dust hard-to-adhere thereto, by incorporating an oxyalkylene polymer having reactive silicon-contg. group with a silicone compound containing long chain hydrocarbon group. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of an oxyalkylene polymer having the main chain constituted of recurring unit of formula II (R<1> is divalent organic group), also having Si- bonded OH or hydrolizable group (pref. alkoxy group) and Si-contg. group crosslinkable by forming siloxane linkage {pref. group of formula I [R<2> is (substituted) 1-20C monovalent organic group or triorganosiloxy group; X is OH or hydrolyzable group; a is 0-2; b: is 0-3, (ma+b)>=1; m is 0-19]} (pref. methoxysilyl group) with (B) 0.1-30 pts.wt. of a silicone compound containing long chain hydrocarbon group (pref. 8-20C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composition that is cured by moisture or the like and provides a cured product with improved surface properties (hard to attract dirt and dust). More specifically, it is an oxyalkylene polymer that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and has a silicon-containing group (hereinafter also referred to as a reactive silicon group) that can be crosslinked by forming a siloxane bond. The present invention relates to a curable composition containing a long-chain hydrocarbon group-containing silicon compound.

[Problems to be Solved by the Prior Art and Inventions Many proposals have been made for organic polymers having at least one reactive silicon group in one molecule. Some, such as organic polymers with silyl groups bonded thereto, are already produced industrially (trade name: MS Polymer, manufactured by Kanekabuchi Kagaku Kogyo ■).

This organic polymer is mixed with various compounding agents and used for applications such as sealants, but depending on the compounding composition and conditions of use, dust and dirt may adhere to the surface of the cured product, and improvement is needed. or desired.

[Means for Solving the Problems] As a result of intensive studies to reduce the adhesion of dirt and dust to the cured product from the organic polymer, the present inventors discovered that long-chain hydrocarbons were added to the organic polymer. It has been discovered that the objective can be achieved by adding a group-containing silicon compound, and the present invention has been achieved.

That is, the present invention provides 100 parts (parts by weight, (same below), the long-chain hydrocarbon group-containing silicon compound is added to
It relates to a curable composition containing within the range of 30 parts.

[Example] In the present invention, an oxyalkylene polymer having at least one reactive silicon group (hereinafter also referred to as oxyalkylene polymer (A)) is used.

The oxyalkylene polymer (A) has already been disclosed in Japanese Patent Publications No. 45-3 [i31.9, No. 4G-12154, No. 4].
9-32 [No. i73, JP-A-50-15 [No. 1599,
No. 51-73581, No. 54-8098, No. 55
No. -82123, No. 55-123820, No. 55-
No. 1251.21, No. 55-131022, No. 55-
These are polymers proposed in publications such as No. 135135 and No. 55-137129.

The molecular chain of the oxyalkylene polymer (A) essentially consists of repeating units represented by the general formula: % (wherein R1 is a divalent organic group). R1 is preferably a divalent alkyl group having 1 to 10 carbon atoms, particularly a divalent alkyl group having 2 to 4 carbon atoms.
Preferably, it is a valent alkyl group. Further, this alkyl group may be a substituted carbon hydrogen group in which some of the hydrogen atoms are substituted with a substituent such as a chlorine atom. Specific examples of R1 include, for example, CH3C285CH3 -CHCH2-1-CHCH2-, -C-CH2-1C
Examples include R3 -CH2CH2CR2CH2-, with CR3 -CHCR3- being particularly preferred. The molecular chain of the oxyalkylene polymer (A) may consist of only one type of repeating unit, or may consist of two or more types of repeating units. Moreover, the molecular chain of the oxyalkylene polymer (A) is -
It may contain units other than R1-〇-, and in this case, the total amount of units represented by -R1-0- is 50% in the polymer.
It is preferable that it is at least % by weight.

The reactive silicon group that can be crosslinked and/or polymerized by forming a siloxane bond in the oxyalkylene polymer (A) is a well-known functional group, and has the characteristic that it can be crosslinked even at room temperature. There is. A typical example of this reactive silicon group is the general formula (■): (wherein, R2 is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms or a triorganosiloxy group, and (m(
2-a) + 3-b) R2 may be different, X is a hydroxyl group or a hydrolyzable group, and (ma+b)
X may be different, a is 0.1 or 2, b
is 0.1.2 or 3, provided that ma+b)≧l, a in m pieces does not need to be the same, m is an integer from θ to 19). Among the reactive silicon groups represented by the general formula (1), from the point of view of economic efficiency, the general formula (■); The groups represented are preferred.

