JP3368057B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
And a curable composition having a low content. [0002] 2. Description of the Related Art Conventionally, a hydroxyl group bonded to a silicon atom or
Has a hydrolyzable group and forms a siloxane bond
Having at least one silicon-containing group crosslinkable by
Compounds useful for curing Japanese hydrocarbon polymers
Various compound parts are known. These compounds
, Dibutyltin dilaurate, tin octylate, octyl
Organometallic compounds such as lead oxide accelerate the curing speed
Used in [0003] However, tin and lead are not
The contained organometallic compounds are not only expensive, but also poisonous.
There was a problem of high performance. To avoid this problem
Use carboxylic acids instead of organometallic compounds.
You could think so. However, when using organometallic compounds
When carboxylic acid is used, the curing speed of the polymer is significantly higher.
It was not practical. [0004] In addition to carboxylic acids, amines or amines
It is conceivable to use carboxylic acid derivatives,
For practical reasons and toxicity, it was not practical. Departure
For the lighter, etc., the curing speed is high and the curing property is low
As a result of intensive research to obtain a resin composition,
Synergistic effect when acid and amine or amine derivative are used together
Can not be imagined from using both alone
As the curing rate of the polymer increases dramatically,
The present invention has been reached. In addition, specific carboxylic acids and amines
Combination improves durability, mechanical properties and rubbery properties
I also found out. [0005] SUMMARY OF THE INVENTION The present invention relates to (A) a silicon source.
Having a hydroxyl group or a hydrolyzable group bonded to a
Silicon-containing groups that can be crosslinked by forming
Below, referred to as a reactive silicon group)
Hydrocarbon-based polymer, (B) having at least a carboxyl group
Compound having one and (C) at least one amino group
The present invention relates to a curable composition containing a compound having the same. [0006] The curable composition of the present invention comprises the component (A)
Have a hydroxyl group or a hydrolyzable group
And silicon that can be crosslinked by forming siloxane bonds
Saturated group having at least one silicon-containing group, ie, a reactive silicon group.
Japanese hydrocarbon polymer (hereinafter referred to as saturated hydrocarbon polymer)
(Also referred to as (A)). As a typical example of the reactive silicon group, general
Equation (1) -[-Si (-R¹ _2-b ) (-X_b ) -O-]_m -Si (-R^Two _3-a ) (-X_a  (1) And the group represented by In the general formula (1), R¹ And R^Two Yes
The shift is also an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 6 to 20 carbon atoms.
Aryl group, aralkyl group having 7 to 20 carbon atoms, or R '_Three SiO- (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different. )so
A triorganosiloxy group represented by¹ Or R^Two
When two or more are the same, they are different
Is also good. X is a hydroxyl group or a hydrolyzable group, and two or more
When present, they may be the same or different. a
Is 0, 1, 2 or 3 and b is 0, 1 or 2
Satisfies a + mb ≧ 1. In addition, m pieces of-[-Si (-
R¹ _2-b ) (-X_b B) in-)-O-]-are the same.
Need not be. m represents 0 or an integer of 1 to 19. The hydrolyzable group is not particularly limited.
It does not need to be a conventionally known hydrolysable group,
Examples of the body include a hydrogen atom, an alkoxy group,
Ruoxy group, ketoxime group, amino group, amide group,
Aminooxy group, mercapto group, alkenyloxy group, etc.
And the commonly used groups of this
Among them, mild hydrolysis is easy to handle.
In this respect, an alkoxy group is particularly preferred. The hydrolyzable group and the hydroxyl group are one silicon source.
Can be bound in the range of 1 to 3
b) preferably ranges from 1 to 5. Hydrolysable
When two or more groups or hydroxyl groups are bonded to the reactive silicon group
May be the same or different. The silicon atom forming the reactive silicon group is 1
May be used, or two or more.
In the case of silicon atoms connected by bonding or the like, 20
It is preferably up to. In particular, the formula: -Si (-R^Two _3-a ) -X_a (Where R^Two , X and a are the same as described above. )
The reactive silicon group to be used is preferable because it is easily available. [0012] The reactive silicon group is formed of a saturated hydrocarbon polymer.
