JP2005042128A - Silane-terminated urethane-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a silane-terminated urethane-containing resin composition which contains a surface-treated calcium carbonate and hence has a high viscosity and good thixotropic properties. <P>SOLUTION: The resin composition comprises the silane-terminated urethane-containing resin and the surface-treated calcium carbonate contained therein. The urethane-containing resin contains polyoxypropylene as the main chain; a urethane group is bonded to each of the terminals of the main chain; and a silane group is bonded to each of the urethane groups. The surface-treated calcium carbonate is characterized by the following: the peak of a highest-probability void diameter in a void diameter distribution curve by a mercury penetration method is less than 0.03 μm; and the highest-probability void volume is 0.05-0.5 cm<SP>3</SP>/g. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silane-terminated urethane-containing resin composition imparted with thixotropic properties by containing surface-treated calcium carbonate.

  In inks, paints, sealing materials, PVC sols, acrylic sols, etc., sols are prepared, and coating, painting, construction, mixing, and the like are performed using the sols. Filling with organic thickeners such as fumed silica, castro wax, and amide wax that can give high viscosity to the sol in a small amount when the filler cannot be added to the sol due to the physical properties of the cured product. The agent is being used.

  However, fumed silica is generally expensive, and organic thickeners such as castro wax and amide wax are also generally expensive. In actual use, it is difficult to adjust the temperature and storage stability. As a substitute for this, a thixotropic agent capable of imparting high viscosity at a low price has been demanded. On the other hand, calcium carbonate is used in many fields as a filler for various polymer materials such as plastics, rubbers, inks, paints, sealants, PVC sols and acrylic sols. Therefore, if high viscosity and high thixotropic property can be imparted by adding calcium carbonate, it can be used as a relatively inexpensive thixotropic imparting material.

  Known sealants that require high viscosity and high thixotropic properties include polyurethane sealants, modified silicone sealants, silicone sealants, polysulfide sealants, and the like. Further, in recent years, as an alternative to the modified silicone sealant, there is a sealant using a silane-terminated urethane-containing resin in which the main chain is polyoxypropylene, urethane groups are bonded to both sides, and silane groups are bonded to both ends. Developed and under consideration. Even in a sealant using such a silane-terminated urethane-containing resin, it is required to impart high viscosity and high thixotropic properties by adding calcium carbonate.

  An object of the present invention is to provide a silane-terminated urethane-containing resin composition imparted with high viscosity and good thixotropic properties by containing surface-treated calcium carbonate.

The present invention relates to a pore size distribution curve obtained by a mercury intrusion method in a silane-terminated urethane-containing resin in which a main chain is polyoxypropylene, urethane groups are bonded to both sides, and silane groups are bonded to both ends. Silane-terminated urethane containing, characterized by containing a surface-treated calcium carbonate having a peak of the most probable void diameter in less than 0.03 μm and a most probable void volume of 0.05 to 0.5 cm ³ / g It is a resin composition.

  In the present invention, high viscosity and good thixotropic properties are imparted by containing the surface-treated calcium carbonate. In the present invention, since it contains surface-treated calcium carbonate, it can be produced at a relatively low cost as compared with conventional fumed silica. In addition, it has good storage stability.

  In addition, when a conventional organic thickener is used, the manufacturing process is complicated such as preparing a pregel in advance, but according to the present invention, it is not necessary to prepare a pregel and the manufacturing is simple. Can do.

The resin composition of the present invention has a surface in which the peak of the most probable void diameter in the void diameter distribution curve by the mercury intrusion method is less than 0.03 μm and the most probable void volume is 0.05 to 0.5 cm ³ / g. Since the treated calcium carbonate is used, the dispersibility of the surface treated calcium carbonate in the resin composition is excellent, and the resin composition has high viscosity and good thixotropic properties.

The surface-treated calcium carbonate in the present invention is preferably calcium carbonate surface-treated with an unsaturated fatty acid (A) and a saturated fatty acid (B). Moreover, it is preferable that the surface treatment is performed on calcium carbonate having a BET specific surface area of 10 to 100 m ² / g.

  The unsaturated fatty acid (A) and the saturated fatty acid (B) may be surface-treated in the form of an acid, or may be surface-treated in the form of a metal salt or ester. The unsaturated fatty acid (A) and the saturated fatty acid (B) are preferably fatty acids having 6 to 31 carbon atoms. Moreover, it is preferable that the mixing ratio (A) / (B) of unsaturated fatty acid (A) and saturated fatty acid (B) is 0.3-5.

