JP5411827B2 - Two-component curable resin composition comprising a surface treated calcium carbonate filler - Google Patents

Description

The present invention relates to a two-curable resin composition obtained by blending the front surface-treated calcium carbonate filler.

Two-component curable resin compositions are used for applications such as architectural sealing materials, paints, automobile manufacturing sealing materials, sealing materials, and adhesives. The two-component curable resin composition is widely used because it has an advantage that the curing reaction rate can be adjusted by mixing the main agent and the curing agent as compared with the one-component curable resin composition. Maintaining the viscosity at which the two liquids of the main agent and the curing agent can be well mixed before is important in the formulation design. For this reason, the filler which is low viscosity and excellent in thixotropy is calculated | required.
Moreover, in the sealing material, it is known from the viewpoint of weight reduction that an organic micro hollow sphere (resin hollow body) is included in a curable resin composed of a room temperature curable polyurethane elastomer or a polysulfide ether polymer and a urethane prepolymer. (Patent Document 1, Patent Document 2).
However, increasing the blending amount of the hollow resin body increases the viscosity and decreases the workability or the durability after construction. Therefore, the blending amount of the hollow resin body is limited, and the sealing material composition There was a problem that the specific gravity of the object could not be reduced sufficiently. In order to solve this problem, a solution has been proposed in which a resin hollow body having a small particle diameter and a resin hollow body having a large particle diameter are mixed and blended in the resin hollow body (Patent Document 3). However, it is problematic in workability to mix a hollow body having a large particle diameter and a hollow body having a small particle diameter in an appropriate amount and to mix them uniformly.

JP-A-1-207351 JP-A-10-306210 JP 2008-285581 A

In view of such circumstances, the present invention is a two-component curable resin composition containing a resin-based hollow body, which is generally improved as a filler and a thixotropy imparting agent, and is improved by two-component liquid before curing. Two-component curing with a filler that can be made into a two-component curable resin composition that has low viscosity and can maintain thixotropy at the time of mixing, and is excellent in elasticity recovery, modulus, and elongation after curing. It is an object to provide a conductive resin composition.

  As a result of earnest research to solve the above problems, the present inventors have performed surface treatment (coating) with a specific surface treatment agent as a calcium carbonate filler to be blended in the main agent and / or curing agent. The surface-treated calcium carbonate filler with the particle size characteristics of the resin is excellent in workability in mixing with the resin and construction, and can be reduced in weight by blending a resin-based hollow body. The present inventors have found that a two-component curable resin composition excellent in both elongation and elongation can be provided, and completed the present invention.

That is, this invention is characterized by the following 1-5.
1 . A surface-treated calcium carbonate surface-treated with a fatty acid-based treating agent selected from fatty acids, fatty acid salts, fatty acid derivatives, and fatty acid derivative salts, and a saturated fatty acid having an alkyl composition of C12 or less. Is 20% or more of the total amount of saturated fatty acids and C16 or more saturated fatty acids is 10% or more of the total amount of saturated fatty acids, the BET specific surface area Sw of the surface-treated calcium carbonate is 3 to 40 m ² / g, and the unit specific surface area the surface treated calcium carbonate filler surface treatment amount Es is 0.20~6.50mg / m ² per characterized by comprising engages coordinating the curable resin comprising the resin hollow body Two-component curable resin composition.

2 . The above two-component curable resin composition, wherein the resin hollow body is at least one selected from acrylonitrile resin, vinylidene chloride resin, styrene resin, phenol resin, epoxy resin, urea resin, polymethacrylate, and polyvinyl alcohol object.

3 . The two-component curable resin composition, wherein the resin hollow body is coated with at least one inorganic filler selected from calcium carbonate, titanium oxide, silicon oxide, talc, clay, and carbon black .

4 . The two-component curable resin composition as described above, wherein the content of the resin-based hollow body is 0.2% by weight or more in the entire composition.

5 . The two-component curable resin composition, wherein the curable resin is at least one selected from a polyurethane resin, a polysulfide resin, a silicone resin, a modified silicone resin, and an acrylic urethane resin.

According to the present invention, excellent mixing time of workability of two liquids, elastic recovery property after curing, excellent in both of the modulus and elongation, two-hardening obtained by blending the front surface-treated calcium carbonate filler A functional resin composition can be provided. In addition, the two-component curable resin composition of the present invention is capable of adjusting the blending viscosity to an appropriate viscosity range, particularly in a system in which a resin-based hollow body is blended. Can be mixed. In addition, combined with the effect of weight reduction, the handling during construction improves, so it can contribute to light fatigue and can reduce the risk of slipping from the joints where it is constructed. Useful.

  In particular, since the sealing material composition comprising the two-component curable resin composition of the present invention is excellent in elastic resilience after curing, for example, it is applied to a joint with movement such as between a curtain wall method or an ALC plate. Even in such a case, the sealing material itself is not broken and the adherend is not damaged, and good water stop performance can be maintained. Further, the cured product made of the two-component curable resin composition of the present invention is very useful as a sealing material because of its low modulus and high elongation.

The two-component curable resin composition of the present invention is a surface-treated calcium carbonate that is surface-treated with a fatty acid-based treating agent comprising at least one selected from fatty acids, fatty acid salts, fatty acid derivatives, and fatty acid derivative salts. The saturated fatty acid having an alkyl composition of C12 or less is 20% or more of the total amount of saturated fatty acids and the saturated fatty acid of C16 or more is 10% or more of the total amount of saturated fatty acids, and the BET specific surface area Sw of the surface-treated calcium carbonate is Surface treated calcium carbonate filler (hereinafter sometimes abbreviated as calcium carbonate filler) having a surface treatment amount Es per unit specific surface area of 0.20 to 6.50 mg / m ^2, which is ³ to 40 m ² / g. ) In a curable resin containing a resin-based hollow body .
However, Es = Tg / Sw [mg / m ² ]
Tg: Surface treatment amount of fatty acid-based treatment agent per gram of calcium carbonate, and loss of heat per gram of surface-treated calcium carbonate at 200 ° C. to 500 ° C. [mg / g]

The calcium carbonate used in the present invention is not particularly limited. For example, it is obtained by mechanically pulverizing and classifying precipitated calcium carbonate and limestone produced by introducing CO ₂ gas into a Ca (OH) ₂ water slurry. Any of the heavy calcium carbonates can be used. In general, precipitated calcium carbonate can be preferably used because finer particles can be easily obtained.
About the particle size of the calcium carbonate in this invention, it selects so that the BET specific surface area Sw of the calcium carbonate surface-treated with the surface treating agent may be 3-40 m < ² > / g, Preferably it is 5-25 m < ² > / g.
If the specific surface area Sw is smaller than 3 m ² / g (particles are large), even if it is a curable resin composition containing surface-treated calcium carbonate, thixotropy may be insufficient. Further, when the specific surface area Sw is larger than 40 m ² / g (particles are small), the particles are strongly aggregated, and even in the curable resin composition containing the surface-treated calcium carbonate, The dispersibility at becomes worse. As a result, in addition to insufficient thixotropy, the obtained curable resin composition is inferior in elongation and cannot sufficiently cope with joint movement.
In the present invention, the specific surface area Sw is the BET specific surface area of the surface-treated calcium carbonate measured by the following method.
[Sample preparation method]
A glass cell is charged with 300 mg of sample, pretreated at 180 ° C. for 1 hour with nitrogen flowing through a flow degasser, and then cooled to room temperature to obtain a measurement sample.
[Measurement method of BET specific surface area]
It is measured by a one-point method using a BET specific surface area meter (NOVA2000, manufactured by Yuasa Ionics).

