JP2003034760A - Surface-treated calcium carbonate heavy and method for producing the same, and resin composition containing surface-treated calcium carbonate heavy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated calcium carbonate heavy having improved dispersibility in and affinity to resins and providing porous films and resin compositions having good physical properties. SOLUTION: The surface-treated calcium carbonate heavy is prepared by surface-treating a calcium carbonate heavy having a specific average particle diameter and a BET specific surface area using a specific amount of surface- treating agents selected from aliphatic acids, alicyclic carboxylic acids and aromatic carboxylic acids, aliphatic, alicyclic and aromatic sulfonic acids, resin acids, and esters, amine salts and metal salts thereof; coupling agents; silicone oil; and paraffin. The surface-treated calcium carbonate heavy satisfies a specific range of the average particle diameter, the BET specific surface area, pH, electric conductivity, and color difference.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface-treated heavy calcium carbonate, a method for producing the same, and a resin composition containing the surface-treated heavy calcium carbonate. More specifically, for example, when it is used for a polyolefin resin, it has excellent dispersibility in the resin, and when it is used for a vinyl chloride resin, it is a surface-treated heavy calcium carbonate that is uniformly dispersed without aggregation during kneading with the resin. And a method for producing the same, and a resin composition containing the surface-treated heavy calcium carbonate.

[0002]

2. Description of the Related Art Calcium carbonate is roughly classified into two types according to the production method, and limestone is mechanically crushed and classified to obtain a desired particle size, and limestone is mixed and burned with coke or the like. After making calcium oxide (quick lime) and reacting it with water to obtain calcium hydroxide (slaked lime),
By reacting with carbon dioxide gas generated during combustion, the desired particle size,
There are synthetic calcium carbonates called light calcium carbonate or colloidal calcium carbonate in particle form.

In particular, heavy calcium carbonate produces a large amount of high quality products in Japan and is provided at a relatively low cost, and thus constitutes various films, sheets and parts for medical, food, industrial and design purposes. It is used as a bulking agent for plastics, interior / exterior materials for construction, electric wire coating materials, electric equipment members, etc.

However, due to rapid technological progress in recent years, heavy calcium carbonate, which was once used only as an extender, influences the moldability, dimensional stability, and thermal stability of products such as vinyl chloride resin. It has become an important material, and in addition to making the grain size and grain shape sharper and more uniform, it has become necessary to have a high degree of dispersion in the resin and compatibility with the resin. In order to meet these requirements, pulverization and classification are carried out, and heavy calcium carbonate whose particle size and grain shape are strictly adjusted is added to fatty acid, alicyclic carboxylic acid, aromatic carboxylic acid, aliphatic, alicyclic, aromatic After surface treatment of heavy calcium carbonate with sulfonic acid, resin acid and their metal salts / amine salts, esters, coupling agents, silicone oil, paraffin, etc., disintegration and advanced dispersion in resin Methods for improving the properties and affinity with resins have been studied.

For example, in Japanese Patent Laid-Open No. 11-35715, a polyolefin resin is blended with an inorganic filler and stretched,
In order to create a void and generate a porous film,
It has been proposed to coat the surface of particles with a higher fatty acid such as stearic acid and lauric acid, or a metal salt thereof, in a heavy calcium carbonate having a limited average particle size to improve dispersibility in a resin. Further, for example, in Japanese Patent Laid-Open No. 05-45618, regarding the surface-treated heavy calcium carbonate used when preparing a porous sheet made of a polyethylene resin, the type and amount of the surface-treatment agent to be used, and the surface-treatment method. Is proposed. Further, JP-A-2000-336197 mentions the pH of calcium carbonate in the same application of a polyolefin-based porous film and improves the problem by coating the particle surface of heavy calcium carbonate more completely with a surface treatment agent. For this purpose, a two-step processing method has been proposed.

However, even if the above-mentioned surface-treated heavy calcium carbonate is used, the dispersibility in the resin cannot be completely satisfied, and the surface-treated heavy calcium carbonate is dispersed in the stretching step during the production of the film or sheet. The defect causes local necking and pinholes to cause unevenness in the film and causes various problems such as uneven thickness of the film itself. In addition, the surface treatment agent that does not chemically react with heavy calcium carbonate and remains or adheres to it causes thermal deterioration due to the heat during film production, which causes yellowing of the sheet and reduces the commercial value, or heavy calcium carbonate. When it is used in applications where the alkali of heavy calcium carbonate precipitates from the film / sheet, etc., and it often comes into contact with the human body, it may have an adverse effect such as stimulating the skin to contact. There is a problem that the use is limited.