At least one, preferably 1.1 to 5 per molecule
Exist. Less than one reactive silicon group in the molecule
, The curability becomes insufficient and good rubber elastic behavior
Is difficult to express. The reactive silicon group is a component of a saturated hydrocarbon polymer.
May be present at the end of the strand,
And may be present in both. Especially reactive silicon groups
Is finally formed when is present at the end of the molecular chain
Effective network of saturated hydrocarbon polymer component contained in cured product
Since the chain amount increases, a high-strength, high-elongation rubber-like cured product can be obtained.
It is preferable in that it can be easily obtained. In addition, these reactions
Saturated hydrocarbon-based polymers having a crystalline silicon group
Or two or more of them may be used in combination. [0014] The saturated hydrocarbon polymer referred to in this specification
Represents a carbon-carbon unsaturated bond other than an aromatic ring.
This is a concept meaning a polymer that does not have
The skeleton of a saturated hydrocarbon polymer having a reactive silicon group
Can be obtained by the following method, etc.
It is. (1) ethylene, propylene, 1-butene, i
An olefinic compound having 1 to 6 carbon atoms such as sobutylene
A method of polymerizing as a main monomer. (2) Diene compounds such as butadiene and isoprene are used alone
Polymerized or the above olefin compound and diene compound
And then hydrogenating. Of these polymers, a functional group is introduced at the terminal.
Easy to enter, easy to control molecular weight, large number of terminal functional groups
Isobutylene-based polymer and
It is preferably a hydrogenated polybutadiene polymer. The isobutylene-based polymer has a monomer unit
May be formed of isobutylene units.
Isobutylene monomer units copolymerizable with sobutylene
50% (wt%, the same applies hereinafter) in the polymer
Or less, more preferably 30% or less, particularly preferably 10% or less.
% Or less. As such a monomer component, for example,
C4-12 olefins, vinyl ethers, aromatics
Vinyl compounds, vinylsilanes, allylsilanes, etc.
I can do it. Specific examples of such a copolymer component include:
For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-
Methyl-1-butene, pentene, 4-methyl-1-pentene,
Hexene, vinylcyclohexane, methyl vinyl ether
, Ethyl vinyl ether, isobutyl vinyl ether
Styrene, α-methylstyrene, dimethylstyrene
, Monochlorostyrene, dichlorostyrene, β-pine
, Indene, vinyltrichlorosilane, vinylmethyl
Dichlorosilane, vinyldimethylchlorosilane, vinyl
Dimethylmethoxysilane, vinyltrimethylsilane, di
Vinyl dichlorosilane, divinyl dimethoxy silane, di
Vinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetra
Methyldisiloxane, trivinylmethylsilane, tetra
Vinylsilane, allyltrichlorosilane, allylmethyl
Dichlorosilane, allyldimethylchlorosilane, allyl
Dimethylmethoxysilane, allyltrimethylsilane, di
Allyl dichlorosilane, diallyldimethoxysilane, di
Allyldimethylsilane, γ-methacryloyloxypro
Piltrimethoxysilane, γ-methacryloyloxyp
And propylmethyldimethoxysilane. These monomers copolymerizable with isobutylene
When vinyl silanes or allyl silanes are used as
The silicon content of the coalesce increases, making it a silane coupling agent.
The number of groups that can act and increase the adhesiveness of the resulting composition
Is improved. Furthermore, hydrogenated polybutadiene-based polymers and other
Even in saturated hydrocarbon polymers, isobutylene-based
As in the case of the body, in addition to the main monomer unit, other
A monomer unit may be contained. The saturated hydrocarbon polymerization used in the present invention
In the body, butadiene as long as the object of the present invention is achieved,
Double bonding after polymerization such as polyene compounds such as isoprene
A small amount of the remaining monomer units, preferably 10% or less,
May be contained in a range of 5% or less, particularly 1% or less.
No. The saturated hydrocarbon polymer (A), in particular
Number of sobutylene polymers and hydrogenated polybutadiene polymers
The average molecular weight should be around 500-100,000
Preferred, especially about 1,000 to 30,000 liquids
It is preferable to use the most fluid because it is easy to handle.