By the way, the BET specific surface area of the surface treated calcium carbonate varies depending on the surface treatment amount of the surface treatment agent of calcium carbonate. That is, even if the BET specific surface area of the calcium carbonate before the surface treatment is the same, as the surface treatment amount increases, the surface irregularities of the primary particles and the surface irregularities of the aggregates (secondary particles) in which the primary particles are aggregated And voids inside the aggregate are easily filled with the surface treatment agent, so that the BET specific surface area of the calcium carbonate after the surface treatment tends to be small. Therefore, the relationship between the BET specific surface area of the calcium carbonate before the surface treatment, the surface treatment amount, and the BET specific surface area of the calcium carbonate after the surface treatment is obtained in advance to obtain the desired BET specific surface area of the surface treated calcium carbonate. Therefore, it is desirable to be able to determine the surface treatment amount and the BET specific surface area of the calcium carbonate to be surface treated. In the range of the surface treatment amount Es per unit specific surface area of the present invention, calcium carbonate having a BET specific surface area that is approximately 1 to 5 m ² / g larger than the BET specific surface area of the desired surface-treated calcium carbonate can be selected.

The surface treatment agent in the present invention is a fatty acid-based surface treatment agent selected from fatty acids, fatty acid salts, fatty acid derivatives, and fatty acid derivative salts.
The fatty acid is not particularly limited, but saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid, resin acid and the like can be preferably used. Specifically, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, neodecanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, myristoleic acid Acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, beef tallow stearic acid, palm kernel fatty acid, palm fatty acid, palm fatty acid, palm stearic acid, beef tallow fatty acid, soybean fatty acid, partially cured palm kernel fatty acid, partially cured palm fatty acid, partial Hardened beef tallow fatty acid, partially hardened soy fatty acid, extreme Fatty acids such as hardened palm kernel fatty acid, extremely hardened palm fatty acid, extremely hardened beef tallow fatty acid, extremely hardened soy fatty acid, unsaturated fatty acid and saturated unsaturated fatty acid, alicyclic carboxylic acid such as naphthenic acid, abietic acid, Examples thereof include resin acids such as pimaric acid, parastrinic acid, and neoabietic acid. These can be used alone or in combination of two or more.

  Among these, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, beef tallow stearic acid, palm kernel fatty acid, partially cured palm fatty acid, extremely cured palm fatty acid, palm fatty acid, partially cured palm fatty acid, Saturation of extremely hardened coconut fatty acid, palm fatty acid, palm stearic acid, beef tallow fatty acid, partially cured beef tallow fatty acid, extremely hardened beef tallow fatty acid, soy fatty acid, partially cured soy fatty acid, extremely hardened soy fatty acid, naphthenic acid, abietic acid, neoabietic acid, etc. Examples include fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids. These saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, resin acids are alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, aluminum salts, iron, zinc, other heavy metal salts and It can also be used as salts such as ammonium salts and esters with lower alcohols such as methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, sec-butyl esters and tert-butyl esters. These can be used alone or in combination of two or more.

Regarding the surface treatment amount of the surface treatment agent in the present invention, the surface treatment amount Es per unit specific surface area is usually 0.20 to 6.50 mg / m ² , preferably 0.80 to 6.00 mg / m ² , and more. preferably from 1.50~5.50mg / m ^2.
However, Es = Tg / Sw [mg / m ² ]
Tg [mg / g]: Surface treatment amount of fatty acid-based treatment agent per gram of calcium carbonate, heat loss per 200 g of surface-treated calcium carbonate at 200 ° C. to 500 ° C. Sw [mg / m ² ]: Surface treatment of calcium carbonate BET specific surface area When the surface treatment amount Es is less than 0.20 mg / m ² , the effect of the surface treatment is insufficient, and the untreated surface is exposed due to insufficient treatment, so that moisture is easily adsorbed. On the other hand, if it exceeds 6.50 mg / m ² , the surplus treating agent acts as a lubricant, which may cause adverse effects such as a decrease in adhesion and a change in viscosity after storage, and is economically disadvantageous. The surface treatment amount Es is preferably varied according to the BET specific surface area Sw of calcium carbonate.
In the present invention, Tg is a treatment amount per gram of calcium carbonate, and is a heat loss per gram of surface-treated calcium carbonate at 200 ° C. to 500 ° C. measured by the following method.
[Measurement method of heat loss]
When using a thermal analyzer (TG8110, manufactured by Rigaku Corporation), 100 mg of surface-treated calcium carbonate was collected in a sample pan (made of platinum) having a diameter of 10 mm, and the temperature was increased from room temperature to 510 ° C at a temperature increase rate of 15 ° C / min. The heat loss of 200 ° C. to 500 ° C. is measured, and the heat loss (mg / g) per 1 g of the surface-treated calcium carbonate is determined.

In the surface treatment agent used in the present invention, saturated fatty acids having fatty acid alkyl composition of C12 or less are 20% or more of the total amount of saturated fatty acids, and saturated fatty acids of C16 or more are those having 10% or more of the total amount of saturated fatty acids. Preferably, C12 or less saturated fatty acid is 30% or more of the total amount of saturated fatty acid, and C16 or more saturated fatty acid is 20% or more of the total amount of saturated fatty acid.
Thus, by adjusting the C12 or lower short-chain saturated fatty acid and the C16 or higher long-chain saturated fatty acid to a specific mixing ratio, the surface treatment agent is uniformly coated on the calcium carbonate surface, and excellent physical properties are exhibited. Therefore, when the saturated fatty acid of C12 or less is less than 20% of the total amount of saturated fatty acid, the resin viscosity and modulus tend to increase as compared with the blending ratio, and the saturated fatty acid of C16 or more is 10% of the total amount of saturated fatty acid. When it is less than%, the surface treatment state of calcium carbonate is deteriorated and moisture is easily attracted, leading to a decrease in elongation, thixotropy, and elastic recovery, and durability is also deteriorated.
The upper limit of saturated fatty acids of C12 or less is 90%, preferably 80% of the total amount of saturated fatty acids, and the upper limit of saturated fatty acids of C16 or more is 80%, preferably 70% of the total amount of saturated fatty acids. When the saturated fatty acid of C12 or less exceeds 90%, the mixing viscosity increases and the thixotropy tends to decrease. Further, when the saturated fatty acid of C16 or more exceeds 80%, the surface treatment state of calcium carbonate is deteriorated as in the case of less than the lower limit, leading to an increase in modulus and a decrease in elongation rate, thixotropy, and elastic recovery rate. Durability also tends to deteriorate.