Specific examples of the hydrolyzable group that is one type of a ketoximate group such as a toximate group, an amino group such as a dimethylamino group, an acid amide group such as an N-methylacetamide group, an aminooxy group such as a dimethylaminooxy group, a mercapto group such as a thiophenoxy group, Examples include alkenyloxy groups such as isopropenyloxy groups. Among these, alkoxy groups such as methoxy group and ethoxy group are preferred because of their mild hydrolyzability.

Specific examples of R2 in general formula (■) include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and .

(R-)35iO- (R- is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, such as a methyl group or a phenyl group, and the three R's do not need to be the same) Examples include triorganosiloxy groups. Among these, methyl group is particularly preferred.

It is sufficient that the number of reactive silicon groups in the oxyalkylene polymer (A) is 1 or more, but from the viewpoint of achieving sufficient curability, the average number of reactive silicon groups is 1.1 or more, and more preferably 1.5 to 4.
Preferably. Further, the reactive silicon group is preferably present at the molecular chain end of the oxyalkylene polymer (A).

The oxyalkylene polymer (A) has a number average molecular weight of 5
00 to 30,000 is preferable, and 3.000 to 1
5,000 is more preferred. The oxyalkylene polymer (A) may be used alone or in combination of two or more.

The oxyalkylene polymer (A) has, for example, the general formula m
A hydrosilyl compound in which a hydrogen atom is bonded to a group represented by the general formula (■): R3(I[D CH2=C-R'-(0)- a monovalent organic group, R4 is a divalent organic group having 1 to 20 carbon atoms, C is 0
Alternatively, it is produced by an addition reaction with an oxyalkylene polymer having an olefin group as shown in 1) using a group Ⅰ transition metal compound such as a platinum compound as a catalyst.

Methods for producing oxyalkylene polymers (A) other than those described above include: (1) reacting a hydroxyl group-terminated oxyalkylene polymer with a polyisocyanate compound such as toluene diisocyanate to obtain an isocyanate group-terminated oxyalkylene polymer; The isocyanate group is then converted to the general formula (IV): (wherein, W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary), Ω, R2, R4, and is the same as above); (1) A method of reacting the ν group of a silicon compound represented by the general formula (III) with the olefin group of an oxyalkylene polymer having an olefin group represented by the general formula (III) in which W is a mercapto group. A method of addition-reacting a mercapto group of a silicon compound shown by
Killing M: Specific examples include a method of reacting a compound represented by 0CNR'-8r-Xn (wherein R2, R4, X and ρ are the same as above), but the method is limited to these methods. It's not a thing.

In the method of reacting a hydrosilyl compound in which a hydrogen atom is bonded to a group represented by the above-mentioned -Satsuri (1) and an oxyalkylene polymer having an olefin group represented by the general formula (111), after reacting them, Some or all of the X groups may be further converted into other hydrolyzable groups or hydroxyl groups. For example, when the X group is a halogen atom or a hydrogen atom, it is preferable to use these groups after converting them into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like.

In general formula (III), R3 is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom. is preferred. Furthermore, R4 is a divalent organic group having 1 to 2 carbon atoms, but -R5-, -R50
A hydrocarbon group (R5-, -R5-0C-1) is preferable, and a methylene group is particularly preferable.

As a specific method for producing an oxyalkylene polymer having an olefin group represented by the general formula (I[l), for example, as disclosed in JP-A-54-0097, Allyl Examples include a method in which an olefin group-containing epoxy compound such as glycidyl ether is added and copolymerized to introduce an olefin group into the side chain.

In the present invention, a long-chain hydrocarbon group-containing silicone compound is used in order to make it difficult for dirt and dust to adhere when the oxyalkylene polymer (A) is cured.

The long-chain hydrocarbon group in the long-chain hydrocarbon group-containing silicon compound is, for example, a long-chain alkyl group to which a silicon group is bonded to one end, a long-chain alkenyl group, or a cyclo group having a long-chain alkyl group or a long-chain alkenyl group. These include alkyl groups, aryl groups, and even long-chain alkylene groups with silicon-based groups bonded to both ends, and the carbon atoms in the hydrocarbon portion (not including carbon atoms forming a ring) that are connected in a straight line. It refers to a hydrocarbon group having 8 or more atoms, preferably 8 to 20 atoms.