The above problems are caused by the fact that the surface treating agents used for the surface treatment of the heavy calcium carbonate do not sufficiently chemically or physically adsorb / bond to the surface of the heavy calcium carbonate particles. That is, the kind and addition amount of the surface treatment agent and the treatment method were examined. But,
None of them have completely met the requirements, and due to recent rapid and advanced technological advances, they have become more and more remarkable, and urgent improvements are required.

On the other hand, inorganic materials (4th July, 1997)
Vol. 330-336), focusing on the difference in reactivity between heavy calcium carbonate and fatty acids of synthetic calcium carbonate,
By spraying steam on the ground calcium carbonate for 1 hour, the surface of the ground calcium carbonate particles is activated to bring it closer to the reactivity of the surface of the synthetic calcium carbonate particles.
It has been proposed to increase reactivity with fatty acids.

However, this method only changes the particle surface of the ground calcium carbonate into calcium hydroxide to enhance the reactivity with fatty acids, and the surface-treated ground calcium carbonate obtained by this method has a pH There is a problem that the color tone is high and the color tone is yellowish.

Further, the temperature condition during the surface treatment is, for example, 13
A method has also been proposed in which the reactivity of the surface treatment agent is increased by heating at a temperature of 0 ° C. or higher for several hours to further enhance the reactivity with the ground calcium carbonate. However, there is a problem in that the original characteristics are impaired due to the tendency of thermal deterioration.

[0011]

DISCLOSURE OF THE INVENTION The present invention overcomes the above problems and provides a surface treatment agent for a particle surface of a heavy calcium carbonate and a surface treatment agent without impairing the properties of the heavy calcium carbonate which is inexpensive and has a sharp particle size. By providing a surface-treated heavy calcium carbonate having good dispersibility in the resin and good affinity to the resin by increasing the reactivity, a method for producing the surface-treated heavy calcium carbonate, and the surface-treated heavy carbonate. A resin composition containing calcium is provided.

[0012]

Means for Solving the Problems The present invention has been earnestly studied to solve the above problems, and as a result, a specific average particle diameter / BE
Using heavy calcium carbonate having a T specific surface area as a raw material, a specific range of average particle diameter, BET specific surface area, pH,
A surface-treated heavy calcium carbonate having an electric conductivity, a color difference, and a treatment amount, a method for producing the surface-treated heavy calcium carbonate, and a resin composition containing the surface-treated heavy calcium carbonate are intended purposes. The inventors have found that they can achieve the above and completed the present invention.

That is, the first aspect of the present invention (claim 1) is
To the heavy calcium carbonate satisfying the following formulas (1) to (5),
Selected from fatty acids / alicyclic carboxylic acids / aromatic carboxylic acids, aliphatic / alicyclic / aromatic sulfonic acids, resin acids, their metal salts / amine salts / esters, coupling agents, silicone oils, and paraffins. A surface-treated heavy calcium carbonate characterized by being surface-treated with at least one surface-treating agent, wherein the surface-treated heavy calcium carbonate satisfies the following formulas (6) to (16): is there.

0.1 ≤ D50A ≤ 40 (1) 0.2 ≤ Sw ≤ 30 (2) 60 ≤ L ₁ ≤ 99.9 (3) -3 ≤ a ₁ ≤ 1 (4) -1.5 ≤ b ₁ ≤ 2.5 (5) 0.15 ≤ D50 ≤ 30 (6) 0.25 ≤ Sw1 ≤ 20 (7) 8 ≤ α ≤ 10 (8) 5 ≤ Sc ≤ 300 (9) 60.5 ≤ L ₂ ≤ 99.5 (10) -2.9 ≤ a ₂ ≤ 0.9 (11)- 1.4 ≤ b ₂ ≤ 2.4 (12) 0 ≤ ΔL ≤ 2 (13) 0 ≤ Δa ≤ 1 (14) 0 ≤ Δb ≤ 2 (15) 0.050 ≤ W / Sw ≤ 0.700 (16)

However, D50A: 50% average particle size [μm] of heavy calcium carbonate measured by Microtrac FRA laser type particle size distribution meter Sw: BET specific surface area [m ² / of heavy calcium carbonate]
g] L ₁ : L value of heavy calcium carbonate obtained by color difference meter [-] a ₁ : a value of heavy calcium carbonate obtained by color difference meter [-] b ₁ : heavy calcium carbonate obtained by color difference meter B value of [-] D50: 50% average particle size of surface-treated heavy calcium carbonate measured by Microtrac FRA laser particle size distribution meter
[μm] Sw 1: BET specific surface area of surface-treated heavy calcium carbonate
[m ² / g] α: pH of surface-treated surface-treated heavy calcium carbonate
[−] Sc: Electric conductivity of surface-treated heavy calcium carbonate [μS
/ Cm] L _2: the surface treatment heavy calcium carbonate obtained by the color difference meter L
Value [-] a _2: a surface treatment heavy calcium carbonate obtained by the color difference meter
Value [−] b ₂ : b of surface-treated heavy calcium carbonate obtained by color difference meter
Value [−] ΔL: Difference in L value of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes [−] Δa: a value of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes Difference [−] Δb: Difference in b value of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes [−] W: Surface treatment agent amount relative to heavy calcium carbonate [% by weight] W / Sw: Heavy Amount of surface treatment agent per 1 m ^{2 of} calcium carbonate [wt% · g / m ² ]

