JPH10245221A - Surface-treated calcium carbonate and one-pack moisture-curing type resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain calcium carbonate high in storage stability, and to obtain the subject resin composition containing the above calcium carbonate, excellent in storage stability and thixotropy and causing no deposition of the ingredient on the surface of the cured product therefrom. SOLUTION: This calcium carbonate is obtained by surface treatment of calcium carbonate >=3m<2> /g in BET specific surface area with a compound of the formula (A is a residue formed by eliminating an isocyanate group from an isocyanate compound, or a residue formed by eliminating an amino group from an amine compound; (n) is an integer of 1-4; R is a hydrocarbon group, at least one of Rs being a >=8C hydrocarbon group) having a melting point of >=50 deg.C and at least one substance selected from the group consisting of carboxylic acid, sulfonic acid and their metal salts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a calcium carbonate surface-treated with a compound represented by the following formula (1) and a carboxylic acid, a sulfonic acid, or a metal salt thereof.
And a one-component moisture-curable resin composition containing the surface-treated calcium carbonate and used as a sealing material, an adhesive, a waterproofing agent, and the like. More specifically, the present invention relates to calcium carbonate having excellent storage stability, and a one-pack moisture-curable resin composition having excellent storage stability and thixotropy and which does not cause precipitation of contained components on the surface of a cured product.

Embedded image (Where A is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R Is a C ₈ or higher hydrocarbon group.)

[0002]

2. Description of the Related Art Conventionally, precipitated calcium carbonate used in a polyurethane one-pack type sealant, which is a typical example of a one-pack hardening composition, has been subjected to a surface treatment with a fatty acid ester from the viewpoint of storage stability. (Japanese Patent Laid-Open No. 2-3830)
9). However, during storage, the fatty acid ester as a surface treating agent dissolves out, and subsequently agglomerates and precipitates, resulting in particles appearing on the sealant surface and impairing the appearance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object to elute a surface treating agent, and then to coagulate and precipitate to generate particles on the surface of a cured product. An object of the present invention is to provide calcium carbonate which is surface-treated with a surface treatment agent having no storage and has excellent storage stability, and a one-pack moisture-curable resin composition which contains the calcium carbonate and has excellent storage properties and thixotropy.

[0004]

The inventors of the present invention have at least one urethane bond in the molecule, and at least one of the urethane bonds has a melting point of 50 ° C. at which at least one urethane bond is bonded to a hydrocarbon group having at least C _8. By using the above compound and a carboxylic acid or a sulfonic acid or a metal salt thereof for surface treatment of calcium carbonate, a one-pack type moisture-curable resin composition containing the calcium carbonate has storage stability,
The inventors have found that there is no generation of particles on the surface of the cured product of the resin composition due to excellent thixotropy, and the surface treatment agent dissolves and then aggregates and precipitates, thereby completing the present invention.

That is, the present invention uses a compound represented by the general formula (1) having a melting point of 50 ° C. or more and at least one selected from the group consisting of carboxylic acids, sulfonic acids, and metal salts thereof. , BET specific surface area 3m
Provided is a surface-modified calcium carbonate obtained by surface-treating ² / g or more of calcium carbonate.

Embedded image (Where A is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R Is a C ₈ or higher hydrocarbon group.)

The present invention further relates to a surface-treated modified calcium carbonate according to claim 1, based on 100 parts by weight of at least one selected from the group consisting of polyurethane, polysulfide, silicone, and modified silicone sealant. Provided is a one-part moisture-curable resin composition containing parts by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The compound represented by the following formula (1) having a melting point of 50 ° C. or more (hereinafter referred to as a compound of the formula (1)) used in the present invention is a surface treating agent, and isocyanate compound (A- (NCO) _n ) is a compound having at least one urethane bond in the molecule, which is synthesized by reacting an alcohol ROH or reacting carbonyl chloride (A- (OCOCl) _n ) with an amine.

Embedded image In the formula, A is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R is C ₈ or higher hydrocarbon group.

Since the compound of the above formula (1) has an NH group capable of hydrogen bonding to calcium carbonate in the molecule, it can be compared with an aliphatic ester compound conventionally used for surface treatment of calcium carbonate. It is considered that the interaction with calcium carbonate is stronger, and therefore, it does not precipitate from the sealant. The compound of the formula (1) is a compound having a melting point of 50 ° C. or higher. When the melting point is less than 50 ° C., elution or the like occurs during production of the one-pack moisture-curable resin composition.