  The ratio of the unsaturated fatty acid in the fatty acid is not particularly limited as long as the saturated fatty acid is blended, but is included in the treatment agent comprising any of fatty acid, fatty acid salt, fatty acid derivative, and fatty acid derivative salt. The proportion of the unsaturated component is preferably 0 to 30% by weight, more preferably 5 to 25% by weight based on the total amount with the saturated component. When the proportion of the unsaturated component is larger than 30% by weight, the viscosity becomes high and the workability is hindered. In addition, unsaturated fatty acids are vulnerable to heat and are susceptible to deterioration, leading to discoloration in the production process of calcium carbonate such as drying, and a decrease in the elongation rate and elastic recovery rate of the resin composition, resulting in poor durability This is not preferable. Furthermore, in the production process of the surface-treated calcium carbonate, if the proportion of the unsaturated component is 5% by weight or more, it is relatively easy to uniformly coat the surface treatment agent on the surface of the calcium carbonate. It is more preferable from the viewpoints of increase in elongation rate, maintenance of elastic recovery rate, and durability.

The surface-treated calcium carbonate used in the present invention is subjected to a surface treatment (coating) using the above-mentioned surface treatment agent, and then pulverized according to a conventional method through steps such as dehydration, drying, and pulverization. There is no particular limitation except that a surface treatment agent is used, and the surface treatment method may be either wet or dry.

  The resin-based hollow body contained in the two-component curable resin composition of the present invention has a structure in which the outer shell of a hollow sphere is coated with a resin and / or a resin and an outer periphery thereof with an inorganic substance. For example, a thermally expandable resin-based hollow body obtained by heating resin particles encapsulating a liquid therein, evaporating the internal liquid, and expanding the resin portion by the pressure to obtain an expanded resin portion as an outer shell, Furthermore, the hollow body which coat | covered the outer periphery with the inorganic powder is mentioned.

Examples of the resin constituting the outer shell of the resin-based hollow body include resins such as acrylonitrile resin, vinylidene chloride resin, styrene resin, phenol resin, epoxy resin, urea resin, polymethacrylate, and polyvinyl alcohol. These can be used alone or in combination of two or more.
Of these, acrylonitrile-based resins and vinylidene chloride-based resins are preferably used from the viewpoints of weather resistance and heat resistance.

  On the other hand, examples of the liquid encapsulated in the resin-based hollow body include hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, and petroleum ether, methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloro. Examples include chlorinated hydrocarbons such as ethylene. These can be used alone or in combination of two or more.

  The manufacturing method of the resin-based hollow body is not particularly limited, and can be manufactured by a conventionally known method.

  In the two-component curable resin composition of the present invention, the resin-based hollow body can be contained in one or both of the main agent and the curing agent, but the curable resin is reactive such as a polyurethane resin. In the case of a rich main agent, if the resin-based hollow body is blended with the main agent, it may react with the moisture taken in at the time of blending, so it is preferably blended only with the curing agent. In the case of other resins, it is more preferably contained in the main agent from the viewpoint of improving workability when the main agent and the curing agent are mixed.

The maximum particle diameter of the resin-based hollow body is not particularly limited as long as the resin-based hollow body used for general purposes has a range, but is preferably 500 μm or less, and more preferably 100 μm or less. The lower limit of the particle diameter of the resin hollow body is not particularly limited, but is preferably about 10 μm from the viewpoint of lowering the specific gravity (weight reduction).
Here, the particle diameter of the resin-based hollow body is measured using a microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd.) based on the laser diffraction method.

  In the present invention, the resin-based hollow body is preferably coated with an inorganic filler from the viewpoint of excellent handling during production of the curing agent and the main agent.

  The inorganic filler used for coating the resin hollow body is not particularly limited, and specific examples thereof include calcium carbonate, titanium oxide, silicon oxide, talc, clay, carbon black and the like. These can be used alone or in combination of two or more.

  The method for coating the resin-based hollow body with an inorganic filler is not particularly limited, and can be coated by a conventionally known method.

  In the two-component curable resin composition of the present invention, the content of the resin hollow body is usually suitably 0.2% by weight or more based on the total amount of the two-component curable resin composition. When the content of the resin hollow body is 0.2% by weight or more, the resulting curable resin composition is excellent in durability, has a small specific gravity, and can be reduced in weight. Preferably, the content of the resin hollow body is 0.2 to 5% by weight. When the inorganic filler is coated, the specific gravity increases and the number of parts by weight increases. However, if the content of the resin hollow body is more than 5% by weight, the resin hollow body can be reduced in weight as much as the curable resin. Therefore, it is difficult to maintain the durability of the curable resin material composition.

  What is necessary is just to set the compounding quantity to the 2 liquid type curable resin of the surface treatment calcium carbonate filler of this invention suitably by the kind and use of resin. For example, in the case of a polyurethane resin or a modified silicone resin, the amount is usually about 10 to 200 parts by weight, preferably about 20 to 150 parts by weight with respect to 100 parts by weight of the resin. If the number of blended parts is too small, the effect of thixotropy and slump resistance cannot be expected. On the other hand, if the number is too large, the viscosity may be too high and workability may be hindered.

The surface-treated calcium carbonate filler of the present invention is blended in a two-component curable resin, has a low viscosity and a thixotropy, and is excellent in any of the elastic recovery rate, modulus, and elongation rate after curing. A liquid curable resin composition is obtained.
The type of resin is not particularly limited as long as the two-component curable resin used in the present invention is a two-component curable resin. Examples of the two-component curable resin include polyurethane resin (urethane prepolymer and polyether polyol), epoxy resin, mixed resin of polyurethane resin and epoxy resin, silicone resin, modified silicone resin, modified silicone / epoxy resin, Special modified silicone / epoxy resin, reactive acrylic resin, polysulfide resin, acrylic urethane resin, and the like. These can be used alone or in combination of two or more.

For example, in the case of a polyurethane sealant, a polyol having a hydroxyl group at the molecular end is used as a curing agent component, and a polyisocyanate urethane prepolymer having an isocyanate group at the molecular end is used as a main component. As the polyol, various polyether polyols, polyester polyols, and other polyols can be used.
Examples of the polyether polyol include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-propylene copolymer polyol, polytetramethylene polyol and the like alone or a mixture of two or more thereof.
Polyester polyols include dicarboxylic acids (adipic acid, succinic acid, maleic acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexane glycol, neopentyl glycol, etc.) Polyols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polypropylene adipate, polyethylene-propylene adipate and the like, and polylactone polyols such as polycaprolactone polyol alone. Alternatively, a mixture of two or more of them, polycarbonate polyol, and the like can be mentioned. These can be used alone or in combination of two or more.
The urethane prepolymer as the main component is synthesized by a reaction between a polyol and an excess of a polyisocyanate compound. Examples of the polyisocyanate compound used in the present invention include 2,4-tolylene diisocyanate, 2,6- Aromatic polyisocyanates such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, carbodiimide modified MDI, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate and alicyclic system A polyisocyanate is mentioned. These can be used alone or in combination of two or more.
The surface-treated calcium carbonate filler of the present invention is usually blended on the curing agent side.