The second aspect of the present invention (claim 2) is to add to the heavy calcium carbonate an energy E [kJ represented by the following formula (17).
/ M ² ], and then fatty acids / alicyclic carboxylic acids / aromatic carboxylic acids, their sulfonic acids, resin acids, aliphatic / alicyclic / aromatic metal salts / amine salts / esters, couplings The present invention relates to a method for producing a surface-treated heavy calcium carbonate, which comprises surface-treating with at least one surface-treating agent selected from agents, silicone oils and paraffin. 10 ≤ E ≤ 1000 (17)

A preferred embodiment of the present invention is characterized in that the time T [sec.] For giving the energy E [kJ / m ² ] to the heavy calcium carbonate is within the range of the following formula (18). The method for producing the surface-treated heavy calcium carbonate according to claim 2. 30 ≤ T ≤ 3600 (18)

In a preferred embodiment, the surface-treated heavy calcium carbonate and the heavy calcium carbonate as a raw material thereof are the BE of the heavy calcium carbonate before the surface treatment.
The ratio of T specific surface area Sw [m ² / g] to Sw1 is expressed by the following formula (1
The method for producing surface-treated heavy calcium carbonate according to claim 1, characterized in that it is within the range of 9). 0.8 ≤ Sw1 / Sw ≤ 1 (19)

A third aspect of the present invention (claim 5) is a resin composition characterized in that the surface-treated heavy calcium carbonate according to claim 1 is mixed with a resin.

A sixth aspect of the present invention is the resin composition according to the fifth aspect, characterized in that the resin is a polyolefin resin.

A seventh aspect of the present invention is a resin composition according to the fifth aspect, characterized in that the resin is a vinyl chloride resin.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION First, the heavy calcium carbonate used as a raw material in the first aspect of the present invention will be described. The average particle diameter D50A (μm) of ground calcium carbonate is
0.1 ≦ D50A ≦ 40 (Equation 1) must be satisfied, 0.35 ≦
D50A ≦ 30 is preferable, and 0.5 ≦ D50A ≦ 20 is more preferable. When the average particle diameter D50A of the ground calcium carbonate exceeds 40 μm, for example, when it is used for a porous film,
The maximum pore size generated in the film after stretching becomes large,
Pore density tends to decrease. On the other hand, the average particle diameter D
If 50 A is less than 0.1 μm, the heavy calcium carbonate particles themselves are likely to be poorly dispersed, resulting in poor formability of the film and uneven stretching, and a uniform porous film cannot be obtained.

In the present invention, the average particle size (D50A) of heavy calcium carbonate is measured by a laser diffraction particle size distribution measuring device (Model Microtrack FR manufactured by Nikkiso Co., Ltd.).
A) was used with water as the solvent.

BET specific surface area Sw of heavy calcium carbonate
(M ² / g) must satisfy 0.2 ≤ Sw ≤ 30 (formula 2), preferably 0.5 ≤ Sw ≤ 20, and more preferably
The range is 1 ≤ Sw ≤ 15. BE of heavy calcium carbonate
When the T specific surface area Sw is less than 0.2 m ² / g, the primary particles of calcium carbonate itself are coarse. Therefore, for example, when used in a porous film, pinholes are generated during stretching of the formed sheet (film), and the desired particles are obtained. I can't get a seat. On the other hand, when the BET specific surface area Sw exceeds 30 m ² / g, the dispersibility of the ground calcium carbonate itself deteriorates, and the handling becomes extremely poor.

In the present invention, B of heavy calcium carbonate
The ET specific surface area Sw was measured using a nitrogen gas with a specific surface area measuring device (NOVA1000 manufactured by Yuasa Ionics).

The L ₁ value of heavy calcium carbonate is 60 ≦ L ₁
It is necessary to satisfy ≦ 99.9 (Equation 3), preferably 65 ≦ L
The range is ₁ ≦ 90, more preferably 70 ≦ L ₁ ≦ 80. The L ₁ value of the heavy calcium carbonate of the present invention shows lightness, and calcium carbonate exceeding 99.9 is not possible according to the studies by the present inventors. Further, when it is less than 60, when blended in a film or the like, the color tone is deteriorated and the commercial value is lowered.