  The total amount of surface treatment with the unsaturated fatty acid (A) and the saturated fatty acid (B) is preferably 1 to 50 parts by weight with respect to 100 parts by weight of calcium carbonate.

Furthermore, if the total amount of surface treatment with unsaturated fatty acid (A) and saturated fatty acid (B) is (C) parts by weight and the BET specific surface area is (D) m ² / g, (C) / (D) is 0.1 to 0.5 is preferable.

  Moreover, it is preferable that the moisture content of surface treatment calcium carbonate is 0.05 to 1.0% with a Karl Fischer moisture measuring machine.

  Hereinafter, the present invention will be described in more detail.

(Calcium carbonate particles)
In the present invention, the calcium carbonate particles used as the target for the surface treatment are not particularly limited as long as they can be used as fillers for various polymer materials. Calcium carbonate includes natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (light (glue) calcium carbonate). Natural calcium carbonate is produced directly from limestone ore, and can be produced, for example, by mechanically crushing and classifying limestone ore.

  Synthetic calcium carbonate is produced from calcium hydroxide, and can be produced, for example, by reacting calcium hydroxide with carbon dioxide gas. Calcium hydroxide can be produced, for example, by reacting calcium oxide with water. Calcium oxide can be produced, for example, by co-firing raw limestone with coke or the like. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.

The calcium carbonate used in the present invention preferably has a BET specific surface area of 10 to 100 m ² / g. When the BET specific surface area is less than 10 m ² / g, in the calcium carbonate after the surface treatment, the peak of the most probable pore diameter and the most probable void volume in the pore diameter distribution curve by the mercury intrusion method are within the scope of the present invention. It may be difficult to get. In general, it is often difficult to produce calcium carbonate having a BET specific surface area of greater than 100 m ² / g. A more preferable value of the BET specific surface area is 20 to 80 m ² / g, and more preferably 30 to 60 m ² / g.

(Unsaturated fatty acid)
In the present invention, as described above, it is preferable that the surface of calcium carbonate is treated with the unsaturated fatty acid (A) and the saturated fatty acid (B). An unsaturated fatty acid is a fatty acid having a double bond in the molecule, and is synthesized in vivo by, for example, a dehydration reaction of a saturated fatty acid. As an unsaturated fatty acid, a C6-C31 unsaturated fatty acid is preferable, More preferably, it is C8-26, More preferably, it is 9-21. Specific examples of the unsaturated fatty acid include obsilic acid, carloleic acid, undecylenic acid, lindelic acid, tuzuic acid, fizeteric acid, molistoleic acid, palmitoleic acid, petroceric acid, oleic acid, elaidic acid, asclebic acid, vacsen Examples thereof include acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, ceracolonic acid, ximenoic acid, lumectric acid, sorbic acid, and linoleic acid. Among these, oleic acid, erucic acid and linoleic acid are particularly preferably used.

  The unsaturated fatty acid may be used as it is in the surface treatment in the form of an acid, but may be used in the form of a metal salt and / or ester. Examples of the metal salt of unsaturated fatty acid include alkali metal salts and alkaline earth metal salts. Among these, water-soluble metal salts are preferably used. Specific examples of the unsaturated fatty acid metal salt include sodium salts, potassium salts and magnesium salts of the unsaturated fatty acids, and sodium oleate, sodium erucate and sodium linoleate are particularly preferably used.

  Examples of the unsaturated fatty acid ester include esters with lower aliphatic alcohols such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, sec-butyl ester, and tert-butyl ester.

  An unsaturated fatty acid, its metal salt, and its ester may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(Saturated fatty acids)
The saturated fatty acid (B) is a fatty acid having no double bond in the molecule, and most of the natural fatty acids are linear monobasic acids. As a saturated fatty acid, a C6-C31 saturated fatty acid is preferable, More preferably, it is C8-26, More preferably, it is 9-21. Specific examples of saturated fatty acids include butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid, behenic acid, lignoceric acid, serotic acid, montan Examples include acid and melicic acid. Among these, palmitic acid, stearic acid, and lauric acid are preferably used.

  The saturated fatty acid may be used for the surface treatment in the form of an acid as it is, but may be used in the form of a metal salt and / or ester. Examples of metal salts of saturated fatty acids include alkali metal salts and alkaline earth metal salts. Among these, water-soluble metal salts are preferably used. Specific examples of the saturated fatty acid metal salt include sodium salts, potassium salts and magnesium salts of the saturated fatty acids, and sodium palmitate, sodium stearate and sodium laurate are particularly preferably used.