No. Furthermore, the molecular weight distribution (M_w / M_n ) Is the same
M in terms of lower viscosity at molecular weight_w / M_n But
The narrower the better. Saturated Hydrocarbon Polymerization Having Reactive Silicon Group
Production method, especially isobutylene-based polymer and
The case of a hydrogenated polybutadiene polymer will be described as an example.
You. The above-mentioned isobutylene polymer having a reactive silicon group
Among them, isobutylene having a reactive silicon group at the molecular terminal
Polymers are based on a polymerization method called inifer method (inifer method).
Specific compounds that are both initiators and chain transfer agents
End-functional type obtained by the cationic polymerization method using
More preferably, it is manufactured using an all-terminal functional isobutylene polymer.
Can be built. Such a manufacturing method is disclosed in
No.-6003, No.63-6041, No.63-2541
No. 49, No. 64-22904, No. 64-38407
It is described in publications and the like. Further, it has a reactive silicon group inside the molecular chain.
Isobutylene-based polymer is a simple substance mainly composed of isobutylene.
Vinyl silanes or ants containing reactive silicon groups
It is produced by adding silanes and copolymerizing.
It is. Further, it has a reactive silicon group at the terminal of the molecular chain.
In the polymerization when producing an isobutylene-based polymer,
Reactive silicon groups other than the main component isobutylene monomer
Vinyl silanes and allyl silanes
After that, by introducing a reactive silicon group into the terminal,
Isobutylene having reactive silicon group at the end and inside the molecular chain
A polymer can be produced. Vinyl silanes having a reactive silicon group
And specific examples of allylsilanes, for example, vinyl
Trichlorosilane, vinylmethyldichlorosilane, vinyl
Dimethyl chlorosilane, vinyl dimethyl methoxy sila
, Divinyldichlorosilane, divinyldimethoxysila
, Allyltrichlorosilane, allylmethyldichlorosilane
Orchid, allyldimethylchlorosilane, allyldimethylme
Toxysilane, diallyldichlorosilane, diallyldimethyl
Toxysilane, γ-methacryloyloxypropyl tri
Methoxysilane, γ-methacryloyloxypropyl
Tildimethoxysilane and the like. A method for producing a hydrogenated polybutadiene polymer is described.
For example, for example, first, a polybutadi
The hydroxyl group of the ene polymer is converted to an oxime such as -ONa or -OK.
After converting to a tall group, the general formula (2):   CH_Two = CH-R^Three -Y (2) [In the formula, Y is a halogen atom such as a chlorine atom and an iodine atom.
R^Three Is -R^Four -, -R^Four -OC (= O)-, -R
^Four -C (= O)-(R^Four Is a divalent carbon having 1 to 20 carbon atoms
Preferred examples of the hydrogen group include an alkylene group and a cycloalkyl group.
Loalkylene group, arylene group, aralkylene group
Is a divalent organic group represented by the formula_Two -And
R "-Ph-CH_Two -(R ″ is a hydrocarbon having 1 to 10 carbon atoms)
An element group, Ph, is a p-phenylene group. 2) selected from
Group is particularly preferable].
Is reacted with water having a terminal olefin group.
Hydrogenated polybutadiene polymer (hereinafter referred to as hydrogenated olefin
Polybutadiene polymer).
Wear. Hydroxy-terminated polybutadiene-based polymerization
As a method of converting the terminal hydroxyl group of the body into an oxymetal group,
Alkali metals such as Na and K; Metal water such as NaH
Hydride; NaOCH_Three Metal alkoxides such as
Method to react with caustic alkalis such as OH and KOH
Can be mentioned. In the above method, the starting material
Was approximately the same as the hydroxy-terminated polybutadiene polymer
Hydrogenated polybutadiene system with terminal olefin having the same molecular weight
A polymer is obtained, but to obtain a higher molecular weight polymer
Is reacted with an organic halogen compound of the general formula (2).