  Curing catalysts include stannous oleate, stannous laurate, stannous acetate, zinc octylate, lead octylate, tin octylate, bismuth octylate, lead naphthenate, bismuth naphthenate, manganese naphthenate, Cobalt manganate, ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth acetate, bismuth oxalate, bismuth citrate, bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth carbonate, bismuth oxide , Acetylacetone calcium, calcium octylate, calcium neodecanoate, triethylamine, N-methylmorpholine, triethanolamine, triethylenediamine, acetylacetone, and the like, and these may be used alone or in combination of two or more. As for the compounding quantity of a curing catalyst, 0.1-10 weight part is preferable with respect to 100 weight part of polyols.

Furthermore, a solvent, a plasticizer, a filler, a pigment, a thickener, a thixotropic agent, a stabilizer, and other additives can be blended as necessary.
Examples of the solvent include aromatic hydrocarbons such as xylene and toluene, mineral spirits, and methyl ethyl ketone.
Examples of the plasticizer include monomer plasticizers such as diisononyl phthalate (DINP), dioctyl adipate (DOA), dioctyl phthalate (DOP), dibutyl phthalate (DBP), tricresyl phosphate (TCP), polyester, and urethane. And oligomer plasticizers such as fluorinated polyester and urethanized polyether. These can be used alone or in combination of two or more. The amount of the solvent and the plasticizer to be blended is increased in a small amount for recent environmental regulations and bleed contamination reduction, and is preferably 0 to 30 parts by weight with respect to 100 parts by weight of the polyol.
Examples of the filler include calcium carbonate, talc, clay, carbon, shirasu balloon, glass balloon, and polyvinyl chloride fine powder. These can be used alone or in combination of two or more.
Examples of the thixotropic agent include colloidal silica, finely divided carbon black, fatty acid amide, and fatty acid metal soap. These can be used alone or in combination of two or more.

  For example, in the case of a polysulfide sealant, a liquid polysulfide polymer having a reactive mercapto group (—SH) at the molecular end can be used as the main component. A modified polysulfide resin having a mercapto group at the molecular weight end and having a urethane bond in the main chain can also be used. It is preferable to react these with an isocyanate-based silane coupling agent to use as a moisture-curing type terminal-modified polysulfide.

  In the case of an isocyanate curable polysulfide sealant, a compound containing two or more isocyanate groups in the molecule used in the present invention (hereinafter simply referred to as an isocyanate group-containing compound) may be an organic polyisocyanate compound and / or an active hydrogen-containing compound. It is preferable to use a urethane prepolymer obtained by reacting an isocyanate compound as a curing agent component.

  As the curing catalyst, a tertiary amine and / or an organometallic compound is used. The tertiary amine includes monoamines, diamines, triamines, polyamines, cyclic amines, alcohol amines, ether amines, and the like, which are used alone or in combination of two or more as necessary. Specific examples of organometallic compounds include tin octylate, bismuth octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin maleate, dioctyltin mercaptide, phenylmercuric propionate, lead octenoate, acetic acid Examples thereof include bismuth, bismuth oxalate, bismuth citrate, bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth carbonate, bismuth oxide, calcium acetylacetone, calcium octylate, and calcium neodecanoate. These may be used alone or in combination of two or more as required.

0.001-5 weight part is preferable with respect to 100 weight part of polysulfide polymers, and, as for the compounding quantity of a curing catalyst, More preferably, it is 0.005-3 weight part. If the content is less than 0.001 part by weight, curing does not proceed and if it exceeds 5 parts by weight, the pot life tends to be short, which is not preferable.
Furthermore, other additives can be contained as required. Examples of additives that can be used include other inorganic fillers, plasticizers, pigments, rubber vulcanizing agents, reinforcing agents, adhesion-imparting agents, ultraviolet rays and ozone degradation inhibitors, and the like. As other inorganic fillers, for example, calcium carbonate powder (untreated), heavy calcium carbonate powder, quartz powder, alumina, calcium oxide, talc, glass powder, various aggregates, and the like can be used. These can be used alone or in combination of two or more.

In the case of a modified silicone sealant, the modified silicone resin that is the main component used in the present invention is known per se, and the Si group has an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, an amide group, an oxime group. It is a polymer having a hydrolyzable silyl group to which a hydrolyzable group such as is bonded at the end of the molecular chain and having a repeating unit of propylene oxide as a skeleton.
The modified silicone is a polymer having a crosslinkable silyl group at the molecular terminal of polyoxyalkylene. Examples of the polyoxyalkylene that becomes the skeleton of the modified silicone include polyoxyethylene, polyoxypropylene, and polyoxybutylene, and polyoxypropylene is preferable. The present invention is not limited to these, and the structure of the main skeleton may be used as long as it has a crosslinkable silyl group in the molecule. A mixture of these may also be used.

  Curing catalysts include butyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, etc., inorganic tin, titanate ester, titanium chelate compound, aluminum alkoxide, aluminum chelate compound, Zirconium alkoxides, zirconium chelate compounds, dibismuth catalysts, metal complexes, platinum catalysts, basic substances and organic phosphorous oxides are used. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, lead octylate, zinc octylate, bismuth octylate, calcium octylate, bismuth versatate, lead naphthenate, bismuth naphthenate , Nickel naphthenate, cobalt naphthenate, bismuth acetate, bismuth oxalate, bismuth citrate, bismuth neodecanoate, calcium neodecanoate, bismuth 2-ethylhexanoate, metal acetyl acetates such as aluminum acetyl acetate complex Examples thereof include metal acetylacetonate complexes such as complexes, acetylacetone bismuth, acetylacetone calcium, and vanadium acetylacetonate complexes. These may be used alone or in combination of two or more. The blending amount of the curing catalyst is preferably 0.5 to 6.0 parts by weight with respect to 100 parts by weight of the modified silicone resin.

As the plasticizer, phthalic esters such as diisononyl phthalate (DINP) and dioctyl phthalate (DOP), fatty acid esters, glycol esters, and the like can be used. These may be used alone or in combination of two or more. The blending amount of the plasticizer is preferably 20 to 80 parts by weight with respect to 100 parts by weight of the resin.
Further, if necessary, one or two of coloring pigments, ultraviolet absorbers, antioxidants, adhesion improvers, anti-aging agents, metal deactivators, ozone degradation inhibitors, light stabilizers, foaming agents, etc. More than seeds may be added.

For example, in the case of a silicone sealant, the silicone resin used in the present invention is known per se, and a linear organopolysiloxane having reactive silanol groups at both ends is used as a main agent.
As the crosslinking agent (curing agent), cyclic and linear siloxanes having aminoxy groups and organopolysiloxanes having alkoxylane functional groups are used. As for the compounding quantity of a crosslinking agent, 50-150 weight part is preferable with respect to 100 weight part of silicone resins.
Furthermore, curing is based on an organopolysiloxane having one hydroxyl group at one end and a silanol group at the other end, and an inert organopolysiloxane having no such functional group and the above-described modified silicone sealant curing catalyst. It can also be used in combination with an agent, and the blending amount of the curing catalyst is in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the silicone resin.

Furthermore, a solvent, a plasticizer, a filler, a pigment, a thickener, a thixotropic agent, a stabilizer, and other additives can be blended as necessary.
Examples of the plasticizer include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, polyether-modified, epoxy-modified, amino-modified, carboxyl-modified, and carbinol-modified silicone oil. These can be used alone or in combination of two or more.
As a compounding quantity of a plasticizer, 0-30 weight part is preferable with respect to 100 weight part of resin. Other examples of the adhesion-imparting agent include titanium-based chelate compounds, amine-based and epoxy-based coupling agents.

