JPH05287190A - Production of curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition good in durability and workability and useful for sealing materials, etc., by adding a pigment component and a curing catalyst component to a reactive silicon group-containing polyoxyalkylene polymer in the other apparatus at the final stage and improving the production processes. CONSTITUTION:100 pts.wt. of a reactive silicon group-containing polyoxyalkylene polymer (e.g. gamma-glycidoxypropyltrimethoxysilane-treated polyoxypropylene), 120 pts.wt. of surface-treated colloidal calcium carbonate, 50 pts.wt. of dioctyl phthalate and 3 pts.wt. of hydrogenated caster oil are mixed with a mixer A. The mixture is further mixed with 3 pts.wt. of vinyltrimethoxysilane and 2 pts.wt. of 7-aminoethyl-beta-aminopropyltrimethoxysilane, and subsequently transferred to a line-mixer C in the other installation. The transferred mixture is mixed with a curing catalyst (e.g. acetylacetonato) and a pigment component fed from a catalyst/pigment tank B, and then charged in containers with a charging machine E to provide the objective one pack type curing composition in good productivity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a one-component curable composition having excellent productivity.

[0002]

2. Description of the Related Art One-component type curable compositions containing a reactive silicon group-containing polyoxyalkylene polymer as an essential component are widely used, for example, for sealing materials because of their excellent durability and workability. Since the above composition is cured by moisture contained in humidity, it is usually produced in a closed-system mixing mixer, but the cleaning work performed by opening the mixer after the production has an effect that the contents are affected by moisture in the air. Since it is hardened by curing, it is a troublesome work, and when the color is changed, the quality (color etc.) of the subsequent product is affected by the trace amount of the residue of the previous product, so thorough cleaning is required. However, the cleaning work was difficult.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a one-component curable composition having excellent productivity by improving the production process.

[0004]

The above object of the present invention is to prepare a one-component type curable composition containing a reactive silicon group-containing polyoxyalkylene polymer as an essential component, in which a curing catalyst component is mixed with a line mixer. This is achieved by a method for producing a curable composition, which comprises adding and mixing in a separate device at the final stage of the process.

That is, in the production of the one-component type curable composition, a curing catalyst component is added and mixed by a line mixer to the composition in which the main filler is already mixed, or at the final stage of the process. By adding and mixing in a separate device, cleaning of the main mixing device of the manufacturing becomes almost unnecessary, and the purpose of the cleaning operation is achieved by cleaning only the small mixing device as needed. The reactive silicon group in the reactive silicon group-containing polyoxyalkylene polymer used in the present invention is not particularly limited,
Typical examples include groups represented by the following general formula (1).

[0006]

[Chemical 1]

[Wherein R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Aralkyl group having 7 to 20 carbon atoms or (R ³ ) ₃ SiO
When a triorganosiloxy group represented by-is present and two or more R ¹ or R ² are present, they may be the same or different. Here, R ³ has 1 to 2 carbon atoms
It is a monovalent hydrocarbon group of 0, and three R ^{3 s} may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they may be the same or different. a is 0,
1, 2 or 3 is shown, and b is 0, 1 or 2. In addition, b in the following m [Chemical Formula 2] groups may be different. m shows the integer of 0-19. However, a + Σ
It is assumed that b ≧ 1 is satisfied. ]

[0008]

[Chemical 2]

The hydrolyzable group represented by X above is not particularly limited and may be any conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group,
Examples thereof include an alkenyloxy group. Among these,
A hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, but an alkoxy group such as a methoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Particularly preferred.

1 to 3 of these hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom, and (a + Σb) is 1
It is preferably -5. When two or more hydrolyzable groups or hydroxyl groups are present in the reactive silicon, they may be the same or different. The reactive silicon may have one silicon atom or two or more silicon atoms, but in the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like, there may be about 20 silicon atoms. Good. The reactive silicon group represented by the following general formula (2) of [Chemical Formula 3] is preferable from the viewpoint of easy availability.

[0011]

[Chemical 3]

[Wherein R ² , X and a are the same as defined above. Specific examples of R ¹ and R ² in the general formula (1) include, for example, alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and benzyl group. An aralkyl group such as R ³ and R ³ is a methyl group or a phenyl group (R ³ ) ₃
Examples thereof include a triorganosiloxy group represented by SiO-. A methyl group is particularly preferable as R ¹ , R ² and R ³ . At least one reactive silicon group, preferably 1.1 to 5 is present in one molecule of the oxyalkylene polymer. When the number of reactive silicon groups contained in one molecule of the polymer is less than 1, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the terminal of the molecular chain of the oxyalkylene polymer or may be present inside. When the reactive silicon group is present at the terminal of the molecular chain, the amount of effective network chains of the oxyalkylene polymer component contained in the finally formed cured product increases, so that high strength, high elongation, and low elastic modulus are achieved. The rubber-like cured product shown is easily obtained.
As the oxyalkylene polymer constituting the polymer chain in the polymer of the present invention, those represented by the following general formula (3) can be used.