The a ₁ value of heavy calcium carbonate is −3 ≦ a ₁
It is necessary to satisfy ≦ 1 (formula 4), preferably −2.5 ≦ a ₁
≦ 0.5, more preferably −2 ≦ a ₁ ≦ 0. Regarding the a ₁ value of ground calcium carbonate, − indicates green and + indicates red. In particular, if the red color of + exceeds 1, for example, a breathable film of white color cannot be obtained.

The b ₁ value of heavy calcium carbonate is −1.5 ≦ b
_It is necessary to satisfy ₁ ≤ 2.5 (Equation 5), preferably -1 ≤ b
The range is ₁ ≤ 2.2, and more preferably -0.5 ≤ b ₁ ≤ 2. Regarding the b ₁ value of ground calcium carbonate, -is blue and +
Indicates yellow. Especially when the yellow color of + exceeds 2.5, for example, a breathable film of white color cannot be obtained.

With the above constitution, when used as a filler for a porous film, it is possible to obtain beautiful glossy physical properties without discoloration during kneading with a resin and heating. In the present invention, the color difference of the surface-treated heavy calcium carbonate was measured by mixing the heavy calcium carbonate of the present invention and dioctyl phthalate in a ratio of 2: 1 and using Nippon Denshoku Industries Z-1001DP.

Next, the surface-treated heavy calcium carbonate of the present invention will be described. The average particle size (D50 μm) of the surface-treated heavy calcium carbonate needs to satisfy 0.15 ≦ D50 ≦ 30 (formula 6), and 0.40 ≦ D50 ≦ 20 is preferable, and 0.55 ≦
D50 ≦ 15 is more preferable. When the average particle diameter D50 of the surface-treated heavy calcium carbonate exceeds 30 μm, for example, when it is used for a porous film, the maximum pore diameter generated in the stretched film tends to be large and the pore density tends to be low. There is. On the other hand, when the average particle diameter D50 is less than 0.15 μm, the surface-treated heavy calcium carbonate particles themselves are apt to cause poor dispersion, resulting in poor moldability of the film and uneven drawing, so that a homogeneous porous film cannot be obtained. .

In the present invention, the average particle size (D50) of the surface-treated heavy calcium carbonate is measured by using a laser diffraction particle size distribution analyzer (Model Microtrack FRA manufactured by Nikkiso Co., Ltd.) and methanol as a solvent. went.

The BET specific surface area Sw1 (m ² / g) of the surface-treated heavy calcium carbonate must satisfy 0.25 ≦ Sw 1 ≦ 20 (formula 7), preferably 0.55 ≦ Sw 1 ≦ 15, and more preferably Is in the range of 1.05 ≦ Sw 1 ≦ 10. BET specific surface area Sw1 of surface-treated heavy calcium carbonate is 0.25 m ²
If it is less than / g, the treatment agent may be coated on the surface of calcium carbonate. For example, when it is used for a porous film, pinholes are generated when the formed sheet (film) is stretched, and thus the desired treatment is desired. I can't get a seat. On the other hand, when the BET specific surface area Sw1 exceeds 20 m ² / g, dispersibility due to aggregation of fine particles deteriorates and handling becomes extremely poor.

In the present invention, the BET specific surface area Sw1 of the surface-treated heavy calcium carbonate was measured by using a specific surface area measuring device (NOVA1000 manufactured by Yuasa Ionics) using nitrogen gas.

PH value of surface-treated heavy calcium carbonate α
Must satisfy the formula 8 ≤ α ≤ 10 (8), preferably in the range of 8.2 ≤ α ≤ 9.7, and more preferably in the range of 8.5 ≤ α ≤ 9.5. If the pH of the surface-treated heavy calcium carbonate exceeds 10, it has a strong basic compound and, for example, when it comes into contact with the human body in the porous film used for paper diapers,
It is not preferable because it irritates the skin. On the other hand, when the pH is less than 8, the surface treating agent is released and the resin is colored to reduce the commercial value.

In the present invention, the pH of the suspension of surface-treated heavy calcium carbonate was measured by shaking 50 g of ion-exchanged water with 5 g of the surface-treated heavy calcium carbonate of the present invention, and leaving still for 20 minutes. Then, it measured using Yokogawa Electric Co., Ltd. model PH81-11-J.

The electric conductivity Sc (μS / cm) of the surface-treated heavy calcium carbonate must satisfy 5 ≦ Sc ≦ 300 (formula 9), preferably 10 ≦ Sc ≦ 250, and more preferably 15 ≦. The range is Sc ≦ 200. If the electric conductivity of the surface-treated heavy calcium carbonate suspension exceeds 300 μs / cm, not only the dispersibility of the particles will be poor, but also the alkalinity of the calcium carbonate surface will increase and agglomerates will form, resulting in dispersibility. Is reduced. On the other hand, when it is less than 5 μS / cm, the surface treatment agent is coated on the surface of the calcium carbonate particles,
The treatment agent for the excessive treatment is released, which causes a decrease in dispersibility in the resin.