  Examples of saturated fatty acid esters include esters with lower aliphatic alcohols such as methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, sec-butyl esters, and tert-butyl esters.

  A saturated fatty acid, its metal salt, and its ester may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(Surface treatment calcium carbonate)
The surface-treated calcium carbonate is calcium carbonate obtained by treating the surface of calcium carbonate to give added value. The treating agents include fatty acids such as (A) and (B), resin acids such as abietic acid, dehydroabietic acid, and dihydroabietic acid, silane coupling agents such as vinylsilane, aminosilane, and mercaptosilane, polyethylene, polypropylene, and urethane resin. However, this is not a limitation. In the present invention, saturated fatty acids and unsaturated fatty acids are preferred.

In the surface-treated calcium carbonate of the present invention, the peak of the most probable void diameter in the void diameter distribution curve by the mercury intrusion method is less than 0.03 μm, and the most probable void volume is 0.05 to 0.5 cm ³ / g. . Fine calcium carbonate particles are very easily aggregated, and the size and number of aggregates vary greatly depending on the surface treatment method. The peak of the most probable void diameter and the most probable void volume vary depending on the size and number of such aggregates. By performing a surface treatment so that the peak of the most probable pore diameter and the most probable void volume are within the scope of the present invention, a thixotropic agent capable of imparting high viscosity and good thixotropic properties can be obtained. it can. The lower limit value of the peak of the most probable void diameter is not particularly limited, but generally, it is difficult to produce one having the peak of the most probable void diameter of less than 0.002 μm. A more preferable range of the peak is 0.002 μm or more and less than 0.03 μm. A more preferable peak range of the most probable void diameter is 0.005 to 0.02 μm. A more preferable range of the most probable void volume is 0.1 to 0.3 cm ³ / g.

  The void diameter and void volume of the surface-treated calcium carbonate can be measured using, for example, a mercury intrusion void diameter measuring device (POROSIMETER 2000, manufactured by CARLO ERBA INSTRUMENTS). For example, it can be measured by setting the maximum press-fitting pressure to 160 MPa · s and the limit minimum gap diameter to 0.002 μm. The void volume can be obtained from the volume when mercury is injected into the gap between calcium carbonate particles, and the void diameter is obtained from the pressure when mercury is injected into the gap between calcium carbonate particles and the surface tension of mercury. Can do. It is possible to measure the central void of the void diameter peak with the highest probability in the void diameter distribution curve as the most probable void diameter, and the void volume contained in this peak as the most probable void volume.

  As described above, the surface-treated calcium carbonate of the present invention is preferably surface-treated with an unsaturated fatty acid (A) and a saturated fatty acid (B). In this case, the ratio (A) / (B) of the unsaturated fatty acid (A) and the saturated fatty acid (B) is preferably 0.3 to 5. The effect of the present invention that a high viscosity and good thixotropic properties can be imparted by the surface treatment using the unsaturated fatty acid (A) and the saturated fatty acid (B) in such a range is more reliable. Is obtained. A more preferable range of (A) / (B) is 0.7 to 4, more preferably 1 to 2. Moreover, it is preferable that the total amount of the surface treatment by the unsaturated fatty acid (A) and the saturated fatty acid (B) is 1 to 50 parts by weight with respect to 100 parts by weight of calcium carbonate. By setting the total amount of the fatty acids for the surface treatment in such a range, the effect of the present invention that a high viscosity and good thixotropic properties can be imparted can be obtained more reliably. The more preferable range of the total amount of the surface treatment is 3 to 30 parts by weight, and more preferably 6 to 20 parts by weight with respect to 100 parts by weight of calcium carbonate.

When the total amount of surface treatment with unsaturated fatty acid (A) and saturated fatty acid (B) is (C) parts by weight and the BET specific surface area is (D) m ² / g, (C) / (D) is 0.1 to 0.5 is preferable. More preferably, it is 0.15-0.45, More preferably, it is 0.2-0.4. The effect of the present invention that the resin composition using the surface-treated calcium carbonate having the total amount of the surface-treated fatty acid in such a range exhibits a high viscosity and good thixotropic properties can be obtained more reliably.