General formula (3)-(R--O) _n- : (R is a divalent alkylene group having 1 to 4 carbon atoms, and n is the number of repetitions) However, from the viewpoint of easy availability. An oxyalkylene polymer having a repeating unit represented by the following general formula (4) is preferable.

General Formula (4) --CH (CH ₃ ) CH ₂ O-- The oxyalkylene polymer may be linear or branched, or may be a mixture thereof. Good. Further, other monomers and the like may be contained, but the monomer unit represented by the above general formula (4) is contained in the polymer in an amount of 50 or more.
It is preferably present in an amount of not less than 80% by weight, preferably not less than 80% by weight.

The oxyalkylene polymer having a reactive silicon group of the present invention is preferably obtained by introducing a reactive silicon group into an oxyalkylene polymer having a functional group. The reactive silicon group may be introduced by a known method. That is, for example, the following method can be used. (1) An oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group reactive with the functional group, or with an unsaturated group-containing epoxy compound An unsaturated group-containing oxyalkylene polymer obtained by the copolymerization of is obtained. Then, the obtained reaction product is hydrosilylated by reacting hydrosilane having a reactive silicon group. (2) The unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1) is reacted with a compound having a mercapto group and a reactive silicon group. (3) An oxypropylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter referred to as Y ¹ functional group) at the above-mentioned terminal has a functional group (hereinafter referred to as a functional group reactive with the Y ¹ functional group). , Y ² functional group) and a compound having a reactive silicon group.

As the silicon compound having the Y ² functional group, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane. Amino group-containing silanes such as; γ-
Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane; such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Epoxy silanes; vinyl-type unsaturated group-containing silane groups such as vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane; γ-chloropropyltrimethoxysilane, etc. Chlorine atom-containing silanes;
γ-isocyanatopropyltriethoxysilane, γ-
Isocyanate-containing silanes such as isocyanate propylmethyldimethoxysilane; hydrosilanes such as methyldiethoxysilane can be specifically exemplified, but not limited thereto. Among the above methods, the method (1) or the method (3) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is preferable.

The above-mentioned reactive silicon group-containing oxyalkylene organic polymer is not particularly limited, but representative ones include, for example, JP-A-50-15659.
No. 9, No. 54-6096, No. 57-126823,
59-78223, 55-82123, 55
-113022, 55-137129, 62-
No. 230822, No. 63-83131, JP-A-3-4
No. 7825, No. 3-72527, No. 3-122152
U.S. Pat. Nos. 3,632,557 and 4,345.
No. 053, No. 4,366, 307, No. 4,960,8
Those disclosed in No. 44 and the like can be exemplified. Among these polymers, JP-A-3-47825 and 3-7252
Nos. 7 and 3-122152, a polymer having a molecular weight distribution (M _w / M _n ) of 1.5 or less has a lower viscosity than a polymer having a molecular weight distribution of more than 1.5. The effect is remarkable. Particularly when the molecular weight is 10,000 or more, the viscosity of (M _w / M _n ) of 1.5 or less is relatively low, and the effect of the present invention is particularly remarkable. The one-component curable composition is a filler such as calcium carbonate, talc, clay and silica, a plasticizer such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin, and a petroleum plasticizer, if necessary, for the above polymer,
Anti-sagging agents such as hydrogenated castor oil, aluminum stearate and fine powder silica, various stabilizers such as antioxidants, UV absorbers, light stabilizers, various silicone compounds for adhesion and dehydration, pigments, curing catalysts And the like can be added to manufacture.

Further, if necessary, an adhesion improver, a physical property adjuster, a storage stability improver, a metal deactivator, an ozone deterioration inhibitor, an amine radical chain inhibitor, a phosphorus peroxide decomposer, Various additives such as a lubricant and a foaming agent can be appropriately added. It is desirable to dry a filler having a high water content before use.

As the curing catalyst referred to in the present invention, conventionally known ones can be widely used. Specific examples thereof include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin acetate, tin octylate and tin naphthenate; dibutyltin oxide and phthalate ester. Reaction products with, dibutyltin acetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate
Chelate compounds such as titanium tetraacetylacetonate; lead octylate; butylamine, octylamine,
Dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (Dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 2-ethyl-4-methylimidazole, 1,8 diazabicyclo (5.4.0) undecene-7 (DB
U) and other amine compounds, or salts of these amine compounds with carboxylic acids and the like; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction products of excess polyamine and epoxy compound; silane coupling agents having amino groups such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; silanol condensation catalysts such as; and other acidic catalysts, basic catalysts such as Known silanol condensation catalysts and the like can be mentioned. These catalysts may be used alone or in combination of two or more.
In the present invention, a pigment can be used, but when it is used together with a curing catalyst, the cleaning work in the process is reduced. Examples of the pigment include inorganic pigments such as iron oxide, chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green.