In the present invention, the electrical conductivity of the suspension of heavy calcium carbonate was measured by adding 47.3 g of ion-exchanged water to 2.7 g of the surface-treated heavy calcium carbonate of the present invention, and then shaking by Yokogawa ( This was performed using an electric conductivity meter model SC-82 manufactured by Co., Ltd.

The L ₂ value of the surface-treated heavy calcium carbonate is
It is necessary to satisfy 60.5 ≦ L ₂ ≦ 99.5 (formula 10), preferably 67.5 ≦ L ₂ ≦ 85.5, more preferably 70.5 ≦ L ₂ ≦
The range is 79.5. The L ₂ value of the surface-treated heavy calcium carbonate shows lightness, and the surface-treated calcium carbonate exceeding 99.5 could not be obtained according to the study by the present inventors. Also, 60.5
When it is less than the above range, the color tone is deteriorated when blended in a film or the like, the commercial value is deteriorated, and the product cannot be used.

The a ₂ value of the surface-treated heavy calcium carbonate is
It is necessary to satisfy -2.9 ≤ a ₂ ≤ 0.9 (formula 11), preferably -2.4 ≤ a ₂ ≤ 0.4, and more preferably -1.9 ≤ a ₂ ≤-.
It is in the range of 0.1. Surface-treated heavy calcium carbonate a ₂
As for the value, − indicates green and + indicates red. Especially + red color
When it exceeds 0.9, for example, a breathable film having a white color cannot be obtained. In addition, those having a value less than -2.9 were not obtained according to the study by the present inventors.

The b ₂ value of the surface-treated heavy calcium carbonate is
It is necessary to satisfy -1.4≤b ₂ ≤2.4 (formula 12), preferably -0.9≤b ₂ ≤2.1, and more preferably -0.4≤b ₂ ≤1.
It is in the range of 9. Regarding the b ₂ value of the surface-treated heavy calcium carbonate, − indicates blue and + indicates yellow. Especially + yellow is 2.
If it exceeds 4, for example, a breathable film of white color cannot be obtained. Further, those of less than -1.4 were not obtained according to the study of the present inventors.

With the above-mentioned constitution, when used as a filler for a porous film, it is possible to obtain beautiful glossy physical properties without discoloration during kneading with a resin and heating. In the present invention, the color difference of the surface-treated heavy calcium carbonate is obtained by mixing the surface-treated heavy calcium carbonate of the present invention and dioctyl phthalate at a ratio of 2: 1 and manufactured by Nippon Denshoku Industries Z-
It was measured using 1001 DP.

The surface treatment agent used in the present invention is a fatty acid
Alicyclic carboxylic acids / aromatic carboxylic acids, aliphatic / alicyclic / aromatic sulfonic acids, resin acids, their metal salts / amine salts / esters, coupling agents, silicone oils,
It is at least one selected from paraffin. Examples of the fatty acid, alicyclic carboxylic acid, aromatic carboxylic acid, and resin acid used in the present invention include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Saturated fatty acids, unsaturated fatty acids such as sorbic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid, alicyclic carboxylic acids such as naphthenic acid having a cyclopentane ring or cyclohexane ring, naphthoic acid, naphthalic acid, etc. Aromatic carboxylic acids such as carboxylic acids of naphthalene, abietic acid, pimaric acid, levopimaric acid, neoabietic acid, parastophosphoric acid, dehydroapietic acid, isopimaric acid, sandaracopimaric acid, commic acid, secodehydroabietic acid, dihydro Resin acids such as abietic acid may be mentioned, among which the surface-treated heavy acid of the present invention is used. The use of palmitic acid or stearic acid is preferable from the viewpoint of imparting the dispersion effect of calcium carbonate.

Examples of the metal salt / amine salt of fatty acid / alicyclic carboxylic acid / aromatic carboxylic acid / resin acid include potassium laurate, potassium myristate, potassium palmitate, barium stearate / calcium / aluminum / zinc.・ Saturated fatty acid salts such as magnesium, unsaturated fatty acid salts such as potassium oleate / sodium / potassium diethanolamine salts, alicyclic carboxylates such as lead naphthenate and lead cyclohexylbutyrate, aromatics such as sodium benzoate and sodium salicylate Examples include carboxylic acid salts. Further, during or before the surface treatment of the present invention, the above fatty acid, alicyclic carboxylic acid, aromatic carboxylic acid, resin acid, lithium, sodium, potassium, rubidium.
Beryllium / magnesium / calcium / strontium / barium / zinc / aluminum / lead / cobalt / Metal compounds of amines, amino acids, alicyclic carboxylic acids, aromatic carboxylic acids, resin acids May be created as appropriate. Among the above metal salts of fatty acids, alicyclic carboxylic acids, aromatic carboxylic acids, and resin acids,
It is preferable to use calcium stearate from the viewpoint of imparting a dispersing effect to the surface-treated heavy calcium carbonate of the present invention.