  The composition of the treatment agent in the surface-treated calcium carbonate can be measured, for example, by gas chromatography. Moreover, content of a surface treating agent can be measured by a differential thermal analysis, for example.

  In addition, if drying is performed so that the amount of moisture is reduced in the manufacturing drying process, the cost increases. On the other hand, if the amount of water is excessively large, problems such as poor storage stability occur when the resin composition is formed. Therefore, an appropriate water value is desirable. The moisture content of the surface-treated calcium carbonate is preferably 0.05 to 1.0% as measured with a Karl Fischer moisture meter. More preferably, it is 0.1-0.9%, More preferably, it is 0.2-0.8%. By using the surface-treated calcium carbonate having a moisture content in such a range, good storage stability can be imparted.

(Manufacture of surface treated calcium carbonate)
The surface-treated calcium carbonate is calcium carbonate obtained by treating the surface of calcium carbonate to give added value. The treating agents include fatty acids such as (A) and (B), resin acids such as abietic acid, dehydroabietic acid, and dihydroabietic acid, silane coupling agents such as vinylsilane, aminosilane, and mercaptosilane, polyethylene, polypropylene, and urethane resin. However, this is not a limitation. In the present invention, saturated fatty acids and unsaturated fatty acids are preferred.

  For example, it can be manufactured by adding a surface treatment agent to a slurry liquid of calcium carbonate particles and stirring, followed by dehydration. When using unsaturated fatty acid (A) and saturated fatty acid (B) as a surface treating agent, these can be mixed and added. The solid content of calcium carbonate in the calcium carbonate slurry can be appropriately adjusted in consideration of the dispersibility of the calcium carbonate particles, the ease of dehydration, and the like. Moreover, it can adjust suitably with the particle diameter etc. of a calcium carbonate particle. Generally, a slurry liquid with an appropriate viscosity can be obtained by adjusting the solid content of the slurry to 2 to 30% by weight, preferably about 5 to 20% by weight. If the amount of water used is too large, dehydration becomes difficult, which is not preferable in terms of wastewater treatment.

  Since the unsaturated fatty acid (A) and the saturated fatty acid (B) are often difficult to be easily dispersed in the slurry liquid in the form of an acid, they are generally saponified to form sodium or potassium salt. It is preferable to add to the calcium carbonate slurry.

  As another method for producing the surface-treated calcium carbonate, there is a method in which the dried calcium carbonate particles are stirred with a stirring mixer such as a Henschel mixer and a surface treating agent is added. This method is suitable for calcium carbonate having a relatively large particle size.

(Silane-terminated urethane-containing resin)
The silane-terminated urethane-containing resin used in the present invention is a resin in which the main chain is polyoxypropylene, urethane groups are bonded to both sides thereof, and silane groups are bonded to both ends thereof. A urethane group exists between the main chain polyoxypropylene and the terminal silane group, and this urethane group is bonded by a urethane bond, a urea bond, or the like. Generally, polyoxypropylene and a silane group are bonded by diisocyanate.

  Diisocyanates include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolidine diisocyanate (TODI), xylene diisocyanate, hexamethylene diisocyanate and its modified products, dicyclohexylmethane diisocyanate (water). Added MDI), isophorone diisocyanate (IPDI) and the like.

Examples of the terminal silane group include those represented by the general formula —SiR _m R ′ _n . In this general formula, m and n are positive numbers and m + n = 3, and R and R ′ are each an OH group; an alkyl group such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group such as a cyclohexyl group; Aryl groups such as phenyl and tolyl groups; alkenyl groups such as vinyl and allyl groups; some or all of hydrogen atoms bonded to carbon atoms are substituted with halogen atoms, amino groups, epoxy groups, carbonyl groups, cyano groups, etc. Monovalent hydrocarbon groups selected from those; alkoxy groups such as methoxy groups and ethoxy groups; oxime groups such as methyl ethyl ketoximo groups, dimethyl ketoximo groups and diethyl ketoximo groups; acetoxy groups; aminoxy groups and the like is there. R and R ′ at this time may be the same or different.

  In addition, examples of the silane-terminated urethane-containing resin used in the present invention include resins generally referred to as SPUR and hybrid PU, and commercially available products include “Polymer ST series” (manufactured by Hanse Chemie).

(Resin composition)
The silane-terminated urethane resin composition of the present invention is a resin composition having high viscosity and high thixotropic property by containing surface-treated calcium carbonate as described above, and can be used as a sealant. is there.