As described above, the method of synthesizing the compound of the formula (1) is a method of reacting an isocyanate compound (A- (NCO) _n ) with an alcohol (ROH) and a method of reacting carbonyl chloride (A- (OCOCl) _n ). And an amine can be used. The former is preferable in consideration of economy and by-products. As the isocyanate compound used for synthesizing the compound of the formula (1), any known isocyanate compound used for synthesizing a urethane resin or the like is a compound having 1 to 4 isocyanate groups in a molecule. Specifically, examples of the monoisocyanate compound include phenyl isocyanate and stearyl isocyanate. Specific examples of the diisocyanate compound include aromatic isocyanates such as paraphenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate; aliphatic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and octadecyl diisocyanate; Alicyclic isocyanates such as isophorone diisocyanate;
Aryl aliphatic isocyanates such as xylene diisocyanate; modified isocyanates of the above isocyanates;
Etc. are exemplified. As the triisocyanate compound,
Specifically, a reaction product of the above diisocyanate compound or the like with a polyhydric alcohol such as glycerin, hexanetriol or trimethylolpropane, or a diisocyanate compound such as tetramethylene diisocyanate or hexamethylene diisocyanate forms an isocyanurate ring. And a compound having three isocyanate groups in one molecule obtained by the above method. As the tetraisocyanate compound, specifically, a diurethane obtained by reacting the above-mentioned diisocyanate compound or the like with a dialcohol, and a compound having four isocyanate groups in one molecule obtained by reacting with two molecules of diisocyanate And the like. These isocyanate compounds may be used alone or in combination of two or more.

The alcohol (ROH) used in the synthesis of the compound of the formula (1) includes methanol, ethanol,
In addition to lower alcohols such as propanol, isopropanol, butanol, pentanol, hexanol, heptanol, benzyl alcohol and allyl alcohol, n-
Higher alcohols such as octyl alcohol, 2-ethylhexanol, nonyl alcohol, n-decyl alcohol, undecyl alcohol, n-tridecyl alcohol, mystyl alcohol, n-hexadecyl alcohol, and stearyl alcohol are exemplified. As a combination of the above-mentioned isocyanate compound and alcohol,
A combination of tolylene diisocyanate and stearyl alcohol is preferred.

The carbonyl chloride (A- (OCOCl) _n ) used in the synthesis of the compound of the formula (1) includes methyl chlorocarbonate, ethyl chlorocarbonate, propyl chlorocarbonate,
Examples thereof include butyl chlorocarbonate, benzyl chlorocarbonate, octyl chlorocarbonate, nonyl chlorocarbonate, decyl chlorocarbonate, undecyl chlorocarbonate, and benzyl chlorocarbonate.
The amine used for the synthesis of the compound of the formula (1) includes
Octylamine, laurylamine, stearylamine,
Oleylamine and the like can be mentioned.

R in the above formula (1) is a hydrocarbon group, and at least one of R must be a hydrocarbon group having 8 or more carbon atoms. If there is no hydrocarbon group having 8 or more carbon atoms in one molecule, the storage stability of the sealant containing the compound of the above formula (1) is deteriorated.

Untreated calcium carbonate using a compound of the formula (1) or carboxylic acid, sulfonic acid,
Alternatively, as a method of surface treatment of calcium carbonate treated with these metal salts, calcium carbonate and the compound of formula (1) are stirred in a water slurry, a hydrated cake, or a solvent with a mixer or the like, or There is a method in which the calcium carbonate and the compound of the formula (1) are thoroughly stirred in a dry system and then heated, but any of these methods may be used. The amount of the compound of the formula (1) is not particularly limited,
The compound of the formula (1) is added to calcium carbonate in an amount of 1 to 20.
% By weight, preferably about 2 to 10% by weight. If the amount is less than 1% by weight, the effect of the treatment cannot be obtained,
If the content is more than 20% by weight, the physical properties of the cured product are undesirably reduced.

In the surface treatment of calcium carbonate with the compound of the formula (1), a carboxylic acid, a sulfonic acid or a metal salt thereof is used in addition to the compound of the formula (1). As the carboxylic acid, sulfonic acid or metal salt thereof (hereinafter also referred to as fatty acid, etc.) used in the present invention, all of those generally used as a treatment agent for calcium carbonate can be used. Specifically, lauric acid,
Examples include fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, resin acids, sulfonic acids such as dodecylbenzenesulfonic acid, and metal salts thereof. Examples of the metal in the metal salt include potassium, sodium, aluminum, calcium, magnesium and the like. Among these, metal salts of fatty acids are particularly preferred.