Examples of the fatty acid / alicyclic carboxylic acid / aromatic carboxylic acid / resin acid ester include, for example, ethyl vinyl caproate, diisopropyl adipate, ethyl caprylate, allyl ethyl vinyl caprate, diethyl sebacate. Diisopropyl, cetyl isooctanoate, octyldodecyl dimethyloctanoate, methyl butyl lauryl laurate, methyl myristate isopropyl cetyl myristyl isocetyl octyldodecyl isotridecyl, methyl palmitate isopropyl octyl cetyl isostearyl Saturated fatty acid ester such as methyl stearate, butyl octyl stearyl cholesteryl, isocetyl isostearate, methyl behenate behenyl, etc., methyl oleate, ethyl linoleate -Unsaturated fatty acid ester such as isopropyl and methyl erucate, long-chain fatty acid higher alcohol ester, neopentyl polyol (including long-chain / medium-chain) fatty acid ester and partial ester compound, dipentaerythritol long-chain fatty acid ester, Complex medium chain fatty acid ester, 12- stearoyl stearate Isocetyl / isostearyl / stearyl, beef tallow fatty acid octyl ester, heat resistant special fatty acid ester such as fatty acid ester of polyhydric alcohol fatty acid ester / alkyl glyceryl ether, benzoic acid ester Among them, there are aromatic esters. Among them, polyhydric alcohol fatty acid stearate polyhydric alcohol stearate polyhydric alcohol stearin from the viewpoint of imparting a dispersing effect to the surface-treated heavy calcium carbonate of the present invention. Or use of palmitic acid.

Examples of the aliphatic / alicyclic / aromatic sulfonic acid include sulfonic acids such as sulfosuccinic acid, dioctyl sulfosuccinic acid, tetradecene sulfonic acid, lauryl, myristyl palmitin, stearin, olein, cetyl and the like. Alkyl sulfuric acid consisting of alkyl groups, polyoxyethylene
(2) Lauryl ether sulfuric acid / polyoxyethylene (3) Lauryl ether sulfuric acid / polyoxyethylene (4) Lauryl ether sulfuric acid / polyoxyethylene (3) Alkyl ether sulfuric acid / polyoxyethylene (4) Nonylphenyl ether nitric acid, straight chain (C ₁₀ , C ₁₂ , C ₁₄ ) Aromatic sulfonic acids such as alkylbenzene sulfonic acid, branched alkylbenzene sulfonic acid, naphthalene sulfonic acid, dodecyl benzene sulfonic acid, etc., and the like, among which dispersed in the surface-treated heavy calcium carbonate of the present invention. Use of dodecylbenzene sulfonic acid is preferable from the viewpoint of imparting the effect.

As an example of the metal salt / amine salt of aliphatic / alicyclic / aromatic sulfonic acid, the above-mentioned sodium salt / amine salt of aliphatic / alicyclic / aromatic sulfonic acid is generally used. However, during or before the surface treatment of the calcium carbonate of the present invention, lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, strontium, barium.
Compounds having zinc, aluminum, lead, cobalt, and amino groups may be mixed and reacted to appropriately form a metal salt or amine salt of an aliphatic, alicyclic, or aromatic sulfonic acid. Above all, it is preferable to use sodium dodecylbenzene sulfonate from the viewpoint of imparting a dispersing effect to the surface-treated heavy calcium carbonate of the present invention.

Examples of coupling agents, silicone oils, and paraffins include silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane, titanium coupling agents such as isopropyltriisostearoyl titanate, and silicones such as fatty acid ester-modified silicone oil. Examples include paraffins such as oil, liquid paraffin, synthetic paraffin, and natural paraffin.

Surface treatment of heavy calcium carbonate at 250 ° C., 1
Difference in heat resistance test for 5 minutes (before heat resistance test-after heat resistance test) ΔL
The value must satisfy 0 ≦ ΔL ≦ 2 (formula 13), preferably 0 ≦ ΔL ≦ 1.5, and more preferably 0 ≦ ΔL
The range is ≤1. ΔL indicates the effect of thermal conditions, ΔL
When the value exceeds 2, the liberated substances of the treating agent are burned and cause discoloration of the resin or the like. For example, when used for a breathable film, the appearance is impaired and it is difficult to use. Further, the closer the ΔL is to 0, the more the surface treatment agent is chemically bonded to calcium carbonate, and, for example, good physical properties can be obtained even when used in a breathable film. It should be noted that, according to the study by the present inventors, ΔL cannot be negative.