  Since the two-component curable resin composition of the present invention can use various curable resins as described above, it can be used in a wide range of applications. Since the composition has a reduced blending viscosity of the main agent (base material) or curing agent, mixing workability is good, and by blending a resin-based hollow body, the specific gravity can be reduced and the weight can be reduced. Since it is excellent in all of resilience, modulus, and elongation, it is suitable for applications such as architectural sealing materials, paints, automotive manufacturing sealing materials, sealing materials, and adhesives.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, it is needless to say that the present invention is not limited to these examples.

Example 1
54.4 g of sodium laurate (alkyl composition) in 1 L of warm water at 80 ° C. with respect to 10 L of precipitated calcium carbonate aqueous slurry with a concentration of 160 g CaCO ₃ / L and a pre-treatment BET specific surface area of 17 m ² / g adjusted to a temperature of 50 ° C. : C12: 100%, the same shall apply hereinafter) and 9.6 g of extremely hardened palm fatty acid sodium (alkyl composition: C16: 56%, C18: 44%, the same shall apply hereinafter) were added and stirred together with the calcium carbonate slurry. . This calcium carbonate slurry was dehydrated to a solid content of 60%, dried in a box dryer at 105 ° C. for 12 hours, and then pulverized to obtain a surface-treated calcium carbonate powder having a BET specific surface area of 15 m ² / g. The proportion of each carbon number in the alkyl composition of the fatty acid of the powder (saturated fatty acids C8 to C18, unsaturated fatty acids C8F1, C18F2), and the proportion of saturated fatty acids of C12 or less in the total amount of saturated fatty acids in the alkyl composition, and Table 1 shows the ratio of saturated fatty acids of C16 or more, the ratio of unsaturated components in the total amount of fatty acids, BET specific surface area Sw, heat loss Tg, and surface treatment agent amount Es per unit specific surface area. Table 1 also shows each ratio, BET specific surface area Sw, heat loss Tg, and surface treatment agent amount Es per unit specific surface area in Examples 2 to 35 below.

Example 2
Example 1 was the same as Example 1 except that 8 g of sodium dodecylbenzenesulfonate was further added.

Example 3
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 56 g of sodium laurate and 8 g of extremely hardened palm fatty acid sodium.

Example 4
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 51.2 g of sodium laurate and 12.8 g of sodium hardened palm fatty acid.

Example 5
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 48 g of sodium laurate and 16 g of extremely hardened palm fatty acid sodium.

Example 6
In Example 1, the BET specific surface area 17 m ² / g before treatment of the precipitated calcium carbonate water slurry was changed to 45 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 23.84 g of sodium laurate. All the same procedures as in Example 1 except that the surface-treated calcium carbonate powder BET specific surface area 15 m ² / g was changed to 40 m ² / g to 8 g of extremely hardened palm fatty acid sodium.

Example 7
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry was 17 m ² / g, 23 m ² / g, sodium laurate 54.4 g, extremely hardened palm fatty acid sodium 9.6 g, and sodium laurate 60 g extremely. the hardened palm fatty acid sodium 20g, the resulting surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 20 m ² / g.

Example 8
In Example 1, the BET specific surface area 17 m ² / g before treatment of the precipitated calcium carbonate water slurry was 10 m ² / g, sodium laurate 54.4 g, extremely hardened palm fatty acid sodium 9.6 g and sodium laurate 60 g extremely the hardened palm fatty acid sodium 20g, the resulting surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 8m ² / g.

Example 9
In Example 1, the pretreated BET specific surface area of precipitated calcium carbonate water slurry was 17 m ² / g to 4 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 25.92 g of sodium laurate. All the same procedures as in Example 1 except that the surface-treated calcium carbonate powder BET specific surface area 15 m ² / g was changed to 3 m ² / g to 9.12 g of extremely hardened palm fatty acid sodium.

Example 10
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 44.8 g of sodium laurate and 19.2 g of extremely hardened palm fatty acid sodium.

Example 11
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of sodium laurate and 32 g of sodium hardened palm fatty acid.

Example 12
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of sodium laurate and 32 g of extremely hardened palm fatty acid.

Example 13
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of lauric acid, 32 g of extremely hardened palm fatty acid and 16 g of dodecylbenzenesulfonic acid.

Example 14
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 25.6 g of sodium laurate and 38.4 g of extremely hardened palm fatty acid sodium.

Example 15
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 19.2 g of sodium laurate and 44.8 g of sodium hardened palm fatty acid.

Example 16
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 16 g of sodium laurate and 48 g of extremely hardened palm fatty acid sodium.

Example 17
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 12.8 g of sodium laurate and 51.2 g of sodium hardened palm fatty acid.

Example 18
In Example 1, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium, 32 g of extremely hardened palm fatty acid sodium and coconut fatty acid sodium (C8: 6%, C10: 6%, C12: 50%, C14: 20) %, C16: 10%, C18: 2% C18F1: 6%) All were the same as in Example 1 except that the amount was changed to 32 g.

Example 19
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 64 g of sodium coconut fatty acid.

Example 20
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of sodium coconut fatty acid and 8 g of sodium dodecylbenzenesulfonate.

Example 21
In Example 1, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to palm kernel fatty acid sodium (C10: 1%, C12: 54%, C14: 17%, C16: 10%, C18: 2%). C18F1: 14%, C18F2: 2%) All were the same as in Example 1 except for changing to 64 g.

Example 22
In Example 1, 54.4 g of sodium laurate, 9.6 g of extremely hardened palm fatty acid sodium, 48 g of palm kernel fatty acid sodium and beef tallow fatty acid sodium (C12: 2%, C14: 5%, C16: 33%, C18: 18% , C18F1: 42%)) All were the same as in Example 1 except that it was changed to 16 g.

Example 23
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 48 g of palm kernel fatty acid sodium, 16 g of beef tallow fatty acid sodium and 8 g of sodium dodecylbenzenesulfonate. .

Example 24
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 44.8 g of sodium laurate and 19.2 g of tallow fatty acid sodium.

Example 25
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of sodium laurate and 32 g of tallow fatty acid sodium.

Example 26
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of sodium laurate and 32 g of beef tallow fatty acid.

Example 27
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 32 g of sodium laurate, 32 g of beef tallow fatty acid sodium and 8 g of sodium dodecylbenzenesulfonate.

Example 28
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 32 g of lauric acid, 32 g of beef tallow fatty acid and 8 g of dodecylbenzenesulfonic acid.

Example 29
In Example 1, the BET specific surface area 17 m ² / g before treatment of the precipitated calcium carbonate water slurry was 23 m ² / g, sodium laurate 54.4 g, extremely hardened palm fatty acid sodium 9.6 g, sodium laurate 40 g and beef tallow fatty acid sodium 40 g, the resulting surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 20 m ² / g.

Example 30
In Example 1, the pre-treatment BET specific surface area of the precipitated calcium carbonate slurry of 17 m ² / g was 10 m ² / g, 54.4 g of sodium laurate, 9.6 g of extremely hardened palm fatty acid sodium, 40 g of sodium laurate and beef tallow fatty acid sodium 40 g, the resulting surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 8m ² / g.