The method of treating calcium carbonate using a carboxylic acid, a sulfonic acid, or a metal salt thereof is not particularly limited. For example, calcium carbonate, a carboxylic acid, a sulfonic acid in a water slurry or a water-containing cake may be used. Or a method of vigorously stirring these metal salts with a mixer or the like. The amount of the carboxylic acid, sulfonic acid, or metal salt thereof is not particularly limited,
It is preferable to use carboxylic acid, sulfonic acid, or a metal salt thereof in an amount of about 0.5 to 10% by weight, preferably about 1 to 8% by weight, based on calcium carbonate. 0.5% by weight
If the amount is less than the above, the effect of the treatment cannot be obtained. If the amount is more than 10% by weight, sufficient storage stability as a one-component moisture-curable resin cannot be obtained, which is not preferable.

The method of adding the compound of the formula (1) and the fatty acid to the surface treatment of the calcium carbonate is not particularly limited. For example, calcium carbonate already treated with the fatty acid and the like may be added to the compound of the formula (1). And heating the mixture to a temperature equal to or higher than the melting point of the compound of formula (1) (dry treatment); mixing the compound of formula (1) with an aqueous slurry of calcium carbonate already treated with a fatty acid or the like; A method of heating to a temperature equal to or higher than the melting point of the compound of formula (1), dehydrating, drying and pulverizing (wet treatment); When producing ordinary precipitated calcium carbonate, a compound of formula (1) having a particle size of preferably 100 μm or less is added,
A method of drying at a temperature equal to or higher than the melting point of the compound of the formula (1) (fatty acids and the like are added at an arbitrary place during this step) and the like. As described above, by using carboxylic acid, sulfonic acid, or a metal salt thereof and the compound of the formula (1) in combination for the surface treatment of calcium carbonate, the storage stability of calcium carbonate is improved, and the calcium carbonate is contained. Storage stability and thixotropy of the one-component moisture-curable resin composition are improved.

As the calcium carbonate used in the present invention
Has a specific surface area of 3 m by the BET method. ^Two/ G or more carbonic acid
Lucium, especially precipitated calcium carbonate, is preferred. Specific surface area
3m ^Two/ G or more, work characteristics such as thixotropy
Because it is good. Also, precipitated calcium carbonate is particularly good.
The reason is that heavy calcium carbonate is treated with a specific surface treatment agent.
Although sufficient storage stability can be obtained without
This is because there is a problem in workability due to lack of fucking.
You.

The one-pack type resin composition containing the compound of the formula (1) and a fatty acid, or the calcium carbonate surface-treated with the compound of the formula (1) and a fatty acid, etc.
There is no particular limitation, and examples thereof include polyurethane, polysulfide, silicone, and modified silicone resin compositions, which are useful as sealing materials. The polyurethane used in the present invention is not particularly limited as long as it is a polyurethane generated from a polyol compound and a polyisocyanate compound. As the polyol, those used in the production of ordinary polyurethane resins can be used. Specifically, polyolefin-based polyols such as polyethylene glycol, polyoxypropylene glycol, and polyisoprene polyol, adipate-based polyol, lactone-based polyol And the like. These compounds may be used alone or in combination of two or more. As the polyisocyanate compound, those used in the production of ordinary polyurethane resins can be used. Specifically, aromatic compounds such as paraphenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and 4,4′-diphenylmethane diisocyanate can be used. Isocyanates; aliphatic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, octadecyl diisocyanate; alicyclic isocyanates such as isophorone diisocyanate;
Aryl aliphatic isocyanates such as xylene diisocyanate; modified isocyanates of the above isocyanates,
Alternatively, triisocyanate, which is a reaction product of a polyhydric alcohol and the above-described diisocyanate compound, may be used. These compounds can be used alone or
More than one species may be used in combination. The polyurethane used in the present invention is produced using the above-mentioned polyol and polyisocyanate compound, and the production conditions may be ordinary polyurethane production conditions.

The polysulfide used in the present invention is
HS- (R-S_m)_n-SH
Well, there is no particular limitation. Where the average value of m is 1.5
To 2 are preferable, and n is preferably 2 to 45. As R
Examples thereof include a divalent aliphatic group. Between carbon atoms of an aliphatic group
May have an oxygen atom interposed. As a specific example of R,
-C_TwoH_Four-, -C_ThreeH₆-,-C_FourH₈-, -C_Two
H_FourOC_TwoH_Four-, -C_ThreeH₆OC_ThreeH₆-, -C_FourH
₈OC_FourH₈-, -C_TwoH_FourOCH_TwoOC_TwoH _Four−, −
C_ThreeH₆OCH_TwoOC_ThreeH₆-, -C_FourH₈OCH_TwoO
C_FourH₈And a divalent aliphatic group such as-. Also good
Aromatic polysulfide or having a mercapto group at the end,
Modifications with predominantly polyether urethane bonds in the main chain
Polysulfides can also be mentioned. These poly
Among sulfides, specifically, Toray Thiokol
Thiocoll LP series is a general-purpose polysulfide
It is preferably used.