Surface treatment of ground calcium carbonate at 250 ° C., 1
Δ of difference in heat resistance test for 5 minutes (after heat resistance test-before heat resistance test)
The value a must satisfy 0 ≦ Δa ≦ 1 (equation 14),
Preferably, 0 ≤ Δa ≤ 0.7, more preferably 0 ≤ Δ
It is in the range of a ≦ 0.4.

Δa indicates the effect of thermal conditions, and the Δa value is 1
When it exceeds the range, when it is used for a product, for example, when it is used for a breathable film, the appearance is damaged and it is difficult to use.
Further, the closer it is to 0, the more the surface treatment agent is chemically bound to calcium carbonate, and good physical properties can be obtained even when it is used for a breathable film, for example. It should be noted that, according to the study by the present inventors, Δa cannot be negative.

The surface-treated heavy calcium carbonate of the present invention is 25
Difference in heat resistance test at 0 ° C for 15 minutes (after burning-before burning) Δb
The value must satisfy 0 ≦ Δb ≦ 2 (formula 15), preferably 0 ≦ Δb ≦ 1.5, more preferably 0 ≦ Δb ≦
It is in the range of 1.

Δb indicates the effect of thermal conditions, and the Δb value is 2
When it exceeds the range, when it is used for a product, for example, when it is used for a breathable film, the appearance is damaged and it is difficult to use. Further, the closer Δb is to 0, the more the surface treatment agent is chemically bound to calcium carbonate, and therefore, good physical properties can be obtained even when used for a breathable film, for example. According to the study by the present inventors, it is impossible that Δb becomes negative.

With the above-mentioned constitution, when used as a filler for a porous film, it is possible to obtain beautiful glossy physical properties without discoloration during kneading with a resin and heating. In the present invention, the surface-treated heavy calcium carbonate is burned by using a MASCDA: tabletop muckle furnace: model NMF-25, and the surface-treated heavy carbonate is applied to substantially the entire surface of the heat-resistant plate (a stainless steel circular plate with a diameter of 120 mm). Spread 10g of calcium evenly,
After burning at 250 ° C for 15 minutes, color difference measurement is performed. The difference in ΔL value is before burning-after burning, and the difference between Δa value and Δb value is after burning-before burning. These values were measured by mixing surface-treated heavy calcium carbonate after combustion and dioctyl phthalate at a ratio of 2: 1 and using Z-1001DP manufactured by Nippon Denshoku Kogyo.

Amount of surface treatment agent W / Sw (weight% · g /
m ² ) needs to be 0.050 ≤ W / Sw ≤ 0.700 (formula 16), preferably 0.100 ≤ W / Sw ≤ 0.500, and more preferably 0.170 ≤ W / Sw ≤ 0.200. If the amount of surface treatment exceeds 0.700% by weight / g / m ² , the amount of treatment agent will be excessive. For example, when used for porous film, discoloration and smoke will occur due to the influence of excessive treatment during stretching, while the amount of surface treatment will be 0.050 weight. If it is less than% · g / m ² , the effect is not sufficiently exhibited. Further, when the surface treating agent is used, it is preferable that the surface treating agent is melted and used in a liquid state because not only the calcium carbonate surface can be uniformly coated but also the fluidity is improved.

The method for producing the surface-treated heavy calcium carbonate of the present invention, which is the second aspect of the present invention, will be described. The present invention provides a specific amount of energy per unit area of heavy calcium carbonate particles before adding a surface treatment agent to the heavy calcium carbonate having a specific average particle diameter and BET specific surface area, and It is characterized by activating the surface of the particles to promote chemical bonding with the surface treating agent. There is no limitation on the method of giving a specific amount of energy per unit surface area of heavy calcium carbonate particles, for example, a method of directly spraying water vapor to calcium carbonate or a method of adding a surface treatment agent while spraying steam, There is a method in which water is added or sprayed directly to a mixer charged with calcium carbonate, and the mixture is mixed and stirred under the temperature condition of 90 to 110 ° C. In terms of uniformity of activation of the particle surface, A method of directly blowing steam onto the ground calcium carbonate is preferred.

The surface treatment which is carried out after applying a specific amount of energy to the unit surface area of the heavy calcium carbonate particles for a specific time can be carried out by a usual method using a Henschel mixer or the like.