Specific examples of the long-chain alkyl group include n-octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, cetyl group, stearyl group,
Specific examples of long chain alkenyl groups such as eicosyl group include octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosyl group, octadecagenyl group, 9,12.15 -oftade trienyl group, 9,11
, 1.3-octadecagenyl group, and long chain alkylene groups include -(CH2) to -
, -(CH2) +2-, -(CI2) M-2(CH
2) +s −, −(CH2) +8−, −(C112
) 20- etc.

Further, the long-chain hydrocarbon group-containing silicon compound contains a reactive silicon group. This reactive silicon group is a group similar to the reactive silicon group possessed by the above-mentioned oxyalkylene polymer (A), but a reactive silicon group having one silicon atom is preferable from the point of view of economy and the like.

Specific examples of the long-chain hydrocarbon group-containing silicon compound include CH3(CH2) to Sj (OCI(3) 3,
CHs (CH2) +78i (OCH3) 3
, CHs (CH2) +7 Si (OCH2C
Hs )3, CH3 (CH2) +7 Si (CH
3) (OCt(3)2, CH3(CH2) to 5
i(OCH2CI3)3,C)+3 (CH2)
1O8i (C)+3 )(OCH3)2, (C113
0) 2(CH3) Si (CH2) to St
<CHs ) (OCH3)2, (C)130)3 5
Examples include i(CH2) lO5j(OCI!3)3.

The amount of the long-chain hydrocarbon group-containing silicon compound used is 0.1 to 30 parts per 100 parts of the oxyalkylene polymer (A).
parts, preferably 0.5 to 20 parts. The usage amount is 0
．． If it is less than 1 part, the effect of preventing the adhesion of dirt and dust, which is the purpose of using a long-chain hydrocarbon group-containing silicon compound, will not be sufficiently achieved, and if it is more than 30 parts, it will become expensive and the tensile properties etc. will be impaired.

Although there are no particular limitations on the method for preparing the composition of the present invention prepared using the oxyalkylene polymer (A) and the long-chain hydrocarbon group-containing silicone compound, one specific method is A method of simply adding a hydrocarbon group-containing silicon compound to the oxyalkylene group type compound (A) is mentioned. In this case, heating and stirring conditions may be appropriately adjusted depending on the properties of the long-chain hydrocarbon group-containing silicon compound to uniformly disperse and dissolve it. However, it is not necessary to have a completely uniform and transparent state, and even in an opaque state, the purpose can be sufficiently achieved as long as it is dispersed. Further, if necessary, a dispersibility improver such as a surfactant may be used in combination.

The composition of the present invention may further include a curing catalyst, an antistatic agent used to reduce dust adhesion due to static electricity, a physical property modifier to improve tensile properties, etc., and reinforcing or non-reinforcing properties. Various additives such as fillers, reinforcing materials, plasticizers, adhesion promoters, anti-sag agents, colorants, anti-aging agents, and flame retardants may be added.

Specific examples of the curing catalyst include organic tin compounds such as tetrabutyl titanate, tetrabutyltitaneraure-1, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, tin octylate, and silver naphthenate. ; Lead octylate; Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylene Diamine, triethylenediamine, guanidine, diphenylguanidine, 2,4゜6-1-lis(dimethylaminomethyl)phenol, morpholine,
N-methylmorpholine, 1,8-diazabicyclo(5,
4,0) Amine compounds such as undecene-7 (DBU) or salts thereof such as carboxylic acids; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid;
A reaction product of an excess polyamine and an epoxy compound; a silane coupling agent having an amino group, such as a known silanol condensation catalyst such as γ-aminopropyltrimethoxysilane or N-(β-aminoethyl)aminopropylmethyldimethoxysilane. etc. These may be used alone or in combination of two or more.

As a specific example of the antistatic agent, for example, r 95g
"G's Chemical Products" pp. 775-776 (January 30, 1985)
Nonionic products such as polyoxyethylene alkylamine, polyoxyethylene alkyl amide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin partial fatty acid ester, sorbitan partial fatty acid ester, etc. described in Nikkagaku Kogyo Nippo Publishing Co., Ltd.) anionic antistatic agents such as alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, and cationic antistatic agents such as quaternary ammonium chloride, quaternary ammonium sulfate, and quaternary ammonium nitrate. Examples include amphoteric antistatic agents such as alkyl betaine type, alkylimidacilline type, and alkylalanine type, and conductive resin type antistatic agents such as polyvinylbenzyl type cation and polyacrylic acid type cation.

