JP2017025194A - Paste-like composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste-like composition capable of providing a cured product having high strength and excellent elongation.SOLUTION: The paste-like composition is provided which comprises: a calcium carbonate particle having a BET specific surface area of 5 to 60 m/g; and a paste-like polymer. In an image of a calcium carbonate particle obtained by observing, using an optical microscope, a film formed by applying the paste-like composition to a transparent film, an area ratio of an agglomerated particle having a particle diameter of 20 μm or more is 30% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a paste-like composition containing calcium carbonate particles and a paste-like polymer.

  The sealing material for construction is required to have various performances such as adhesion to an adherend and joint followability. As a sealing material excellent in joint followability, a sealing material excellent in elongation is required. However, it is generally known that a sealing material having high strength is difficult to stretch.

  Patent Document 1 describes that a modified silicone resin composition exhibiting a high elongation with a low modulus can be obtained by using a surface-treated calcium carbonate containing a specific amount of alkali metal.

JP 2013-47300 A

  An object of the present invention is to provide a paste-like composition from which a cured product having high strength and excellent elongation can be obtained in a paste-like composition containing calcium carbonate particles and a paste-like polymer.

The present invention relates to a paste-like composition comprising calcium carbonate particles having a BET specific surface area of 5 to 60 m ² / g and a paste-like polymer, and a film formed by applying the paste-like composition on a transparent film In an image of calcium carbonate particles when observed using an optical microscope, the area ratio of the image of aggregated particles having a particle diameter of 20 μm or more is 30% or less.

  Examples of the pasty polymer in the present invention include polyurethane resins and terminal silyl group resins.

  The paste-like composition of the present invention can be used, for example, for a sealant.

  According to the present invention, a cured product having high strength and excellent elongation can be obtained.

It is a microscope picture which shows an example of the image of a calcium carbonate particle when the film | membrane formed by apply | coating a paste-form composition on a transparent film is observed using an optical microscope.

  Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.

<Calcium carbonate particles>
The calcium carbonate particles used in the present invention are preferably surface-treated calcium carbonate particles. As calcium carbonate particles to be surface-treated, for example, conventionally known calcium carbonate can be used. Specific examples of calcium carbonate include synthetic calcium carbonate and natural calcium carbonate (heavy calcium carbonate). The calcium carbonate is preferably synthetic calcium carbonate.

  Synthetic calcium carbonate is not particularly limited. Examples of the synthetic calcium carbonate include precipitated (collaged) calcium carbonate and light calcium carbonate. Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide. 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. 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.

  Natural calcium carbonate is obtained by pulverizing naturally produced calcium carbonate ore by a known method. Examples of the method for pulverizing the raw calcium carbonate include a roller mill, a high-speed rotation mill (impact shear mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, and a jet mill.

(fatty acid)
The calcium carbonate particles of the present invention are preferably surface-treated with a fatty acid.

  Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms.

  Specific examples of saturated fatty acids include 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, montanic acid, Examples include melicic acid. Among these, lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid and the like are preferably used.

  Specific examples of the unsaturated fatty acid include obsylic acid, carloleic acid, undecylenic acid, Linderic acid, tuzuic acid, fizeteric acid, molistoleic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclebic acid , Vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, brassic acid, ceracolic acid, ximenoic acid, lumectric acid, sorbic acid, linoleic acid and the like.

  The form of the fatty acid when the surface treatment of calcium carbonate with the fatty acid is not particularly limited, and the surface treatment can be performed in the form of a metal salt of a fatty acid, an acid form, an ester form, or the like. If necessary, these forms may be used in combination for surface treatment.

  Examples of the metal salt of fatty acid include alkali metal salts such as sodium salt and potassium salt of the above fatty acid, and alkaline earth metal salts such as magnesium salt and calcium salt. Among these, alkali metal salts such as sodium salts and potassium salts of the above fatty acids are preferable.

  Examples of fatty acid esters include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, and the like.

  As a more preferable form of the fatty acid for the surface treatment, a sodium salt or potassium salt of a saturated fatty acid having 9 to 21 carbon atoms can be mentioned. Among these, sodium salts such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid are particularly preferable.

(Surface treatment method)
Examples of the method for surface treatment of calcium carbonate include a wet treatment method and a dry treatment method.

  Examples of the wet processing method include a method of adding a solution containing a fatty acid to a slurry containing calcium carbonate and water, followed by dehydration and drying. Examples of the solution containing a fatty acid include a solution containing a fatty acid in the form of a metal salt such as an alkali metal salt, an acid form, or an ester form. Among these, those containing an alkali metal salt form of a fatty acid as the main component of the fatty acid are preferably used.