Example 31
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry of 17 m ² / g is 12 m ² / g, 54.4 g of sodium laurate, 9.6 g of extremely hardened palm fatty acid sodium, 24 g of sodium laurate and beef tallow The same procedure as in Example 1 was conducted except that the surface-treated calcium carbonate powder BET specific surface area 15 m ² / g was changed to 10 m ² / g to 24 g of fatty acid sodium.

Example 32
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry was 17 m ² / g, 23 m ² / g, 54.4 g of sodium laurate, 9.6 g of extremely hardened palm fatty acid sodium, 24 g of sodium laurate and tallow The same procedure as in Example 1 was conducted except that the surface-treated calcium carbonate powder BET specific surface area 15 m ² / g was changed to 20 m ² / g to 24 g of fatty acid sodium.

Example 33
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 19.2 g of sodium laurate and 44.8 g of tallow fatty acid sodium.

Example 34
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 16 g of sodium laurate and 48 g of beef tallow fatty acid sodium.

Example 35
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 16 g of sodium laurate and 48 g of beef tallow fatty acid.

(Table 1) continued 1

Comparative Example 1
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 59.2 g of sodium laurate and 4.8 g of sodium hardened palm fatty acid. The proportion of each carbon number in the alkyl composition of the fatty acid of the powder (saturated fatty acids C8 to C18, unsaturated fatty acids C8F1, C18F2), and the proportion of saturated fatty acids of C12 or less in the total amount of saturated fatty acids in the alkyl composition, and Table 2 shows the ratio of saturated fatty acids of C16 or higher, the ratio of unsaturated components in the total amount of fatty acids, BET specific surface area Sw, heat loss Tg, and surface treatment agent amount Es per unit specific surface area. Table 2 also shows each ratio, BET specific surface area Sw, heat loss Tg, and surface treatment agent amount Es per unit specific surface area in Comparative Examples 2 to 18 below.

Comparative Example 2
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 59.2 g of sodium laurate and 4.8 g of extremely hardened palm fatty acid.

Comparative Example 3
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 60.8 g of sodium laurate and 3.2 g of extremely hardened palm fatty acid sodium.

Comparative Example 4
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 11.2 g of sodium laurate and 52.8 g of extremely hardened palm fatty acid sodium.

Comparative Example 5
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry was 17 m ² / g, 18 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to sodium laurate 11. All were the same as Example 1 except for changing to 2 g, extremely hardened palm fatty acid sodium 52.8 g, and sodium dodecylbenzenesulfonate 8 g.

Comparative Example 6
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were changed to 3.2 g of sodium laurate and 60.8 g of extremely hardened palm fatty acid sodium.

Comparative Example 7
In Example 1, the BET specific surface area 17m ² / g before treatment of the precipitated calcium carbonate water slurry was changed to 46 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 23.84 g of sodium laurate. and the extremely hardened palm fatty acid sodium 8 g, except for changing the obtained surface treated calcium carbonate powder BET specific surface area of 15 m ² / g to 41m ² / g was the same as in example 1.

Comparative Example 8
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry of 17 m ² / g was 3 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 14.4 g of sodium laurate. and the extremely hardened palm fatty acid sodium 7.2 g, the obtained surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 2m ² / g.

Comparative Example 9
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of sodium laurate.

Comparative Example 10
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of sodium laurate and 8 g of sodium dodecylbenzenesulfonate.

Comparative Example 11
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of extremely hardened palm fatty acid sodium.

Comparative Example 12
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate water slurry of 17 m ² / g was 3 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 14.4 g of sodium laurate. and a tallow fatty acid sodium 7.2 g, the obtained surface treated calcium carbonate powder BET specific surface area of 15 m ² / g were the same as in example 1 except for changing the 2m ² / g.

Comparative Example 13
In Example 1, the pretreated BET specific surface area of the precipitated calcium carbonate aqueous slurry was 17 m ² / g, 6 m ² / g, sodium laurate 54.4 g, extremely hardened palm fatty acid sodium 9.6 g, sodium laurate 32 g and beef tallow. The same procedure as in Example 1 was conducted except that the surface-treated calcium carbonate powder BET specific surface area 15 m ² / g was changed to 4 m ² / g to 16 g of fatty acid sodium.

Comparative Example 14
In Example 1, the BET specific surface area 17 m ² / g before treatment of the precipitated calcium carbonate water slurry was changed to 55 m ² / g, sodium laurate 54.4 g, extremely hardened palm fatty acid sodium 9.6 g, sodium laurate 32 g and beef tallow. The same procedure as in Example 1 was carried out except that 16 g of fatty acid sodium was changed to a surface-treated calcium carbonate powder BET specific surface area of 15 m ² / g of 50 m ² / g.

Comparative Example 15
In Example 1, the BET specific surface area 17m ² / g before treatment of the precipitated calcium carbonate water slurry was changed to 34 m ² / g, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to 6.4 g of sodium laurate. and a tallow fatty acid sodium 3.2 g, except for changing the obtained surface treated calcium carbonate powder BET specific surface area of 15 m ² / g to 30 m ² / g was the same as in example 1.

Comparative Example 16
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of beef tallow fatty acid sodium.

Comparative Example 17
Example 1 was the same as Example 1 except that 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were replaced with 64 g of beef tallow fatty acid sodium and 8 g of sodium dodecylbenzenesulfonate.

Comparative Example 18
In Example 1, 54.4 g of sodium laurate and 9.6 g of extremely hardened palm fatty acid sodium were added to palm oil, palm kernel mixed fatty acid sodium (C12: 13.3%, C14: 6%, C16: 47.5%, C18). : 3.7%, C18F1: 27.3%, C18F2: 2.2%) All were the same as in Example 1 except for changing to 64 g.

Examples 36 to 70, Comparative Examples 19 to 36
Using the surface-treated calcium carbonate fillers obtained in Examples 1 to 35 and Comparative Examples 1 to 18, a two-component polyurethane sealant was prepared by the following test method (1), and the physical properties were evaluated. The results are shown in Tables 3 and 4.

(Test method (1): Reaction-curing two-component polyurethane sealant)
[Combination]
(Curing agent)
Polyether polyol (Accor 8734, manufactured by Mitsui Takeda Chemical Co., Ltd.)
100 parts by weight Bismuth octylate (Neostan U660, manufactured by Nitto Kasei Co., Ltd.) 3.7 parts by weight Heavy calcium carbonate coated acrylonitrile resin balloon (MFL-60CA, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 9.3 parts by weight Heavy carbonic acid Calcium (Super S, Maruo Calcium Co., Ltd.) 136 parts by weight Surface treated calcium carbonate filler 93 parts by weight
Curing agent total 342 parts by weight (base)
Urethane prepolymer (Takenate L-1032, manufactured by Mitsui Takeda Chemical Co., Ltd.)
85.5 parts by weight
Base + curing agent total 427.5 parts by weight

[Kneading method]
The curing agent compounding raw material is put into a 2L universal mixing stirrer (manufactured by Dalton Co., Ltd.), preliminarily stirred for 15 minutes at low speed, scraped off the filler adhering to the mixing stirrer, and then kneaded at high speed for 30 minutes to harden It was created. This was filled into a 100 ml PP cup and covered with PE film.