Examples of physical property modifiers that improve the tensile properties include various silane coupling agents, such as γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and N-(β-aminoethyl)amino. Alkoxysilanes with functional groups such as propylmethyldimethoxysilane, N-(β-aminoethyl)aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, dimethyldiisopropenoxysilane Examples include impropenoxysilanes having a functional group such as and γ-glycidoxypropylmethyldiisopropenoxysilane.

Further, as specific examples of those that lower the hardness of the cured product to increase elongation, for example, (CI-13)isioll, (CsHs)2si
(C)13)011, (CH3)2Si (C6H5
) OH.

(CH3)35ide)lx, (CHa)35iOC
H2CH3, (CH3>35jOCsH5, (CH3)
35iNSi(CH3)3, etc.
Examples include, but are not limited to, the compounds described in Publication No. 1-3408 [i].

Specific examples of the fillers and reinforcing materials include colloidal lucium carbonate, heavy or light calcium carbonate; fatty acids, resin acids,
Calcium carbonate surface-treated with cationic surfactants, anionic surfactants, etc.; magnesium carbonate; talc; titanium oxide; barium sulfate; alumina; metal powders such as aluminum, zinc, iron; bentonite; kaolin;
Commonly used materials include clay; fumed silica; quartz powder; white carbon, carbon black; asbestos and glass fiber.

In particular, it is possible to create a sealant with excellent transparency by using a filler or reinforcing material that imparts transparency, such as fumed silica. The fillers and reinforcing materials may be used alone or in combination of two or more.

Specific examples of the plasticizer used for controlling physical properties and properties include dibutyl phthalate,
Phthalic acid esters such as dioctyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, butylbenzyl phthalate, butyl phthalyl butyl glycolate; dioctyl adipate, dioctyl/l/
Non-aromatic dibasic acid esters such as esters; polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphoric acid esters such as tricrenyl phosphate; chlorinated paraffins; alkyldiphenyl , hydrocarbon oils such as partially hydrogenated terphenyl, etc. These can be used alone or in a mixture of two or more, but this is not always necessary. In addition, these plasticizers may be added at the time of polymer production.

The oxyalkylene polymer (A) itself of the adhesion promoter has good adhesion to glass, ceramics other than glass, metals, etc., and can be bonded to a wide range of materials by using various primers. Therefore, although it is not necessarily necessary, it is possible to further increase the amount by using one or more of epoxy resins, phenol resins, various silane coupling agents already described as physical property modifiers, alkyl titanates, aromatic polyisocyanates, etc. Adhesion to various types of adherends can be improved.

Examples of the anti-sagging agent include hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; however, depending on the purpose of use and the filler or reinforcing material to be mixed, it may not be necessary. be.

As the colorant, common inorganic pigments, organic pigments, dyes, etc. may be used as necessary.

Examples of the anti-aging agent include ordinary antioxidants, ultraviolet absorbers, and the like.

The composition of the present invention may contain a solvent to improve workability and reduce viscosity, such as aromatic hydrocarbon solvents such as toluene and xylene, ethyl acetate, butyl acetate, amyl acetate, and acetic acid. Specific examples include ester solvents such as cellosolve, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. These solvents may be used during polymer production.

For example, when the composition of the present invention is used as a sealant, it may be prepared as a one-component type in which all the ingredients are mixed in advance and stored in a sealed container, and then cured by the moisture in the air after application. Ingredients such as a curing catalyst, filler, plasticizer, and water are separately blended in advance, and the compound (shrine)
and the composition of the invention may be prepared as a two-component product, which is mixed before use.

In the case of one-component type sealants, all the ingredients are mixed in advance, so ingredients containing water should be dehydrated and dried before use, but they should also be depressurized during mixing and kneading. Dehydration is preferred.

If the sealant is a two-component type, the main component containing the oxyalkylene polymer (A) and the long-chain hydrocarbon group-containing silicone compound does not contain a curing catalyst, so the main component contains some water. However, if long-term storage stability is required, dehydration and drying are preferred.

As the dehydration/drying method, a heat drying method is suitable for solid materials such as powder, and a vacuum dehydration method or a dehydration method using synthetic zeolite, activated alumina, silica gel, etc. is suitable for liquid materials. It is.

Alternatively, a small amount of an isocyanate compound may be blended, and the isoneane-1 group and water may be reacted for dehydration.