  Examples of the dry treatment method include a method of adding a surface treatment agent to calcium carbonate while stirring the calcium carbonate. The surface treatment agent may be added as a solution, or calcium carbonate may be added while heating to a temperature equal to or higher than the melting point of the surface treatment agent. In this case, the fatty acid may be in the form of an acid, may be in the form of an ester, or may be in the form of a metal salt. Further, the calcium carbonate may be calcium carbonate that has been surface-treated by wet treatment or the like.

(BET specific surface area)
BET specific surface area of the calcium carbonate particles of the present invention ^is in the range of 5m ² / g~60m 2 / ^g, preferably in the range of ^{8m 2 / g~45m 2 / g,} 10m 2 / g~ More preferably, it is within the range of 40 m ² / g. If the BET specific surface area of the calcium carbonate particles is too low, the paste-like composition cannot have high thixotropic properties, and the function as calcium carbonate particles may be impaired. When the BET specific surface area of calcium carbonate is too high, the cohesive force is generally strong and the dispersibility may be deteriorated.

<Paste polymer>
Examples of the pasty polymer in the present invention include polyurethane resins and terminal silyl group resins.

(Polyurethane resin)
About the polyurethane resin of the type which mixes an isocyanate and a polyol, one of isocyanate or polyol can be used as a pasty polymer, and calcium carbonate particles can be mixed therewith.

  Isocyanates 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 polyol include dicarboxylic acids such as adipic acid, phthalic acid, sebacic acid, and dimer acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, hexanetriol, and trimethylolpropane. Can be mentioned. Examples of other polyols include esters of the type obtained by ring-opening polymerization of caprolactone.

  The pasty polymer may be mixed with a plasticizer and a catalyst. 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.

  When one of the isocyanate and polyol is used as a pasty polymer to prepare a paste-like composition of the present invention, a cured product can be obtained by adding the other of the isocyanate and polyol to the pasty polymer. it can.

(Terminal silyl group resin)
As terminal silyl group resin, what contains terminal silyl group polyether resin or terminal silyl group polyurethane resin as a main component is mentioned. The terminal silyl group polyether resin is known as a modified silicone resin.

(Modified silicone resin)
The modified silicone resin is mainly composed of a silyl group-terminated polyether having a reactive silyl group introduced at the terminal. For example, when the modified silicone resin composition is used as a sealant, the modified silicone resin preferably forms a siloxane bond by moisture curing. Examples of the modified silicone resin include polymers formed by using a linear or branched polyoxyalkylene polymer as a main chain and introducing a silyl group at the hydroxyl group terminal. The modified silicone resin may be a known one. Commercial products are easily available for the modified silicone resin. Examples of commercial products of the modified silicone resin include MS polymer S810, MS polymer S202, MS polymer S203, MS polymer S303 manufactured by Kaneka Corporation, and EXESTER manufactured by Asahi Glass Co., Ltd.

  When the modified silicone resin is used as a pasty polymer, a plasticizer may be added. Examples of the plasticizer include those described above. Moreover, an adhesion imparting agent, a dehydrating agent, a catalyst, or the like may be added. Examples of the adhesion imparting agent include hydrolyzable organic silicone compounds. Examples of the dehydrating agent include a silane coupling agent. Examples of the catalyst include known curing catalysts such as organic tin compounds such as dibutyltin diacetylacetonate.

(Terminal silyl group polyurethane resin)
The terminal silyl group polyurethane resin is mainly composed of a silyl group-terminated polyurethane having a reactive silyl group introduced at the terminal. For example, when a silyl group-terminated polyurethane resin composition is used as a sealant, the silyl group-terminated polyurethane resin preferably forms a siloxane bond by moisture curing. Examples of the silyl group-terminated polyurethane resin include a polymer formed by introducing a silyl group into the hydroxyl terminal of a polyurethane having a linear or branched polyoxyalkylene polymer as a main chain. The silyl group-terminated polyurethane resin may be a known one. Commercially available products are readily available for the silyl group-terminated polyurethane resin. Examples of commercially available silyl group-terminated polyurethane resins include GENIOSIL STP-E10, GENIOSIL STP-E15, GENIOSIL STP-E30, and GENIOSIL STP-E35 manufactured by WACHER.

  In addition to the silyl group-terminated polyurethane resin, the silyl group-terminated polyurethane resin composition may contain a plasticizer, a filler, an adhesion-imparting agent, a dehydrating agent, a catalyst, and the like. These plasticizer, filler, adhesion-imparting agent, dehydrating agent, and catalyst may be the same as those used in the modified silicone resin composition. The silyl group-terminated polyurethane resin composition may contain one or more plasticizers, fillers, adhesion-imparting agents, dehydrating agents, and catalysts, respectively, or may contain a plurality of types.