Methylene chloride, bis (chloromethyl) benzene,
Halogens in one molecule such as
Reaction with a polyvalent organic halogen compound containing two or more
After increasing the molecular weight, the organic compound represented by the general formula (2)
When reacted with a halogen compound, it has a higher molecular weight and
Obtain hydrogenated polybutadiene polymer having olefin group
Can be The organic halogen represented by the general formula (2)
Specific examples of the compound include, for example, allyl chloride,
Allyl bromide, vinyl (chloromethyl) benzene,
Allyl (chloromethyl) benzene, allyl (bromomethyl
Le) benzene, allyl (chloromethyl) ether, ant
(Chloromethoxy) benzene, 1-butenyl
Tyl) ether, 1-hexenyl (chloromethoxy) ben
Zen, allyloxy (chloromethyl) benzene, etc.
But not limited thereto.
Of these, they react cheaply and easily.
Allyl chloride is preferred. Hydrogenated polybutadiene based olefin polymerization
The reactive silicon group is introduced into the body by adding reactive silicon
As in the case of the isobutylene polymer having a group,
For example, a hydrogen atom is bonded to a group represented by the general formula (1).
Hydrosilane compounds, preferably of the general formula: H-Si (-R^Two _3-a ) -X_a  (Where R^Two , X and a are the same as described above. )
Of the compound to be added using a platinum-based catalyst
Manufactured. A hydrogen atom is added to the group represented by the general formula (1).
Specific examples of the hydrosilane compound to which
For example, trichlorosilane, methyldichlorosilane,
Halogen such as tylchlorosilane and phenyldichlorosilane
Silanes; trimethoxysilane, triethoxysila
, Methyldiethoxysilane, methyldimethoxysila
, Alkoxysilanes such as phenyldimethoxysilane
: Methyldiacetoxysilane, phenyldiacetoxy
Acyloxysilanes such as silane; bis (dimethylketoki)
(Simate) methylsilane, bis (cyclohexyl ketoki)
Ketoximate silanes such as shimate) methyl silane
But are not limited to these. This
Of these, halogenated silanes, alkoxy
Silanes are preferred. The carboxyl group which is the component (B) of the present invention
Having at least one (hereinafter referred to as a carboxyl group)
Is not particularly limited, and various compounds
Can be used. Of carboxyl group-containing compounds
Specific examples are as follows. (1) Saturated monocarboxylic acid (A) formic acid, acetic acid, acetoacetic acid, ethyl methyl acetic acid, professional
Pionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, ethoxy vinegar
Acid, valeric acid, isovaleric acid, hexanoic acid, 2-ethylhexa
Acid, octanoic acid, decanoic acid, undecanoic acid, glyoxy
Saturated monocarbo such as silic acid, glycolic acid, gluconic acid
Acid, (b) acrylic acid, methacrylic acid, angelic acid,
Crotonic acid, isocrotonic acid, 10-undecenoic acid, gills
Olefin monoca, such as icidic, erucic and oleic acids
Acetylene monocarboxylic acid such as rubonic acid and (c) propiol
Acid, (d) linoleic acid, linoleic acid, etc.
Carboxylic acid, (e) linolenic acid, arachidonic acid, etc.
Unsaturated monocarboxylic acid, (f) chloroacetic acid,
Monohalo of monocarboxylic acids such as lylic acid and chlorobenzoic acid
Gen-substitute, (2) Aliphatic dicarboxylic acid (a) adipic acid, azelaic acid, ethylmalonic acid, glue
Talic acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid
(B) maleic acid, fumaric acid,
Unsaturated dicarbo such as cetylenedicarboxylic acid and itaconic acid
Acid, (3) Aliphatic polycarboxylic acid (a) Trica such as aconitic acid, citric acid, and isocitrate
Rubonic acid, (4) Aromatic carboxylic acid (a) Benzoic acid, 9-anthracene carboxylic acid, atorolac
Formic acid, anisic acid, isopropyl benzoic acid, salicyl
Acid, aromatic monocarboxylic acid such as toluic acid, (b) phthalic acid
Acid, isophthalic acid, carboxyphenylacetic acid, pyromelli
Aromatic polycarboxylic acids such as citric acid, (5) Other Alanine, leucine, threonine, aspartic acid,
Glutamic acid, arginine, cysteine, methionine,
Amines such as phenylalanine, tryptophan and histidine
Acid. Thus, at least one molecule in one molecule
Any compound having a carboxyl group
May be. These compounds may be used alone.
Alternatively, two or more kinds may be used in combination. The above compounds
In addition, an aliphatic monocarboxylic acid is preferable, and has 2 to 3 carbon atoms.