  In addition to the surface-treated calcium carbonate, various additives can be added to the silane-terminated urethane-containing resin composition of the present invention as necessary. For example, a plasticizer, a filler, and other additives can be added.

  Plasticizers include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP) , Diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA), adipine Diisodecyl acid (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), diacid maleate Chill (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris (2-ethylhexyl) phosphate (TOP), tri (chloroethyl) phosphate (TCEP), trisdichloropropyl phosphate (CRP), tributoxyethyl phosphate (TBXP), tris (β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyl diphenyl Phosphate (CDP), acetyl triethyl citrate, tributyl acetyl citrate, etc. Other trimellitic acid plasticizer, polyester plasticizer, chlorinated paraffin, stearic acid available There are plasticizers and dimethylpolysiloxane.

  Examples of the filler (including a thickener) include inorganic and organic materials. Inorganic fillers include calcium carbonate (natural and synthetic products), calcium and magnesium carbonate (natural and synthetic products), basic magnesium carbonate, quartz powder, quartzite powder, and finely divided silicic acid (dry and wet products). , Gel method product), finely powdered calcium silicate, finely powdered aluminum silicate, kaolin clay, pyrophyllite clay, talc, sericite, mica, bentonite, nepheline sinite, aluminum hydroxide, magnesium hydroxide, barium sulfate, carbon black ( Furnace, thermal, acetylene), graphite, acicular / fibrous, sepiolite, wollastonite, zonotlite, potassium titanate, carbon fiber, mineral fiber, glass fiber, shirasu balun, fly ash balun, glass balun, silica beads, alumina beads ,Glass beads Etc., and the like. Organic fillers include wood powder, walnut powder, cork powder, wheat flour, starch, ebonite powder, rubber powder, lignin, phenolic resin, high styrene resin, polyethylene resin, silicon resin, urea resin, etc. or beads And fibrous materials such as cellulose powder, pulp powder, synthetic fiber powder, amide wax, and castor oil wax.

  The compounding ratio of the surface-treated calcium carbonate in the silane-terminated urethane-containing resin composition of the present invention is 5 to 400 parts by weight with respect to a total of 100 parts by weight of the resin component (including the plasticizer) and the liquid additive. Is more preferable, and more preferably 10 to 300 parts by weight.

  The silane-terminated urethane-containing resin composition of the present invention is provided with high viscosity and good thixotropic properties by containing surface-treated calcium carbonate. Therefore, it can be produced at a relatively low cost, has little change in viscosity with time, and has excellent storage stability. Further, it is not necessary to prepare a pregel or the like, and it can be easily manufactured.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented without departing from the scope of the present invention. It is.

<Manufacture of surface treated calcium carbonate>
(Example 1)
To 2 kg of synthetic calcium carbonate having a BET specific surface area of 40 m ² / g, water adjusted to 80 ° C. so as to have a solid content of 10% by weight was added, and a calcium carbonate slurry liquid was prepared using a stirring type disperser. While stirring the slurry liquid with a disperser, 200 g of mixed fatty acid (100 g of oleic acid and 100 g of stearic acid) in a mixing ratio of saponified oleic acid / stearic acid = 1.0 was added to this calcium carbonate slurry liquid. After stirring for a minute, press dewatered. The obtained dehydrated cake was dried and then pulverized to obtain about 2 kg of surface-treated calcium carbonate surface-treated with unsaturated fatty acid and saturated fatty acid.

  The BET specific surface area was measured using a specific surface area measuring apparatus Flow Soap II 2300 (manufactured by Micromeritic).

(Example 2)
A surface-treated calcium carbonate surface-treated with an unsaturated fatty acid and a saturated fatty acid was produced in the same manner as in Example 1 except that synthetic calcium carbonate having a BET specific surface area of 25 m ² / g was used.

(Example 3)
Surface treatment was performed with unsaturated fatty acid and saturated fatty acid in the same manner as in Example 1 except that 200 g of mixed fatty acid (67 g of oleic acid and 133 g of stearic acid) having a mixing ratio of oleic acid / stearic acid = 0.5 was used. Surface treated calcium carbonate was produced.

(Example 4)
Surface treatment was carried out with an unsaturated fatty acid and a saturated fatty acid in the same manner as in Example 1 except that 200 g of mixed fatty acid (130 g of oleic acid and 70 g of stearic acid) having a mixing ratio of oleic acid / stearic acid of 1.9 was used. Surface treated calcium carbonate was produced.