[Mixed viscosity measurement method]
Weigh 120g of curing agent and base 30g (mixing ratio 4: 1) left at 23 ° C for 1 day in a 300ml cup, knead with a spatula for 3 minutes, and then a planetary defoaming stirrer (Mazerustar KK). -500 manufactured by Kurabo Industries Co., Ltd.) under kneading conditions 9-4-6.
In the kneading conditions “abc”, “a” represents revolution conditions, “b” represents rotation conditions, “c” represents time, and means c × 10 seconds.
The mixture was measured using a BS type viscometer (VISCOMETER TV-20, manufactured by Tokimec Co., Ltd.) (rotor No. 7).
1 rpm viscosity was a value after 3 minutes, and 10 rpm was a value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 1 rpm viscosity value by the 10 rpm viscosity value.

[Viscosity criteria]
Judgment criteria vary depending on the purpose of use, application, desired level, etc., and thus cannot be defined unconditionally. However, for reference, the following criteria are shown. The same applies to the following criteria.
(1 rpm) Less than 2,000 Pa · s: Good, 2,000 Pa · s or more: Bad (10 rpm) Less than 350 Pa · s: Good, 350 Pa · s or more: Bad (TI value) 6.00 or more: Excellent, 5.50 Less than ~ 6.00: Good, Less than 5.00-5.50: Somewhat bad, Less than 5.00: Bad

[Tensile test method]
Apply a primer (NO.30 made by Yokohama Rubber Co., Ltd.) to the surface of an aluminum plate (50 mm x 50 mm x 3 mm), dry for 60 minutes, and then fill with the mixed sealing material (shape 12 mm x 12 mm x 50 mm), In accordance with JIS A 1439 “Building Sealant 5.17.2 Durability, Production of Tensile Test Specimen”, an H-type test specimen was prepared.
This specimen was cured at 23 ° C. × 7 days + 50 ° C. × 7 days, and measured after 23 ° C. × 1 day using a tensile tester (Autograph AG-1 manufactured by Shimadzu Corporation).
50% tensile stress: Value obtained by dividing the load when stretched at a rate of 50 mm per minute and stretched at 50% elongation (6 mm) by the cross-sectional area of the sealing material (600 mm ² ) Maximum tensile stress: 50 mm per minute Pulled at the speed, the largest load divided by the cross-sectional area of the sealing material Elongation rate: Value obtained by dividing the displacement at the maximum tensile stress by the shape at the time of filling (12 mm) and multiplying by 100

[Criteria for tensile test]
(50% tensile stress) 0.12 N / mm less than ^2: Yu, less than 0.12-0.15 N / mm ^2: good, than 0.15 to 0.20 N / mm ^2: Slightly poor, 0.20 N / mm ² or more: poor (maximum tensile stress ) Indicates the measured value.
(Elongation rate) 600% or more: Excellent, 500 to less than 600%: Good, 400 to less than 500%: Somewhat bad, Less than 400%: Bad

[Elastic recovery]
Apply a primer (NO.30 made by Yokohama Rubber Co., Ltd.) on the surface of aluminum plate (75mm × 12mm × 6mm), let it dry for 60 minutes, then fill the above mixed sealing material (shape 12mm × 12mm × 50mm), In accordance with JIS A 1439 “Building Sealant 5.3.2 Preparation of Tensile Properties Test Specimens”, elastic resilience test samples were prepared.
23 ° C x 28 days + 70 ° C x 3 days + 23 ° C water x 1 day + 70 ° C x 2 days + 23 ° C water x 1 day, 24 mm extension (L1) for 1 hour. The width after elongation release (L2) was measured, and the elastic resiliency was calculated from the shape (L0) at the time of filling by the following formula.
Elastic resilience (%) = [(L1-L2) / (L1-L0)] x 100

[Criteria for elastic resilience]
95.0% or more: Excellent, 90.0 to less than 95.0%: Good, 85.0 to less than 90.0%: Somewhat bad, Less than 85.0%: Bad

[Durability test]
In accordance with JIS A 1439 “Building Sealant 5.17.2, Preparation of Durability and Tensile Test Specimen”, an H-type test specimen was prepared, and 23 ° C. × 7 days + 50 ° C. × as in the tensile test method. Cured for 7 days.
After 23 ° C x 1 day, test conditions for general durability classification of two-component polyurethane sealant (8020; heat resistance 80 ° C, 20% expansion and contraction test);
(50 ° C hot water x 1 day + 23 ° C x 1 day + 80 ° C 20% compression x 7 days + 23 ° C x 1 day + (-10 ° C) 20% elongation x 1 day + 23 ° C x 1 day)
Was carried out for 2 cycles.
Thereafter, a ± 20% stretching repetition test (maximum extension width 14.4 mm, minimum compression width 9.6 mm) was performed 2000 times at a rate of 5 times per minute at 23 ° C.

[Durability criteria]
Cracks do not occur in the sealing material after the durability test: good, cracks occur: poor

  From Tables 3 and 4, the two-component polyurethane sealants of Examples 36 to 70 blended with the surface-treated calcium carbonate fillers of Examples 1 to 35 showed low viscosity and high thixotropy, low modulus and elongation. It can be seen that it is high and exhibits high resilience and excellent durability.

Examples 71-99, Comparative Examples 37-51
The surface-treated calcium carbonate filler obtained in Examples 1, 3 to 12, 14 to 17, 19, 20, 22 to 24, 27 to 35, Comparative Examples 1 to 4, 6 to 9, 11 to 16, and 18. Then, a two-component modified silicone sealant was prepared by the following test method (2), and its physical properties were evaluated. The results are shown in Tables 5 and 6.

(Test method (2): Reaction curing type two-component modified silicone sealant)
[Combination]
(Base)
Modified silicone resin (MS polymer S810 manufactured by Kaneka Corporation) 100 parts by weight Plasticizer DINP (manufactured by Jplus Co., Ltd.) 70 parts by weight Heavy calcium carbonate coated acrylonitrile resin balloon (MFL-60CA Matsumoto Yushi Pharmaceutical Co., Ltd.) 8 parts by weight Heavy calcium carbonate (Super S manufactured by Maruo Calcium Co., Ltd.) 42 parts by weight Surface treated calcium carbonate filler 110 parts by weight
Total 330 parts by weight of base (curing agent)
Tin octylate 28% (Neostan U-28, manufactured by Nitto Kasei Co., Ltd.) 3 parts by weight Laurylamine (1st grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 0.7 part by weight Plasticizer DINP (manufactured by J-Plus Co., Ltd.) 7 parts by weight Heavy calcium carbonate (Super 3S, manufactured by Maruo Calcium Co., Ltd.) 20 parts by weight Calcium carbonate (Calfine 200M, manufactured by Maruo Calcium Co., Ltd.) 2.5 parts by weight
Hardener total 33.2 parts by weight
Base + curing agent total 363.2 parts by weight

[Kneading method]
Put the base compounding raw material into a 2L universal mixing stirrer (manufactured by Dalton Co., Ltd.) Created. This was filled into a 100 ml PP cup and covered with PE film.
The raw material containing the curing agent was also subjected to the same kneading conditions, filled in a 100 ml PP cup, and covered with a PE film.