Is more preferable. The amino group which is the component (C) of the present invention has a small content.
At least one compound (hereinafter referred to as an amino group-containing compound)
) Is not particularly limited, and various compounds may be used.
Can be. Specific examples of the amino group-containing compound are given below.
You. (1) Primary amine (a) methylamine, ethylamine, propylamine, a
Sopropylamine, isopropyl alcoholamine,
Tylamine, 1-ethylbutylamine, isobutylamido
, Pentylamine, octylamine, laurylamine
, Monoethanolamine, diethylaminopropyl alcohol
Min, oleylamine, cyclohexylamine, benzi
Luamine, guanidine, 2-ethylhexylamine, triamine
Aliphatic primary amines such as ethylenetetramine;
, Benzylaniline, nitroaniline, phenylene
Amine, toluidine, toluylamine, xylene diamine
2,3-xylidine, anisidine, phenetidine, ben
Aromatic compounds such as dizine, benzylamine and naphthylamine
1 amine, (2) Secondary amine (a) dimethylamine, diethylamine, diethanol alcohol
Min, diethylenetriamine, dibutylamine, piperi
Gin, diisopentylamine, pyrrolidine, morpholy
Aliphatic secondary amines such as butane, 2-ethyl-4-methylimidazole, etc.
Min, (b) N-ethylnaphthylamine, acetanilide,
Aromas such as acetamidonaphthalene and diphenylguanidine
Aromatic second amine, (3) Tertiary amine (a) trimethylamine, triethylamine, triethano
Amine, tripropylamine, tributylamine,
1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-di
Aliphatic compounds such as azabicyclo [5.4.0] undecene-7 (DBU)
3-amine, (b) N, N-dimethylaniline, N, N-dibenzyl
Aniline, dimethylaminobenzoic acid, 2,4,6-tris
Aromatic tertiary amino acids such as methylaminomethyl) phenol
N. Thus, at least one compound in one molecule
Any compound having an amino group
Good. These compounds may be used alone or in combination of two
These may be used in combination. In addition, among the above compounds, the first
Amines and tertiary amines are preferred in terms of activity,
Min is more preferred. These carboxyl group-containing compounds and amino acids
The amount of the hydroxyl group-containing compound used depends on the amount of the saturated carbon
100 parts by weight of hydrogen-based polymer (hereinafter simply referred to as "parts")
To 20 parts by weight, preferably 0.1 to 20 parts by weight.
1 to 10 parts is more preferred. This amount is less than 0.01 parts
When full, the curing speed may slow down,
It may be difficult to proceed sufficiently. Effective if over 20 parts
Fruits do not change much and costs are unnecessarily high
In addition, problems such as coloring and water resistance may occur.
You. Carboxyl-containing compound and amino-containing
There are no particular restrictions on the compounding ratio with the compound, but the molar ratio
Ruboxyl group-containing compound / amino group-containing compound)
0.01 to 50 is preferable, and 0.1 to 20 is more preferable.
No. The curing speed can be adjusted by changing the mixing ratio of the two.
Can be knotted. In preparing the compositions of the present invention,
Hydrocarbon polymer, carboxyl group-containing compound and amine
In which order
The spider is not particularly limited. For saturated hydrocarbon polymers
The carboxyl group-containing compound may be added first,
The group-containing compound may be added first. Carboxyl group included
Even if a saturated hydrocarbon polymer is added first to an existing compound
Alternatively, the amino group-containing compound may be added first. Ma
A carboxyl group-containing compound and an amino group-containing compound;
May be added at the same time, or
To form a salt or complex, and add this to the polymer.
May be adopted. In the composition of the present invention, if necessary,
Improves the phenol condensation catalyst (curing catalyst), tensile properties, etc.