(Example 5)
Surface treatment was carried out with an unsaturated fatty acid and a saturated fatty acid in the same manner as in Example 1, except that 200 g of mixed fatty acid (100 g of oleic acid and 100 g of palmitic acid) having a mixing ratio of oleic acid / palmitic acid = 1.0 was used. Surface treated calcium carbonate was produced.

(Example 6)
In the same manner as in Example 1 except that 200 g of mixed fatty acid (oleic acid 100 g, stearic acid 50 g, palmitic acid 50 g) having a mixing ratio of oleic acid / (stearic acid + palmitic acid) = 1.0 was used. Surface-treated calcium carbonate surface-treated with saturated fatty acids and saturated fatty acids was produced.

(Example 7)
In the same manner as in Example 1 except that 200 g of mixed fatty acid (oleic acid 100 g, stearic acid 50 g, lauric acid 50 g) having a mixing ratio of oleic acid / (stearic acid + lauric acid) = 1.0 was used. Surface-treated calcium carbonate surface-treated with saturated fatty acids and saturated fatty acids was produced.

(Example 8)
Example above except that 200 g of mixed fatty acid (oleic acid 100 g, stearic acid 34 g, palmitic acid 33 g, lauric acid 33 g) with a mixing ratio of oleic acid / (stearic acid + palmitic acid + lauric acid) = 1.0 is used. In the same manner as in Example 1, surface-treated calcium carbonate surface-treated with unsaturated fatty acid and saturated fatty acid was produced.

Example 9
(Oleic acid + linoleic acid) / (Stearic acid + palmitic acid + lauric acid) = 1.0 g of mixed fatty acid with a mixing ratio of 1.0 (oleic acid 80 g, linoleic acid 20 g, stearic acid 34 g, palmitic acid 33 g, lauric acid 33 g ) Was used in the same manner as in Example 1 except that surface-treated calcium carbonate surface-treated with an unsaturated fatty acid and a saturated fatty acid was produced.

(Comparative Example 1)
A surface-treated calcium carbonate surface-treated with an unsaturated fatty acid and a saturated fatty acid was produced in the same manner as in Example 1 except that 2 kg of synthetic calcium carbonate having a BET specific surface area of 15 m ² / g was used.

(Comparative Example 2)
Surface treated with unsaturated fatty acid and saturated fatty acid in the same manner as in Example 1 above, except that 60 g of mixed fatty acid (30 g of oleic acid and 30 g of stearic acid) in a mixing ratio of oleic acid / stearic acid = 1.0 was used. Treated calcium carbonate was produced.

(Comparative Example 3)
Oleic acid / stearic acid = 0, that is, surface-treated calcium carbonate surface-treated with an unsaturated fatty acid and a saturated fatty acid was produced in the same manner as in Example 1 except that only 200 g of stearic acid was used without using oleic acid. did.

<Powder test>
For the surface-treated calcium carbonate obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the most probable void diameter and the most probable void volume were measured using a mercury intrusion void diameter measuring device. The measurement conditions were a press-fit maximum pressure of 160 MPa · s and a limit minimum void diameter of 0.002 μm.

  Moreover, the total amount of fatty acids treated with unsaturated fatty acids and saturated fatty acids was measured by differential thermal analysis. Further, the ratio of unsaturated fatty acid / saturated fatty acid in the surface-treated calcium carbonate was measured by gas chromatography. These results are shown in Table 1.

Table 1 shows the values of (C) / (D) when the total amount of surface treatment of unsaturated fatty acids and saturated fatty acids is (C) parts by weight and the BET specific surface area is (D) m ² / g. Show.

  Table 1 shows the water content of the surface-treated calcium carbonate measured with a Karl Fischer moisture measuring machine.

<DOP sol viscosity test>
About the surface treatment calcium carbonate of Examples 1-9 and Comparative Examples 1-3, DOP sol was produced and the viscosity was measured. The DOP sol was sufficiently kneaded with 200 g of surface-treated calcium carbonate and 200 g of DOP (dioctyl phthalate, manufactured by J Plus), and the initial viscosity of the obtained DOP sol was measured at 20 ° C. Moreover, the viscosity after 20 degreeC x 7 days was measured at 20 degreeC. The viscosity was measured at 2 rpm and 20 rpm with a BH viscometer (manufactured by TOKIMEC). The measurement results are shown in Table 2. The viscosity increase rate indicates the rate of increase in viscosity after 7 days with respect to the viscosity immediately after kneading.

