JPH05295248A - Settable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having large tackiness-reducing effect immediately after and good storage stability by blending a silicon- containing polymer compound having a hydrolyzable silicon group with an oxidation curing type unsaturated group-containing compound and a lig curable unsaturated group-containing compound. CONSTITUTION:The objective composition is obtained by blending (A) 100 pts.wt. silicon-containing polymer compound containing a hydrolyzable silicon group with (B) 0.1-20 pts.wt. oxidationcurable unsaturated group-containing compound (e.g. tung oil or linseed oil) and (C) 0.001-20 pts.wt. compound containing a light-curable unsaturated group [preferably a compound having (meth) acrylic group such as propylene glycol diacrylate]. The component A is obtained by reacting, e.g. terminals of polyoxyalkylene compound having functional groups with a compound of the formula [R<1> is a 1-20C monovalent organic group; X is hydrolyzable group; (a) is 1-3; R<2> is a 1-17C divalent hydrocarbon]. As this polyoxyalkylene compound, polyoxypropylene diol or polyoxypropylene triol is preferably used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hydrolyzable silicon group-containing polymer, a compound containing an oxidative curing type unsaturated group, and a tack immediately after curing containing a compound containing a photocurable unsaturated group as an active ingredient. The present invention relates to a composition having a large reduction effect and good storage stability.

[0002]

2. Description of the Related Art A composition in which various compounding agents are mixed with a compound having at least one hydrolyzable silicon group in the molecule is
Used in sealing materials, adhesives, etc.

[0003]

However, depending on the compounding composition and the use conditions, tackiness (stickiness) remains on the surface immediately after curing of the composition, and dirt such as dust adheres to the surface, which is a cause of impairing the appearance.

For example, Japanese Patent Laid-Open No. 1-146959 discloses a curable composition comprising a polyoxyalkylene polymer containing a hydrolyzable silicon group, an air-curable compound and a curing catalyst to reduce tackiness. Is disclosed to be effective. However, there is a problem that the flexibility of the cured product of the composition is affected and the weather resistance decreases.

Further, Japanese Patent Publication No. 62-26349 discloses that a curable composition obtained by adding a photocurable substance to an organic polymer containing a hydrolyzable silicon group is effective in reducing tack. Has been done. However, this method has problems such as low storage stability of the composition and high viscosity increase.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have investigated additives to be added to a silicon-containing polymer having a hydrolyzable silicon group for the purpose of improving tackiness and storage stability. As a result, by adding a compound containing an oxidative-curable unsaturated group and a compound containing a photo-curable unsaturated group, the tackiness-reducing effect immediately after curing the composition can be achieved, and the storage stability of the composition is improved. It was found that the cured product also had good weather resistance, and the present invention was achieved.

The present invention is, namely, at least 1 in the molecule.
0.1 to 20 parts by weight of a compound (B) containing an oxidative-curable unsaturated group, and photocuring per 100 parts by weight of a silicon-containing polymer compound (A) having one hydrolyzable silicon group. The compound (C) containing a type unsaturated group is added to 0.001
The curable composition is characterized by containing 20 to 20 parts by weight.

In the present invention, the compound (A) is a compound which undergoes hydrolysis and crosslinking reaction due to moisture to change into a rubber-like elastic body.

Examples of such moisture-curable compounds include:
Many compounds have been studied so far, for example, JP-A-3-47820, JP-A-3-72027, JP-A-3-79627, and JP-B-46-307.
No. 11, Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 4
No. 6-17553 is proposed.

Particularly, the compound (A) of the present invention is preferably a compound whose main chain is composed of polyoxyalkylene as described below. Such a compound is produced, for example, by introducing a hydrolyzable silicon group into the terminal of a polyoxyalkylene compound having a functional group. Such a compound is liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and has desirable properties when used as a sealing material, an adhesive or the like.

The polyoxyalkylene compound is obtained by reacting an initiator such as a hydroxy compound having at least one hydroxyl group in the presence of a catalyst such as an alkali metal catalyst, a complex metal cyanide complex catalyst, or a metal porphyrin with a monoepoxide such as alkylene oxide. A hydroxyl group-terminated one produced by the above method is preferable. The number of functional groups of the polyoxyalkylene compound is preferably 2 or more, and particularly preferably 2 or 3.