Physical property modifier, reinforcing or non-reinforcing filler, plasticizer,
Adhesion promoter, anti-sag, colorant, anti-aging agent, flame retardant
And other additives may be used. Specific examples of such a silanol condensation catalyst include
For example, tetrabutyl titanate, tetrapro
Titanates such as pyrtitanate; dibutyltindi
Laurate, dibutyltin maleate, dibutyltin diacetate
Tin carboxylic acid such as tin, tin octylate, tin naphthenate
Salts: The reaction between dibutyltin oxide and phthalic acid ester
Corresponding substance: dibutyltin diacetylacetonate; aluminum
Mutris acetylacetonate, aluminum trisue
Tilacetoacetate, diisopropoxy aluminum
Organoaluminum compounds such as ethyl acetoacetate
And zirconium tetraacetylacetonate, titanium
Chelating compounds such as tetraacetylacetonate;
Lead citrate; obtained from excess polyamine and polybasic acid
Low molecular weight polyamide resin; excess polyamine and epoxy
Reaction product with a compound; γ-aminopropyltrimethoate
Xysilane, N- (β-aminoethyl) aminopropyl
Silane having amino group such as methyldimethoxysilane
Silanol condensation catalysts such as coupling agents, and other acidic
Examples include known silanol condensation catalysts such as catalysts and basic catalysts.
Can be shown. These catalysts may be used alone,
More than one species may be used in combination. As the above fillers and reinforcing materials, concretely
Are, for example, heavy and light calcium carbonate;
Expressed as fatty acid, cationic surfactant, anionic surfactant, etc.
Surface treated calcium carbonate; magnesium carbonate;
Luc; Titanium oxide; Barium sulfate; Alumina; Aluminum
Metal powders such as um, zinc and iron; bentonite, kao link
Ray; fumed silica; quartz powder; white carbon;
Carbon black; usually talc, asbestos, glass fiber, etc.
Those used are listed. Especially fumed silica
The use of fillers and reinforcing materials that give transparency to
It is also possible to make a sealed sealant. these
Only one type of filler may be used, or two or more types may be used together.
May be used. Further, for adjustment of physical properties and properties, etc.
As the plasticizer used, specifically, for example, jib
Tyl phthalate, diheptyl phthalate, di (2-ethyl
Hexyl phthalate, butyl benzyl phthalate, butyral
Phthalates such as luphthalylbutyl glycolate
And dioctyl adipate, dioctyl sebacate, etc.
Non-aromatic dibasic acid esters; diethylene glycol di
Benzoate, triethylene glycol dibenzoate
Esters of polyalkylene glycols such as
Phosphoric acid such as zyl phosphate and tributyl phosphate
Stels; chlorinated paraffins; alkyldiphenyl, parts
Hydrocarbon oils such as hydrogenated terphenyls, process oils
And plasticizers such as alkylbenzenes.
You. These plasticizers may be used alone or in combination of two or more.
Can, but need not be.
Further, these plasticizers may be blended at the time of polymer production.
No. However, it is preferable to select one with good compatibility.
No. As the above-mentioned anti-aging agent, amine-based, fluorinated
Enol-based, imidazole-based, amine-aldehyde-based,
Normal antioxidants such as amine-ketone, sulfur and phosphorus
Agents, ozone deterioration inhibitors, ultraviolet absorbers and the like. The curable composition of the present invention can be used as an industrial elastic material.
Materials, sealing composition materials, adhesive materials, potting materials, packaging
As material, waterproofing agent, molding material, binder, modifier
Can be usefully used. Above all, sealants,
Application to adhesives is particularly useful. [0048] Next, the present invention will be described specifically with reference to examples.
However, the present invention is not limited to these. Production Example 1 In a four-necked flask equipped with a stirrer and nitrogen line
560 mL of dried methylene chloride and n-hexane 116
0 mL, α-methylpyridine 940 mg, p-dimethylcum loli
After weighing 22 g of the solution to make a uniform mixed solution,
And cooled under reduced pressure to 570 mL of isobutylene monomer.
Charged through a Molecula sieves tube. Up to -70 ° C
In the cooled reaction solution, polymerize
Catalyst solution (titanium tetrachloride 14mL / methylene chloride 80mL)
Was added all at once to initiate the polymerization. Once to -54 ° C
After the temperature was raised, the temperature was lowered to -70 ° C in about 17 minutes. Polymerization
About 20 minutes after the start, 132 g of 1,9-decadiene was added,
Stirring was further continued at -70 ° C for 4 hours. Yellow-colored reaction
The solution is placed in 3 L of warm water (about 45 ° C.) and stirred for about 2 hours.