  As is apparent from the results shown in Table 2, it can be seen that the DOP sol using the surface-treated calcium carbonate of Examples 1 to 9 according to the present invention has high viscosity and good thixotropic properties. Moreover, it turns out that it is excellent also in storage stability.

  DOP sols are included as plasticizers in most sealants. In general, there is a correlation between the DOP viscosity and the sealant viscosity. Therefore, it can be said that the viscosity of the sealant using the surface-treated calcium carbonate of Examples 1 to 9 according to the present invention also shows a high viscosity and good thixotropic properties.

<Preparation and evaluation of silane-terminated urethane-containing resin composition>
Using the surface-treated calcium carbonate of Examples 1 to 9 and Comparative Examples 1 to 3, silane-terminated urethane-containing resin compositions were prepared as follows.

  Silane-terminated urethane-containing resin (trade name “Polymer ST65”, manufactured by Hanse Chemie AG) 100 g, surface-treated calcium carbonate 15 g, white glaze CCR (manufactured by Shiroishi Kogyo Co., Ltd.) 85 g, DOP 50 g, heavy calcium carbonate (trade name “Whiteon 305 “Shiraishi Kogyo Co., Ltd.” 35 g, Trimethoxyvinylsilane (trade name “KBM # 1003”, Shin-Etsu Chemical Co., Ltd.) 3.4 g, and Catalyst (trade name “# 918”, Sansha Gosei Co., Ltd.) 2.5 g By sufficiently kneading, a silane-terminated urethane-containing resin composition was prepared.

  For the silane-terminated urethane-containing resin composition prepared as described above, the initial viscosity and the viscosity after 7 days were measured in the same manner as in the case of the above DOP sol. Table 3 shows the measurement results.

  As is apparent from the results shown in Table 3, the silane-terminated urethane-containing resin compositions containing the surface-treated calcium carbonates of Examples 1 to 9 according to the present invention all exhibit high viscosity and good thixotropic properties. Yes. Moreover, it turns out that storage stability is also favorable.

Claims (8)

The most probable void in the pore size distribution curve by the mercury intrusion method is applied to a silane-terminated urethane-containing resin in which the main chain is polyoxypropylene, urethane groups are bonded to both sides, and silane groups are bonded to both ends. A silane-terminated urethane-containing resin composition comprising a surface-treated calcium carbonate having a diameter peak of less than 0.03 μm and a most probable void volume of 0.05 to 0.5 cm ³ / g.   The silane-terminated urethane-containing resin composition according to claim 1, wherein the surface-treated calcium carbonate is surface-treated with (A) an unsaturated fatty acid and (B) a saturated fatty acid. The silane-terminated urethane-containing resin composition according to claim 1 or 2, wherein the surface-treated calcium carbonate is a surface-treated calcium carbonate having a BET specific surface area of 10 to 100 m ² / g. Calcium carbonate obtained by surface-treating calcium carbonate having a BET specific surface area of 10 to 100 m ² / g with (A) unsaturated fatty acid and (B) saturated fatty acid, and the peak of the most probable pore diameter in the pore diameter distribution curve by mercury porosimetry Is less than 0.03 μm, and the surface-treated calcium carbonate having a most probable void volume of 0.05 to 0.5 cm ³ / g, the main chain is polyoxypropylene, and urethane groups are bonded to both sides thereof, Furthermore, the silane terminal urethane containing resin composition characterized by containing in the silane terminal urethane containing resin which the silane group couple | bonded with the both terminal each.   The silane-terminated urethane-containing resin according to any one of claims 2 to 4, wherein the unsaturated fatty acid (A) and the saturated fatty acid (B) are surface-treated in the form of a metal salt or an ester, respectively. Composition.   The silane-terminated urethane-containing resin composition according to any one of claims 2 to 5, wherein the unsaturated fatty acid (A) and the saturated fatty acid (B) are fatty acids having 6 to 31 carbon atoms.   The mixing ratio (A) / (B) of unsaturated fatty acid (A) and saturated fatty acid (B) is 0.3 to 5, silane according to any one of claims 2 to 6 Terminal urethane-containing resin composition.   The total amount of the surface treatment with the unsaturated fatty acid (A) and the saturated fatty acid (B) is 1 to 50 parts by weight with respect to 100 parts by weight of calcium carbonate. The silane-terminated urethane-containing resin composition described in 1.