Specific examples of the polyoxyalkylene compound include polyoxyethylene compounds, polyoxypropylene compounds, polyoxybutylene compounds, polyoxyhexylene compounds, polyoxytetramethylene compounds and / or copolymers thereof. ..

Particularly preferred polyoxyalkylene compounds are polyoxypropylene compounds, specifically polyoxypropylene diol and polyoxypropylene triol. When used in the following methods (a) and (d), an olefin-terminated polyoxyalkylene compound such as an allyl-terminated polyoxypropylene monool can also be used.

The hydrolyzable silicon group in the present invention may be any silicon group which can undergo a hydrolysis and a crosslinking reaction in the presence of moisture to form a siloxane bond, and a generally known hydrolyzable silicon group can be used. ..

For example, a silyl group represented by the general formula (1) is preferable. -SiXa R13-a (1) In the formula, R1 is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Is. Particularly preferred are methyl group, ethyl group, propyl group, propenyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X is a hydrolyzable group, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, an acid amide group and a hydride group.

Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. Preferred hydrolyzable groups are lower alkoxy groups having 4 or less carbon atoms, especially methoxy group, ethoxy group, propoxy group,
A propenyloxy group etc. can be illustrated. a is 1, 2 or 3, and particularly preferably 2 or 3.

The method of introducing the silyl group represented by the general formula (1) into the polyoxyalkylene compound is not particularly limited, but it can be introduced, for example, by the following method.

(A) A method of reacting a polyoxyalkylene compound having a functional group with an olefin group introduced at the terminal and a hydrosilyl compound represented by the general formula (2). HSiXa R13-a (2) (wherein R1, X and a are the same as above)

As a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene compound and bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond or the like. Or a method of introducing an olefin group into a side chain by copolymerizing by adding an olefin group-containing epoxy compound such as allyl glycidyl ether when polymerizing an alkylene oxide.

(B) A method of reacting the terminal of a polyoxyalkylene compound having a functional group with a compound represented by the general formula (3). R13-a-SiXa-R2 NCO ... (3) (wherein R1, X and a are the same as above. R2 has 1 to 1 carbon atoms.
A divalent hydrocarbon group of 7. )

(C) A polyoxyalkylene compound having a functional group is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, and then the silicon group represented by the general formula (4) is added to the isocyanate group. A method of reacting a W group of a compound.

R13-a-SiXa-R2 W (4) (wherein R1, R2, X and a are the same as above. W is a hydroxyl group,
An active hydrogen-containing group selected from a carboxyl group, a mercapto group and an amino group (primary or secondary). )

(D) An olefin group is introduced at the terminal of a polyoxyalkylene compound having a functional group, and the olefin group is reacted with the mercapto group of the silicon compound represented by the general formula (4) in which W is a mercapto group. How to make.

The number of hydrolyzable silicon groups is preferably 50% or more, and more preferably 70% or more on average in all the terminal groups.

The compound (A) of the present invention has a molecular weight of 80.
From 00 to 50,000 organic polymers can be used. When the molecular weight of the compound (A) is lower than 8000, the cured product becomes hard and has a low elongation. When the molecular weight exceeds 50,000, flexibility and elongation of the cured product are not a problem, but the viscosity of the compound (A) itself is low. It becomes extremely large and the practicality becomes low. The molecular weight is particularly preferably 10,000 to 30,000.

Examples of the compound (B) containing an oxidative-curable unsaturated group in the present invention include drying oil and its derivatives. Tung oil, linseed oil, eno oil, soybean oil,
Examples include sunflower oil and hemp seed oil. As the compound (B), a derivative obtained by modifying these drying oils can also be used. Examples of the derivative include a reaction product of a drying oil and a functional polyoxyalkylene, a reaction product of an isocyanate compound (urethane oil), and the like. The compound (B) may be a mixture of two or more kinds.

Known compounds can be used as the compound (C) containing a photocurable unsaturated group in the present invention.
In particular, a compound having at least one acryl group or methacryl group at the terminal is preferable. The compound (C) may be a monomer, an oligomer, or a mixture thereof.

Specifically, propylene glycol diacrylate, propylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate. , Monomers such as neopentyl glycol dimethacrylate, and oligoesters thereof. The molecular weight of oligoester is 1000
It is preferably 0 or less.