Stir, separate the organic layer, and wash with pure water three times.
Was. The colorless and transparent organic layer thus obtained was concentrated under reduced pressure,
Approximately 4 isobutylene oligomers having vinyl groups at both ends
00g was obtained. Next, the vinyl group-containing a thus obtained
400 g of sobutylene oligomer is added to 200 mL of n-heptane
And heated to about 70 ° C.
Silane 1.5 [eq / vinyl group], platinum (vinyl siloxa
N) Complex 1 × 10^-Four[Eq / vinyl group]
A silylation reaction was performed. Reaction tracking by FT-IR
It is 1640cm in about 4 hours^-1Olefin absorption disappears
Was. By concentrating the reaction solution under reduced pressure,
A molecular weight of 5,300 having reactive silicon groups at both ends
Was obtained.   [Structural formula]   Me (MeO)_Two Si (CH_Two )₈ CHClCH_Two −   − (C (Me)_Two CH_Two )_n C (Me)_Two (C₆ H_Four ) C (Me)_Two −                 − (CH_Two C (Me)_Two )_m CH_Two CHCl (CH_Two )₈ −                                                 -SiMe (OMe)_Two Production Example 2 In Production Example 1, allylmethyene was used in place of 1,9-decadiene.
Production Example 1 was repeated except that 24 g of silane was used.
The structure of the production intermediate has a partially different molecular weight of 4,400.
An isobutylene oligomer was obtained. [0051]   [Structural formula]   Me (MeO)_Two Si (CH_Two )_Three (C (Me)_Two CH_Two )_n −     -C (Me)_Two (C₆ H_Four ) C (Me)_Two − (CH_Two C (Me)_Two )_m −                                     − (CH_Two )_Three SiMe (OMe)_Two Production Example 3 In a four-necked flask equipped with a stirrer and nitrogen line
560 mL of dried methylene chloride and n-hexane 116
0 mL, α-methylpyridine 940 mg, p-dimethylcum loli
After weighing 22 g of the solution to make a uniform mixed solution,
And cooled under reduced pressure to 570 mL of isobutylene monomer.
Charged through a Molecula sieves tube. Up to -70 ° C
In the cooled reaction solution, polymerize
Catalyst solution (titanium tetrachloride 14mL / methylene chloride 80mL)
Was added all at once to initiate the polymerization. Once to -54 ° C
After the temperature was raised, the temperature was lowered to -70 ° C in about 17 minutes. Polymerization
After the start, stirring was continued for about 60 minutes. Yellow-colored reaction solution
Into 3L of warm water (about 45 ° C) and stir for about 2 hours
Then, the organic layer was separated, and the washing with pure water was repeated three times.
The colorless and transparent organic layer thus obtained was concentrated under reduced pressure.
Isobutylene oligomer having a tertiary chloro group at its end
400 g were obtained. Further, the isobutylene oligomer is reduced.
By continuing heating at 170 ° C. under pressure for 2 hours,
Performs thermal dehydrochlorination and has an isopropenyl group at both ends.
The obtained isobutylene oligomer was obtained. Then, the isopropenyl thus obtained is obtained.
400 g of a group-containing isobutylene oligomer is added to n-heptane
Dissolve in 200 mL and heat to about 100 ° C in a pressure vessel
After that, methyl dichlorosilane 1.5 [eq / vinyl group],
Platinum (vinylsiloxane complex 1 × 10^-Four[Eq / vinyl
And a hydrosilylation reaction was carried out. FT-I
Follow the reaction with R, and 1640 cm in about 10 hours^-1of
Olefin absorption disappeared. Cool the reaction solution to 60 ° C
And then an excess of [/ methyldichlorosilane] in methanol
And the mixture was stirred for about 4 hours to complete the methoxylation.
I let you. Concentrate the reaction solution under reduced pressure to obtain the target
Isomers having a reactive silicon group at both ends and having a molecular weight of 4,300
A butylene oligomer was obtained. [0054]   [Structural formula]   Me (MeO)_Two SiCH_Two CH (Me) CH_Two −       − (C (Me)_Two CH_Two )_n C (Me)_Two (C₆ H_Four ) C (Me)_Two −                   − (CH_Two C (Me)_Two )_m CH_Two CH (Me) CH_Two −                                                 -SiMe (OMe)_Two Example 1 As the component (A), 100 parts of the polymer obtained in Production Example 1 was used.