[Mixed viscosity measurement method]
Weigh 150 g of base and 15 g of curing agent (mixing ratio 10: 1) left at 23 ° C. for 1 day in a 300 ml cup, knead with a spatula for 3 minutes, and then use a planetary defoaming stirrer (Mazerustar KK). -500 manufactured by Kurabo Industries Co., Ltd.) under kneading conditions 9-4-6.
In the kneading conditions “abc”, “a” represents revolution conditions, “b” represents rotation conditions, “c” represents time, and means c × 10 seconds.
The mixture was measured using a BS type viscometer (VISCOMETER TV-20, manufactured by Tokimec Co., Ltd.) (rotor is NO. 7).
1 rpm viscosity was a value after 3 minutes, and 10 rpm was a value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 1 rpm viscosity value by the 10 rpm viscosity value.

[Viscosity criteria]
(1 rpm) Less than 2,000 Pa · s: Good, 2,000 Pa · s or more: Bad (10 rpm) Less than 400 Pa · s: Good, 400 Pa · s or more: Bad (TI value) 6.00 or more: Excellent, 5.50 Less than ~ 6.00: Good, Less than 5.00-5.50: Somewhat bad, Less than 5.00: Bad

[Tensile test method]
Apply a primer (NO. 40 made by Yokohama Rubber Co., Ltd.) to the surface of an aluminum plate (50 mm x 50 mm x 3 mm), dry for 60 minutes, and then fill the mixed sealing material (shape 12 mm x 12 mm x 50 mm), In accordance with JIS A 1439 “Building Sealant 5.17.2 Durability, Production of Tensile Test Specimen”, an H-type test specimen was prepared.
This specimen was cured at 23 ° C. × 7 days + 50 ° C. × 7 days, and measured after 23 ° C. × 1 day using a tensile tester (Autograph AG-1 manufactured by Shimadzu Corporation).
50% tensile stress: Value obtained by dividing the load when stretched at a rate of 50 mm per minute and stretched at 50% elongation (6 mm) by the cross-sectional area of the sealing material (600 mm ² ) Maximum tensile stress: 50 mm per minute Pulled at the speed, the largest load divided by the cross-sectional area of the sealing material Elongation rate: Value obtained by dividing the displacement at the maximum tensile stress by the shape at the time of filling (12 mm) and multiplying by 100

[Criteria for tensile test]
(50% tensile stress) 0.12 N / mm less than ^2: Yu, less than 0.12-0.15 N / mm ^2: good, than 0.15 to 0.20 N / mm ^2: Slightly poor, 0.20 N / mm ² or more: poor (maximum tensile stress ) Indicates the measured value.
(Elongation rate) 700% or more: Excellent, 600 to less than 700%: Good, 500 to less than 600%: Somewhat bad, Less than 500%: Bad

[Elastic recovery]
Apply primer (NO.40 made by Yokohama Rubber Co., Ltd.) to the surface of aluminum plate (75mm x 12mm x 6mm), dry for 60 minutes, and then fill the above mixed sealing material (shape 12mm x 12mm x 50mm) In accordance with JIS A 1439 “Building Sealant 5.3.2 Preparation of Tensile Test Material”, an elastic resilience test sample was prepared.
The test conditions for elastic resilience are 23 ° C × 28 days + 70 ° C × 3 days + 23 ° C water × 1 day + 70 ° C × 2 days + 23 ° C water × 1 day, and 24 mm extension (L1) is performed for 1 hour. The width after elongation release (L2) was measured, and the elastic resiliency was calculated from the shape (L0) at the time of filling by the following formula.
Elastic resilience (%) = [(L1-L2) / (L1-L0)] x 100

[Criteria for elastic resilience]
95.0% or more: Excellent, 90.0 to less than 95.0%: Good, 85.0 to less than 90.0%: Somewhat bad, Less than 85.0%: Bad

[Durability test]
In accordance with JIS A 1439 “Building Sealant 5.17.2, Preparation of Durability and Tensile Test Specimen”, an H-type test specimen was prepared, and 23 ° C. × 7 days + 50 ° C. × as in the tensile test method. Cured for 7 days.
Test conditions for general durability classification (9030; heat resistance 90 ° C, 30% expansion and contraction test) of two-component modified silicone sealant after 23 ° C x 1 day;
(50 ° C warm water x 1 day + 23 ° C x 1 day + 90 ° C 30% compression x 7 days + 23 ° C x 1 day + (-10 ° C) 30% elongation x 1 day + 23 ° C x 1 day)
Was carried out for 2 cycles.
Thereafter, a ± 30% stretch repetition test (maximum extension width 15.6 mm, minimum compression width 8.4 mm) was conducted 2000 times at 23 ° C. at a rate of 5 times per minute.

[Durability criteria]
Cracks do not occur in the sealing material after the durability test: good, cracks occur: poor

  From Table 5 and Table 6, the binary component modification of Examples 71-99 which compounded the surface treatment calcium carbonate filler of Examples 1, 3-12, 14-17, 19, 20, 22-24, 27-35. It can be seen that the silicone sealant exhibits low viscosity and high thixotropy, low modulus and high elongation, and high resilience and durability.

As the ordination, high thixotropy at very low viscosity According to the present invention, there is provided a low modulus, high elongation, high elastic recovery property, and the two-component curable resin composition having excellent durability be able to.

Claims (5)

A surface-treated calcium carbonate surface-treated with a fatty acid-based treating agent selected from fatty acids, fatty acid salts, fatty acid derivatives, and fatty acid derivative salts, and a saturated fatty acid having an alkyl composition of C12 or less. Is 20% or more of the total amount of saturated fatty acids and C16 or more saturated fatty acids is 10% or more of the total amount of saturated fatty acids, the BET specific surface area Sw of the surface-treated calcium carbonate is 3 to 40 m ² / g, and the unit specific surface area A surface-treated calcium carbonate filler having a surface treatment amount Es of 0.20 to 6.50 mg / m ² ,
2 part curable resin composition characterized by comprising combined distribution in the curable resin comprising the resin hollow body.
However, Es = Tg / Sw [mg / m ² ]
Tg: Surface treatment amount of fatty acid-based treatment agent per gram of calcium carbonate, and loss of heat per gram of surface treated calcium carbonate at 200 ° C. to 500 ° C. [mg / g] The two-component liquid according to claim 1 , wherein the resin-based hollow body comprises at least one selected from acrylonitrile-based resin, vinylidene chloride-based resin, styrene-based resin, phenol resin, epoxy resin, urea resin, polymethacrylate, and polyvinyl alcohol. Mold curable resin composition. The two-component mold according to claim 2 , wherein the resin-based hollow body is coated with at least one inorganic filler selected from calcium carbonate, titanium oxide, silicon oxide, talc, clay, and carbon black. Curable resin composition. The two-component curable resin composition according to any one of claims 1 to 3 , wherein the content of the resin-based hollow body is 0.2% by weight or more in the entire composition. The two-component curable resin according to any one of claims 1 to 4 , wherein the curable resin is at least one selected from a polyurethane resin, a polysulfide resin, a silicone resin, a modified silicone resin, and an acrylic urethane resin. Composition.