The amount of the compound (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the silicon group-containing polymer (A). The amount of the compound (C) used is 0.00 based on 100 parts by weight of the silicon group-containing polymer (A).
1 to 20 parts by weight, particularly 0.05 to 5 parts by weight are preferred.

In particular, the weight ratio of compound (B) to compound (C) is (C) / (B) = 0.01 to 1.0, especially (C) /
(B) = 0.05 to 0.7 is preferable. If it is less than 0.01, the effect of reducing the residual tack in the initial stage is insufficient, and if it exceeds 1.0, the storage stability of the composition decreases.

There is no particular limitation on the method for preparing the curable composition of the present invention prepared from the compound (A), the compound (B) and the compound (C). In addition, when it is used as a two-component type sealing agent, etc., a curing catalyst can be used, if necessary, in addition to the compound (A), the compound (B) and the compound (C).

As the catalyst, tetrabutyl titanate,
Titanium esters such as tetrapropyl titanate: Organotin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate and tin octylate: Organometallic compounds such as lead octylate, zinc octylate and cobalt naphthenate.

Butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine,
Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Morpholine, N-methylmorpholine, 1,8-diaza-
Amine compounds such as bicyclo [5.4.0] undecene-7 (DBU) or salts thereof such as carboxylic acids;
Low molecular weight polyamide resin obtained from excess polyamine and polybasic acid, reaction product of excess polyamine and epoxy compound, γ-aminopropyltrimethoxysilane, N
A silane coupling agent having an amino group such as-(β-aminoethyl) aminopropylmethyldimethoxysilane,
And other known silanol condensation catalysts. These may be used alone or in combination of two or more.

A photosensitizer may be added to the composition of the present invention, if necessary. Further, if necessary, various known fillers, plasticizers, other additives, etc. may be included.

As the filler, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, carbon black, heavy and soft calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, second oxide. Fillers such as iron, zinc oxide, activated zinc oxide, and silas balloons, and fibrous fillers such as asbestos, glass fibers and filaments can be used.

As the plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate and butyl oleate; glycol esters such as pentaerythritol ester; trioctyl phosphate, phosphorus Phosphoric acid esters such as tricresyl acid; epoxy plasticizers such as benzyl epoxystearate; chlorinated paraffins and the like can be used alone or as a mixture of two or more kinds.

Other additives include hydrogenated castor oil,
Anti-sagging agents such as silicic acid anhydride and organic bentonite, adhesion-imparting agents such as phenolic resins and epoxy resins, pigments, various anti-aging agents, and ultraviolet absorbers can be used.

[0039]

EXAMPLES Examples of the present invention will be given below, but the invention is not limited thereto. Compound a: Propylene oxide polymer having an average molecular weight of 17,000 containing a dimethoxysilyl group at 75% of all terminals Compound b: Propylene oxide polymer having an average molecular weight of 30,000 containing a dimethoxysilyl group at 78% of all terminals

Compound c: Tung oil (Hayashi Chemical) Compound d: Flaxseed oil (Yoshihara Oil)

Compound e: Oligoester acrylate (Toagosei Chemical Industry, Aronix M8030) Compound f: Oligoester acrylate (Toagosei Chemical Industry, Aronix M8060)

(Examples and Comparative Examples) Compounds a to f were used in the proportions shown in Table 1 and stirred at 40 ° C. with a three-one motor in a nitrogen atmosphere to prepare a uniform polymer mixture. For 100 parts by weight of this mixture, 130 parts by weight of calcium carbonate, 16 parts by weight of dioctyl phthalate, 20 parts by weight of titanium oxide, 1 part by weight of hydrogenated castor oil, antioxidant [Irganox 245 (manufactured by Nippon Ciba Geigy)].
5 parts by weight, dibutyltin dilaurate and 3 parts by weight were added and mixed well with a three-roll paint roll to obtain a composition.

This is formed into a sheet having a thickness of about 3 mm and 50
It was put in a thermo-hygrostat at 65 ° C and a humidity of 65% for 2 days to obtain a cured sheet.

[0044]

[Table 1]

(Evaluation) The polymer mixture and the cured sheet were evaluated as follows. The results are shown in Table 2.

Storage stability: immediately after mixing the polymer mixture,
And the viscosity at 25 ° C. after 14 days storage at 50 ° C. was measured (BL type, unit cps).