  When the terminal silyl group polyurethane resin is used as a pasty polymer, a plasticizer may be added. Moreover, an adhesion imparting agent, a dehydrating agent, a catalyst, or the like may be added. As these plasticizer, adhesion-imparting agent, dehydrating agent, and catalyst, the same ones as in the case of the modified silicone resin can be used.

<Paste-like composition>
The content of calcium carbonate particles in the paste-like composition is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 60% by weight, and in the range of 15 to 50% by weight. Is more preferable.

  In the present invention, in the image of the calcium carbonate particles when the film formed by applying the paste-like composition on the transparent film is observed using an optical microscope, the area ratio of the image of the aggregated particles having a particle diameter of 20 μm or more Is 30% or less. In order to reduce the area ratio of the image of aggregated particles having a particle diameter of 20 μm or more to 30% or less, the calcium carbonate particles are preferably finely pulverized using a pulverizer having higher pulverization performance than before. Moreover, it is preferable to pulverize the paste-like composition to which calcium carbonate particles have been added through a mill or the like.

  Hereinafter, the present invention will be described with reference to specific examples. However, the following examples are merely illustrative, and the present invention is not limited to the following examples.

Example 1
Water was added to 2000 g of synthetic calcium carbonate having a BET specific surface area of 20 m ² / g so that the solid content would be 10% by weight, and stirred at 40 ° C. to prepare a calcium carbonate slurry. Next, 600 g of a mixed fatty acid sodium salt adjusted to 10% by weight was mixed with this slurry to prepare a slurry of calcium carbonate and a fatty acid salt. Next, the obtained slurry was dehydrated to obtain a cake having a solid content of 60% by weight. The obtained cake was dried with a dryer and pulverized at a pulverization speed of 10,000 rpm using a pin mill type pulverizer (Coroplex manufactured by Hosokawa Micron Corporation) to obtain surface-treated calcium carbonate. The obtained surface-treated calcium carbonate had a BET specific surface area of 17.9 m ² / g.

  Next, 520 parts by weight of the surface-treated calcium carbonate obtained, 80 parts by weight of bifunctional polypropylene glycol (average molecular weight 3000), 160 parts by weight of trifunctional polypropylene glycol (average molecular weight 5000), 16 parts by weight of lead catalyst, and plasticizer ( (DINP) 130 parts by weight were mixed for 20 minutes to obtain a paste-like composition as a polyurethane pre-composition.

[Measurement of area ratio]
The area ratio of the aggregated particles of calcium carbonate in the paste-like composition obtained in Example 1 was measured as follows.

  On the transparent film, the paste composition was applied so as to have a thickness of 25 μm. Subsequently, the coating film of the obtained paste-like composition with a thickness of 25 μm was observed using a digital microscope (KH-8700, manufactured by HIROX). Specifically, it was observed from above with a digital microscope in a state where light was irradiated from below the transparent film.

FIG. 1 is a photomicrograph showing an example of an image of calcium carbonate particles when a film formed by applying a paste-like composition on a transparent film is observed using an optical microscope. In FIG. 1, the aggregated particles of calcium carbonate are observed as gray particles. Using image analysis software (Winroof), only the aggregated particles of calcium carbonate having a particle diameter of 20 μm or more were counted, and the total area of the images of the aggregated particles of calcium carbonate in the observation region was obtained. The particle diameter was determined as the equivalent circle diameter. The area of the region to be observed is preferably in the range of ² to 100 mm2. Here, the area of the region to be observed is 20 mm ² .

  Moreover, the theoretical area of all the calcium carbonate particles in the observation region was obtained. Specifically, the volume content of calcium carbonate particles contained in the coating film of the paste-like composition was determined, and the theoretical area of all calcium carbonate particles in the observation region was calculated from this volume content.

  From the area of the image of the aggregated particles of calcium carbonate having a particle diameter of 20 μm or more determined as described above and the theoretical area of the calcium carbonate particles, the area ratio was calculated by the following formula.

  Area ratio (%) = [area of image of aggregated particles of calcium carbonate having a particle diameter of 20 μm or more / theoretical area of calcium carbonate particles] × 100

  In the present invention, the paste-like composition is prepared so that the area ratio thus obtained is 30% or less. Specifically, the calcium carbonate particles are finely pulverized using a pulverizer, or the paste-like composition to which the calcium carbonate particles are added is passed through a roller mill or the like. In this example, the area ratio was 28.6%.

[Measurement of elongation]
The elongation percentage of the cured product obtained from the paste-like composition obtained in Example 1 was measured as follows.