Colloidal calcium carbonate (Shiraishi Industry Co., Ltd., trade name
120 parts of Scolite-R, process oil (PS-3)
2) 90 parts, hindered amine anti-aging agent (Ouchi Shinko
Chemical Co., Ltd., trade name Nocrack NS-6) 1 part, cross-linked
As an agent, 5 parts of sodium sulfate hydrate was added. Furthermore,
Add 1 part of laurylamine and 2 parts of 2-ethylhexanoic acid
After thoroughly kneading, remove three small paint rolls
The sheet was passed through to produce a sheet having a thickness of 3 mm. After that,
The sheet is cured at 23 ° C / 50% RH and the sheet hardens.
Was measured. In addition, judgment whether or not
Is the tack free time of JIS A5758 (necessary for curing
The measurement was performed by touching the finger according to the measurement method described in (1). That
The results are as shown in Table 1. Comparative Example 1 Without adding 2-ethylhexanoic acid, add 3 parts of laurylamine.
The procedure was performed in the same manner as in Example 1 except for the above. The results are shown in Table
As shown in FIG. Comparative Example 2 Without adding laurylamine, add 3 parts of 2-ethylhexanoic acid.
The procedure was performed in the same manner as in Example 1 except for the above. The results are shown in Table
As shown in FIG. Comparative Example 3 Without adding 2-ethylhexanoic acid, instead dibutyltin
Example 1 with the exception that 3 parts of dilaurate (DTL) were added.
Performed similarly. The results are as shown in Table 1. [0055]               Table-1   Polymer of Production Example 1:Example Comparative example                                     1 1 2 3   Laurylamine (parts) 130   2-ethylhexanoic acid (parts)   Dibutyltin dilaurate (parts) 0 0 0 3   Tack free time (hours) 3.7 24 <24 <5.5 As is clear from Table 1 above, 2-ethylhexanoic acid
When used in combination with laurylamine,
The time required for curing is significantly shorter than when used in
With dibutyltin dilaurate (DTL).
Cured at about the same speed. In place of the polymer obtained in Production Example 1,
Using the polymer obtained in Production Example 2 or 3, Examples 1 and
2. When evaluated in the same manner as Comparative Examples 1 to 3,
The same effect as in the case was obtained. Examples 2 to 6 Lauri with 2 parts of 2-ethylhexanoic acid and the ratio shown in Table-2
Luamine and mixed with each other.
Leatime was measured (23 ° C./50% RH). The result
The results are as shown in Table-2. Note that the result of Example 1 is also
I will write it together. [0058]               Table-2   Using the polymer of Production Example 1:                           Molar ratio Tack free time           (2-ethylhexanoic acid / laurylamine) (time)   Example 1 2.6 3.7   Example 2 0.5 4.0   Example 3 1.0 3.5   Example 4 1.5 3.1   Example 5 2.5 3.4   Example 6 20.0 1.6 As is clear from Table 2 above, 2-ethylhexanoic acid
Very fast curing speed due to combined use of lactone and laurylamine
A curable resin composition was obtained. In Production Examples 2 and 3,
The obtained polymer was evaluated in the same manner as described above.
As a result, almost the same results were obtained. [0059] According to the present invention, inexpensive and less toxic hard
A curable composition can be provided. Moreover, the curable composition
The curing speed is remarkably fast.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-279570 (JP, A) JP-A-6-49363 (JP, A) JP-A-5-186694 (JP, A) JP-A-2- 185565 (JP, A) JP-A-2-97562 (JP, A) JP-A-1-252670 (JP, A) JP-A-1-170658 (JP, A) JP-A-1-168764 (JP, A) JP-A-1-167371 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C06K 3/00-13/08

Claims (1)

(A) Saturated having (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond. (B) 0.01 to 20 parts by weight per 100 parts by weight of the component (A)
A compound having at least one carboxyl group in parts by weight and a molar ratio of (C) (B) / (C) of 0.01 to 5;
A curable composition containing a compound having at least one amino group which is 0.