The silicone used in the present invention is not particularly limited as long as it is a silicone which is obtained by hydrolyzing an organohalogensilane or an organoalkoxysilane, subjecting it to polycondensation, and having a molecular end blocked with silanol or alkoxysilyl. For example, the main chain includes dimethyl silicone, a diphenyl derivative of dimethyl silicone, a methylphenyl derivative of dimethyl silicone, and the like. Preferably, the main chain includes dimethyl silicone.

The modified silicone resin used in the present invention is not particularly limited. In particular, a resin having a main chain consisting essentially of polyether and having at least one alkoxysilyl group in the molecule is mentioned, and specifically, an MS polymer of Kanegafuchi Chemical is mentioned.

The method for producing the one-pack moisture-curable resin composition of the present invention is as follows. The calcium carbonate which has been surface-treated and dried by the above-mentioned methods and the like is usually combined with a resin such as polyurethane, polysulfide, silicone or modified silicone. Is exemplified.

The amount of the surface-treated calcium carbonate of the present invention to be added to the resin such as polyurethane, polysulfide, silicone or modified silicone sealing agent is 10 to 200 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the resin. It is preferably about 30 to 200 parts by weight. If the amount is less than 10 parts by weight, sufficient thixotropy cannot be obtained, and if the amount is more than 200 parts by weight, the viscosity becomes high, which causes a problem in workability. The one-pack moisture-curable resin composition of the present invention, in which the surface-treated calcium carbonate of the present invention is blended, is moisture-cured at room temperature, and no component is precipitated on the surface of the cured product even after one week. The resin composition to which the surface treatment agent of the present invention or the calcium carbonate surface-treated with the surface treatment agent is blended is not limited to a one-pack type resin composition, and may be added to a two-pack type resin composition. Good.

The one-pack moisture-curable resin composition of the present invention may contain, in addition to the above compounds, a filler, a plasticizer, an antioxidant, an antioxidant, a pigment or dye, an adhesion-imparting agent, a flame retardant, an antistatic agent. An agent, a dehydrating agent, a dispersant, a solvent and the like may be blended.

As the filler, magnesium carbonate, carbon black, silica, clay, talc and the like are used. As a plasticizer, dioctyl phthalate (DO
P), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate;
Pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like are used. These plasticizers may be used alone or as a mixture of two or more, and DOP is particularly preferred. The mixing amount is preferably from 10 to 150 parts by weight based on 100 parts by weight of the resin from the viewpoint of workability.

As antioxidants, butylhydroxytoluene (BHT), butylhydroxyanisole (BH)
A) and triphenyl phosphite.

Examples of the anti-aging agent include hindered phenol compounds, benzotriazole compounds, hindered amine compounds and the like.

The pigment includes an inorganic pigment and an organic pigment.
Examples of the inorganic pigment include titanium dioxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate and the like.
Examples of the organic pigment include an azo pigment and a copper phthalocyanine pigment.

Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins,
Xylene resin and the like can be mentioned.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, diethyl bishydroxyethyl aminoethyl phosphate, neopentyl bromide polyether, brominated polyether and the like. No.

Examples of the antistatic agent include an anionic activator such as an alkylbenzene sulfonate, a cationic activator such as an alkyltrimethylammonium salt, a nonionic activator such as a fatty acid alkylolamide, and an amphoteric activator. Examples of the dehydrating agent include polysiloxane having an acyloxysilyl group.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

1) Surface treatment agent A As the surface treatment agent, a compound represented by the following formula (2) was used.