Surface residual tack: 23 ° C. of the cured sheet
The sample was left in a room having a humidity of 55%, and after 1 day, 3 days, and 14 days, it was measured with a 500 g load of a Picco Mac Tester (manufactured by Toyo Seiki Seisakusho) (unit: gf).

Tensile strength: Hardened sheet at 23 ° C., 55%
Tensile strength physical properties after curing for 14 days in a humidity room were taken as initial physical properties and measured according to JIS K6301 (unit:
Kg / cm2). The strength after a heat resistance test in a gear oven at 100 ° C. for 7 days was defined as the post-heat resistance physical property, and the same measurement as the initial physical property was performed. The result was expressed with the initial physical property as 100% (unit:%).

[0049]

[Table 2]

The cured product obtained by using the compound (A), the compound (B) and the compound (C) as essential components has a great effect of reducing tack immediately after curing. The polymer mixture had no problem with storage stability. Further, the result was obtained that the physical properties after the heat resistance test were also good.

Comparative Example 1 contains only the compound (A) as an essential component, and shows that the surface residual tack is clearly large. In Comparative Examples 2 to 5, the compound (A) and the compound (B) were used as essential components. If the amount of the compound (B) was increased, the surface residual tack was reduced, but the physical properties after the heat resistance test were significantly deteriorated. ing. Comparative Examples 6 to 8 are compounds (A),
The compound (C) was used as an essential component, and when the amount of the compound (C) was increased, the surface residual tack was reduced, but the polymer mixture was thickened.

[0052]

EFFECTS OF THE INVENTION The curable composition of the present invention has a particularly large tack reduction effect immediately after curing and has good storage stability. The curable composition of the present invention also has excellent weather resistance.

[Procedure amendment]

[Submission date] September 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 5

[Correction method] Change

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[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

For example, a silyl group represented by the general formula (1) is preferable. —SiX _a R ¹ _3-a (1) In the formula, R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, or a phenyl group. And a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, propenyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

(A) A method of reacting a polyoxyalkylene compound having a functional group with an olefin group introduced at the terminal and a hydrosilyl compound represented by the general formula (2). HSiX _a R ¹ _3-a (2) (wherein R ¹ , X and a are the same as above)

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

(B) A method of reacting the terminal of a polyoxyalkylene compound having a functional group with a compound represented by the general formula (3). ^{_{R 1 3-a -SiX a -R}} 2 NCO ··· (3) ( wherein R ^1, X, a carbon number in the same .R ² is above 1 to 1
A divalent hydrocarbon group of 7. )

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

R ¹ _3-a -SiX _a -R ² W (4) (wherein R ¹ , R ² , X and a are the same as above. W is a hydroxyl group,
An active hydrogen-containing group selected from a carboxyl group, a mercapto group and an amino group (primary or secondary). )

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Tensile strength: Hardened sheet at 23 ° C., 55%
Tensile strength physical properties after curing for 14 days in a humidity room were taken as initial physical properties and measured according to JIS K6301 (unit:
Kg / cm ² ). The strength after a heat resistance test in a gear oven at 100 ° C. for 7 days was defined as the post-heat resistance physical property, and the same measurement as the initial physical property was performed. The result was expressed with the initial physical property as 100% (unit:%).

Claims (5)

[Claims] 1. A silicon-containing polymer compound (A) having at least one hydrolyzable silicon group in a molecule and 100 parts by weight of the polymer compound (B) containing an oxidative-curable unsaturated group is used in an amount of 0. 1 to 20 parts by weight, and 0.001 to 20 parts by weight of the compound (C) containing a photocurable unsaturated group, a curable composition. 2. The curable composition according to claim 1, wherein the weight ratio of the compound (B) to the compound (C) is (C) / (B) = 0.01 to 1.0. 3. The curable composition according to claim 1, wherein the compound (B) is at least one compound selected from a drying oil and its derivatives. 4. The compound (C) is a compound having at least one acryl group or methacryl group at the terminal.
The curable composition of claim 1. 5. The curable composition according to claim 1, wherein the hydrolyzable silicon group is represented by the following general formula (1). --SiXa R13-a ... (1) (wherein R1 is a substituted or unsubstituted 1 to 20 carbon atom)
Valent hydrocarbon group, X is a hydrolyzable group, and a is 1, 2 or 3. )