In addition to such dehydration/drying methods, lower alcohols such as methanol and ethanol: n-propyltrimethoxine, vinylmethyldimethoxine, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane, γ-glyside Storage stability is further improved by adding an alkoxysilane compound such as oxypropyltrimethoxysilane.

The curable composition of the present invention thus obtained can be usefully used as adhesives, pressure-sensitive adhesives, paints, sealants, sealants, waterproofing agents, spraying agents, molding materials, casting rubber materials, etc. Can be done. Among these, application to sealants is particularly useful.

Hereinafter, the composition of the present invention will be specifically explained with reference to Examples.

Examples 1 to 11 and Comparative Example 1 Approximately 2 dimethoxysilyl groups (-3i (C
H3) (OCH3)2 ) containing average molecular weight 96
To 100 g of propylene oxide polymer No. 00, a long-chain hydrocarbon group-containing silicon compound not shown in Table 1 was added in the amount shown in Table 1, and then 150 g of colloidal calcium carbonate (manufactured by Shiraishi Kogyo ■, trade name OCR) was added. , 65 g of dioctyl phthalate, 1 g of a hindered phenol anti-aging agent (manufactured by Iruchisho Shinko Kagaku ■, trade name: Tsukrak N5-(i)), 3 g of tin [I] octylate, and 1 g of laurylamine were added.
After thoroughly kneading, pass through 3 small paint rolls 3 times.
A sheet with a thickness of about 3 mm was produced. After that, 23℃,
After curing for 1 day at 65% RH, exposed to the outdoors, south facing 4
5 degree inclination), and the state of dust adhesion was observed. The results are shown in Table 1 along with the case of Comparative Example 1 in which no long-chain hydrocarbon group-containing silicon compound was added.

In the dust adhesion evaluation in Table 1, ◯ indicates that hardly any dust adheres, △ indicates that a little dust adheres, and × represents that dust adheres to a large extent.

[Margin below] From the results in Table 1, it can be seen that the addition of the long-chain hydrocarbon group-containing silicon compound reduces the amount of dust attached.

Examples 12 to 16 and Comparative Example 2 An average of 2.7 dimethoxysilyl groups (-3j
3 g of C6)150Si (CI+3) 3 was added to 100 g of a propylene oxide polymer with an average molecular distance of 10000 containing (CH3) (OCH3)2), and 8
The same procedure as in Examples 1 to 11 was used except that the long-chain hydrocarbon group-containing silicon compound shown in Table 2 was added to 100 g of the product after stirring at 0°C for 2 hours for the period shown in Table 2. The evaluation was conducted under the following conditions. The results are shown in Table 2.

[Margin code below] 30 - From the results in Table 2, C6f150S i (CH3)
It can be seen that the same improvement effects as in Examples 1 to 11 can be obtained also for the polymers subjected to the modification treatment in accordance with Example 3.

[Effects of the Invention] By using the composition of the present invention, a cured product that is less likely to attract dust can be obtained.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of an oxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond. On the other hand, a curable composition containing a silicon compound containing a long-chain hydrocarbon group in an amount of 0.1 to 30 parts by weight. 2 The oxyalkylene polymer has a main chain consisting essentially of repeating units represented by the general formula: -R^1-O- (wherein R^1 is a divalent organic group) The composition according to claim 1, which is a polymer. 3 The silicon-containing group has the general formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein R^2 is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms or It is a triorganosiloxy group,
(m(2-a)+3-b) R^2 may be the same or different, X is a hydroxyl group or a hydrolyzable group, and (ma+b) X are the same. may be present or different, a is 0, 1 or 2, is 0,
1, 2 or 3, but (ma+b)≧1, there are m ▲mathematical formulas, chemical formulas, tables, etc.▼, where a does not have to be the same, m is 0 or 1~
The composition according to claim 1, which is a group represented by (an integer of 19). 4 X in general formula (I) is a hydrogen atom, a halogen atom,
A hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group, and when two or more Xs are present, they may be the same or different. 4. The composition according to claim 3, which may be 5. The composition according to claim 3, wherein X in general formula (I) is an alkoxy group. 6. The composition according to claim 1 or 3, wherein the silicon-containing group is a methoxysilyl group (Si-OCH_3). 7. The composition according to claim 1, wherein the long-chain hydrocarbon group-containing silicon compound is an alkyl group-containing silicon compound having 8 to 20 carbon atoms.