Embedded image

2) Formation of Surface-treated Calcium Carbonate 1 Calcium Carbonate 1 1000 g of white glossy CC (fatty acid-treated calcium carbonate, manufactured by Shiraishi Industry Co., Ltd.) was treated with 50 parts of treating agent A having an average particle size of 30 μm.
g, using a Nauter mixer at room temperature for 15 minutes, 1
The mixture was stirred and treated at 10 ° C. for 1 hour in a dry system to obtain the desired product. Calcium carbonate 2 100 precipitated sedimentary calcium carbonate having an average particle size of 0.08 μm
0 g, 50 g of treating agent A having an average particle size of 30 μm was added, and a Nauter mixer was used for 15 minutes at room temperature and 1 hour at 110 ° C.
The mixture was stirred and processed in a dry system for a time to obtain the desired product. Calcium carbonate 3 concentration 150 [g / L], 5 L of a water slurry of precipitated calcium carbonate having an average particle size of 0.08 μm,
37 g, sodium laurate 2 g (calcium carbonate 1
4.9 parts by weight of the surface treating agent and 0.27 parts by weight of sodium laurate) were added to 00 parts by weight, and the mixture was vigorously stirred at 110 ° C. Dehydrate this calcium carbonate slurry,
Drying and pulverization gave the desired product. Calcium carbonate 4 The desired calcium carbonate 4 was obtained in the same manner as the calcium carbonate 3 except that sodium dodecylbenzenesulfonate was used instead of sodium laurate. Calcium carbonate 5 Except not using sodium laurate, the target calcium carbonate 5 was obtained in the same manner as the above calcium carbonate 3.

3) Synthesis of urethane prepolymer 850 g of polypropylene glycol having a number average molecular weight of 3000 (Exenol 3020; manufactured by Asahi Glass Co., Ltd.), 150 g of polypropylene triol having a number average molecular weight of 3000 (Exenol 3030; manufactured by Asahi Glass Co., Ltd.), and 300 g of dioctyl phthalate are mixed. Then, 135 g of diphenylmethane diisocyanate was added, and the mixture was added at 80 ° C. for 10 hours.
By stirring and reacting, a urethane prepolymer containing 1.05% of an isocyanate group was synthesized.

4) Synthesis of one-pack moisture-curable resin composition (Example 1) Calcium carbonate 1 (white glossy CC, Shiraishi Kogyo Co., Ltd.) 100 surface-treated with a fatty acid was added to 100 parts by weight of the urethane prepolymer. Parts by weight, 3 parts by weight of an acyloxypolysiloxane represented by the following formula (3), 40 parts by weight of dioctyl phthalate (DOP), 15 parts by weight of xylene, and 5 parts by weight of titanium oxide, and kneaded with a universal stirrer.
A one-part moisture-curable resin composition was obtained.

[0037]

Embedded image

Example 2 The same procedure as in Example 1 was carried out except that 100 parts by weight of calcium carbonate 3 was used instead of calcium carbonate 1. (Example 3) The same procedure as in Example 1 was carried out except that calcium carbonate 4 was used instead of calcium carbonate 1. (Comparative Example 1) The same procedure as in Example 1 was carried out except that calcium carbonate 2 was used instead of calcium carbonate 1. (Comparative Example 2) The same operation as in Example 1 was performed except that calcium carbonate 5 was used instead of calcium carbonate 1.

The following characteristics of the resins obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured and evaluated. 1) Viscosity After completion of kneading, the mixture was stored at 20 ° C. for 1 day, and then the viscosity [PS] was measured with a BS viscometer (using a No. 7 rotor). Thereafter, after storage at 70 ° C. for 1 day, the temperature was returned to 20 ° C., the viscosity was measured again, the ratio to the initial viscosity was determined, and the number of times the initial viscosity was calculated. 2) Slump resistance 60 ° C using a jig specified in JIS A5758
Was evaluated by a slump test under the following conditions. As for the length of dripping, ○ indicates 0 to 1.5 mm, and X indicates 2 mm or more. The results are shown in the table below.

[0040]

[0041]

According to the present invention, the one-pack moisture-curable resin composition containing calcium carbonate of the present invention, which has been surface-treated with a compound of the formula (1) and a carboxylic acid, a sulfonic acid or a metal salt thereof, has excellent storage properties. It has stability and thixotropy. Further, no precipitation of contained components occurs on the surface of the one-part moisture-curable resin composition.

Claims (2)

[Claims] 1. A BET method using a compound represented by the general formula (1) having a melting point of 50 ° C. or more and at least one selected from the group consisting of carboxylic acids, sulfonic acids, and metal salts thereof. Surface-treated calcium carbonate obtained by surface-treating calcium carbonate having a specific surface area of 3 m ² / g or more. Embedded image (Where A is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R Is a C ₈ or higher hydrocarbon group.) 2. The surface-treated calcium carbonate according to claim 1, which is contained in an amount of 10 to 200 parts by weight based on 100 parts by weight of at least one selected from the group consisting of polyurethane, polysulfide, silicone, and modified silicone sealant. One-part moisture-curable resin composition.