In order to produce by the method according to the present invention, a mixing machine for mixing a curing catalyst component, optionally a curing catalyst and components other than the pigment component, and the curing catalyst, if necessary, together with the pigment into other components. A device for adding and mixing is essential. There are various types of the former, but those that can be heated and can be deaerated in vacuum are preferable. An example is a planetary mixer manufactured by Inoue Seisakusho. As the latter device, a mixer is installed in the pipeline while the contents are sent out from the mixer and transferred to the filling machine by the pipeline, and the curing catalyst is added to the other components together with the pigment as needed in front of the mixer. In addition, a line mixer suitable for efficiently mixing these components while moving in the pipeline is preferable. Since the composition used in the present invention has a high viscosity, an extruder may be used as a line mixer. Examples of the line mixer include a static type in-pipe mixer (Hi-Mixer) manufactured by Toray Engineering Co., Ltd.

FIG. 1 shows a schematic diagram of a manufacturing flow used in the present invention. A specific example of the method for producing the curable composition of the present invention will be described below according to the production flow of FIG. However, the invention is not limited by this description.

In FIG. 1, in the mixer A, components other than the curing catalyst component of the curable composition of the present invention and, if necessary, components other than the curing catalyst and the pigment component are mixed. Here, since the curing catalyst component is not contained. The components are stable, and are stable even when exposed to the air for a long time. Therefore, it is easy to wash the mixer A after use. Since the colors such as pigments are switched after the catalyst / pigment storage tank B, the mixer A is washed less frequently. If there are many types of pigments and catalysts and it is necessary to switch frequently, it is possible to cope with this by increasing the number of catalyst / pigment storage tanks B so that the tanks B can be switched easily.

The pigment added at the position of the catalyst / pigment storage tank B and the curing catalyst component are mixed with another curable composition in the mixer C of the line. Since the mixing in the line mixer C is performed continuously, the line mixer C can be a relatively small device,
Therefore, cleaning is easy. The valve D is used to control the operation / stop of the manufacturing flow for switching the tank B and the line mixer C (operation / stop of the curable composition to be transferred). The curable composition having undergone the mixing operation is sent to a filling machine E, where it is filled in a container without being exposed to air.

[0025]

【Example】

(Example 1) In a planetary mixer manufactured by Inoue Seisakusho Co., Ltd., 85% of all terminals were (CH ₃ O) ₂ Si (CH ₃ ) CH _2.
100 parts by weight of a polyoxypropylene polymer containing a CH ₂ CH ₂ — group, having a number average molecular weight of 17,000 as measured by gel permeation chromatography and a molecular weight distribution (M _w / M _n ) = 1.3, Surface treated colloidal calcium carbonate 12
0 parts by weight, 50 parts by weight of dioctyl phthalate and 3 parts by weight of hydrogenated castor oil were charged and dehydration was performed at 110 ° C. for 3 hours under reduced pressure. After the dehydration treatment, 3 parts by weight of vinyltrimethoxysilane and 2 parts by weight of γ-aminoethyl-β-aminopropyltrimethoxysilane were added and mixed well.

The contents were extruded by a press, and a mixture of 2 parts by weight of diacetylacetonate as a curing catalyst and 5 parts by weight of a black pigment paste, which had been previously adjusted in the catalyst / pigment storage tank by the production line shown in FIG. The mixture was mixed with a static type in-tube mixer manufactured by Toray Engineering Co., Ltd., and then used for cartridge filling. After the above mixing operation was completed, the planetary mixer was opened and left for 1 day. However, no thickening of the residue was observed at all, and it is used as it is for the production of the composition for charging the next batch of pigments of different colors. I was able to.

Comparative Example 1 After preparing a base composition in a planetary mixer as in Example 1, the same curing catalyst and pigment as in Example 1 were thoroughly mixed in the same planetary mixer. After mixing, the cartridge was directly filled with a press to perform the filling operation. After the operation, when the planetary mixer was opened, skinning was observed on the surface of the residue within 30 minutes, which hindered the cleaning work. Also, a black residue was deposited in the planetary mixer, which required thorough washing before the next batch of preparation of the composition charged with differently colored pigments.

[0028]

EFFECTS OF THE INVENTION In the production of a one-component curable composition, the productivity of production is increased by the production method of the present invention in which a curing catalyst component is optionally added together with a pigment in a separate device at the final stage of the process. Was significantly improved.

[Brief description of the figure]

FIG. 1 is a schematic diagram of a manufacturing flow used in the present invention.

[Explanation of symbols]

 A mixer B catalyst / pigment storage tank C line mixer D valve E filling machine

[Procedure amendment]

[Submission date] June 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

Claims (3)

[Claims] 1. In the production of a one-component curable composition containing a reactive silicon group-containing polyoxyalkylene polymer as an essential component, a pigment component and a curing catalyst component are added in a separate device at the final stage of the process. A method for producing a curable composition, which comprises mixing. 2. In the production of a one-component type curable composition containing a reactive silicon group-containing polyoxyalkylene polymer as an essential component, the curing catalyst component is already mixed with a main filler by a line mixer. A method for producing a curable composition, which comprises adding to and mixing with a polymer composition. 3. A polyoxyalkylene polymer having a molecular weight of 1
The method for producing a curable composition according to claim 1 or 2, wherein the polymer has a molecular weight distribution represented by a ratio of weight average molecular weight to number average molecular weight of 10,000 or more and 1.5 or less.