  A PP sheet is stretched on a glass plate, a glass spacer having a thickness of 3.0 mm is pasted on the sheet, and 600 parts by weight of the paste-like composition obtained in Example 1 and tolylene diisocyanate ( (NCO% = 3.0%) A sealant mixed with 150 parts by weight is filled so as not to contain bubbles. Then, it was cured at 23 ° C. for 7 days and then at 50 ° C. for 7 days. After punching out the sheet with dumbbell-shaped No. 2 defined in JIS K6251 and leaving the test piece to stand at 23 ° C. for 1 day or longer, the thickness of the test piece is measured, and the test is carried out with an autograph at a tensile speed of 200 mm / min. The elongation between the marked lines was measured. The measurement results are shown in Table 1.

[Measurement of 50% modulus and tensile strength]
The 50% modulus and tensile strength of the cured product obtained from the paste-like composition obtained in Example 1 were measured as follows.

  Cured under the same conditions as the measurement of elongation, punched out the sheet in dumbbell shape No. 2 specified in JIS K6251, left the test piece at 23 ° C for one day or more, then measured the thickness of the test piece, The test is performed using a graph at a tensile speed of 200 mm / min. The stress when the elongation between 20 mm marked lines was 50% was measured as 50% modulus, and the maximum stress at break was measured as tensile strength. The measurement results are shown in Table 1.

(Example 2)
Surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that the pulverization speed of the pin mill type pulverizer was changed to 14000 rpm. The obtained surface-treated calcium carbonate had a BET specific surface area of 17.7 m ² / g. Using this surface-treated calcium carbonate, a paste-like composition was produced in the same manner as in Example 1. Using this paste-like composition, in the same manner as in Example 1, the area ratio of the aggregated particle image in the paste-like composition, the elongation percentage of the cured product obtained from the paste-like composition, 50% modulus, and tensile The strength was measured. The measurement results are shown in Table 1.

(Example 3)
A surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that the pulverization speed of the pin mill type pulverizer was changed to 14000 rpm and the kneading time of the paste-like composition was changed from 20 minutes to 30 minutes. The obtained surface-treated calcium carbonate had a BET specific surface area of 17.7 m ² / g. Using this surface-treated calcium carbonate, a paste-like composition was produced in the same manner as in Example 1. Using this paste-like composition, in the same manner as in Example 1, the area ratio of the aggregated particle image in the paste-like composition, the elongation percentage of the cured product obtained from the paste-like composition, 50% modulus, and tensile The strength was measured. The measurement results are shown in Table 1.

(Comparative Example 1)
A surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that the pulverization speed of the pin mill type pulverizer was changed to 6000 rpm. The obtained surface-treated calcium carbonate had a BET specific surface area of 18.1 m ² / g. Using this surface-treated calcium carbonate, a paste-like composition was produced in the same manner as in Example 1. Using this paste-like composition, in the same manner as in Example 1, the area ratio of the aggregated particle image in the paste-like composition, the elongation percentage of the cured product obtained from the paste-like composition, 50% modulus, and tensile The strength was measured. The measurement results are shown in Table 1.

(Comparative Example 2)
A paste-like composition was prepared in the same manner as in Comparative Example 1 except that the amount of the plasticizer (DINP) was changed from 130 parts by weight to 180 parts by weight. Using this paste-like composition, in the same manner as in Example 1, the area ratio of the aggregated particle image in the paste-like composition, the elongation percentage of the cured product obtained from the paste-like composition, 50% modulus, and tensile The strength was measured. The measurement results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 3 using a paste-like composition having an area ratio of 30% or less, 50% modulus and tensile strength comparable to those of Comparative Example 1 are maintained, and high strength is achieved. On the other hand, the elongation is higher than that of Comparative Example 1. Therefore, according to the present invention, a paste-like composition can be obtained from which a cured product having high strength and excellent elongation can be obtained.

  In Comparative Example 2, a large amount of plasticizer is used to increase the elongation, but in this case, it can be seen that the 50% modulus and tensile strength are reduced.

Claims (3)

A paste-like composition comprising calcium carbonate particles having a BET specific surface area of 5 to 60 m ² / g and a paste-like polymer,
In an image of calcium carbonate particles when a film formed by applying the paste-like composition on a transparent film is observed using an optical microscope, the area ratio of the image of aggregated particles having a particle diameter of 20 μm or more is 30% or less. A paste-like composition.   The paste-like composition according to claim 1, wherein the paste-like polymer is a polyurethane resin or a terminal silyl group resin.   The paste-like composition according to claim 1 or 2, which is used for a sealant.