The amount of energy applied per unit area of the heavy calcium carbonate particles is preferably 10 ≦ E ≦ 1000 (formula 17), more preferably 15 ≦ E ≦ 700, and further preferably 20.
The range is ≤E≤400. Energy given per unit surface of heavy calcium carbonate particles is 1000 (kJ / m ² )
When it exceeds, the surface of the heavy calcium carbonate particles is excessively activated, the heavy calcium carbonate particles agglomerate, and a part of them becomes quick lime. Thus, the surface-treated heavy calcium carbonate aimed at by the present invention can be obtained. Can not. On the other hand, when the energy is less than 10 (kJ / m ² ), the surface of calcium carbonate cannot be sufficiently activated, and it is meaningless to simply adsorb water on the surface of calcium carbonate.

The time T (second) for applying a specific amount of energy to the heavy calcium carbonate particles is preferably 30 ≦ t ≦ 3600 (formula 18), more preferably 45 ≦ t ≦ 1800, and further preferably 60 ≦ t ≦. It is in the range of 600. When the time T for giving energy to the surface of the heavy calcium carbonate exceeds 3600 seconds, the surface of the heavy calcium carbonate particles is overactivated, the heavy calcium carbonate particles agglomerate, and a part thereof becomes quick lime. The target surface-treated heavy calcium carbonate cannot be obtained. On the other hand, when the time T (second) is less than 30 seconds, the surface of calcium carbonate cannot be sufficiently activated, and it is meaningless to simply adsorb water on the surface of calcium carbonate.

The BET specific surface area ratio Sw 1 / Sw produced by applying a specific amount of energy to the heavy calcium carbonate particles within a specific time and performing surface treatment is 0.8 ≦ Sw.
1 / Sw ≦ 1 (formula 19) is preferable, and 0.85 ≦ is more preferable.
Sw1 / Sw ≦ 0.98, more preferably 0.90 ≦ Sw1 / S
The range is w ≦ 0.95. If the amount of change in the BET specific surface area before and after the surface treatment, Sw1 / Sw, is less than 0.8, the surface of the heavy calcium carbonate particles is overactivated, causing aggregation of the heavy calcium carbonate particles, and part of them becomes quick lime. The surface-treated heavy calcium carbonate targeted by the invention cannot be obtained. It should be noted that the change amount Sw1 / Sw exceeds 1 is not possible according to the study by the present inventors. After the surface treatment, crushing is carried out by a conventional method to obtain the surface-treated heavy calcium carbonate of the present invention.

The resin composition containing the surface-treated heavy calcium carbonate of the present invention, which is the third aspect of the present invention, will be described. The resin to which the surface-treated heavy calcium carbonate of the present invention is added is not particularly limited, and examples thereof include phenol-based resins used for plastics, urea-based resins, melamine-based resins, polyimide-based thermosetting resins, vinyl chloride-based resins, and acetic acid. Examples include thermoplastic resins such as vinyl-based, polyester-based, styrene-based, vinylidene chloride-based polyethylene-based, polypropylene-based, ABS-based, polyamide-based, polyacetal-based, polycarbonate-based, polyethylene terephthalate-based, fluorine-based, etc., which may be used alone or Used in combination of two or more.

For example, a porous film made of a linear low-density polyethylene resin composition containing the surface-treated heavy calcium carbonate of the present invention is prepared, for example, by first adding the resin and the surface-treated heavy calcium carbonate of the present invention in a small amount. The solvent is melt-kneaded using a twin-screw extruder or various mixers with excellent kneading ability under a temperature condition of about 200 ° C to obtain compound pellets, and the pellets are further heated at about 240 ° C using an extruder. It can be obtained by kneading, melting and extruding under temperature conditions to prepare a film by a T-die method or an inflation method, and stretching the film in a uniaxial direction and a biaxial direction. By the above method, voids communicating with the front and back of the film are generated, and the film has excellent air permeability.

The blending amount of the surface-treated heavy calcium carbonate of the present invention into the resin varies depending on the type and application of the resin.
It is preferable to mix the resin within the range of 70 to 30% by weight with respect to the resin of 30 to 70% by weight. When the amount of the surface-treated heavy calcium carbonate of the present invention is less than 30% by weight, the voids adjacent to each other due to the interfacial peeling between the linear low-density polyethylene resin and the surface-treated heavy calcium carbonate of the present invention do not communicate with each other, which is good. A porous film having excellent air permeability and moisture permeability cannot be obtained. Further, the amount of the surface-treated heavy calcium carbonate of the present invention is 70
If the content exceeds 10% by weight, the stretch ratio during film formation will decrease,
It is not preferable because molding defects such as stretch breakage occur. Incidentally, the linear low-density polyethylene film of the present invention, various fatty acids, fatty acid amides, ethylenebisstearic acid amide, if necessary, within a range that does not impair the efficacy of the present invention.
A lubricant such as sorbitan fatty acid ester and a stretching aid, a stabilizer such as a plasticizer, and an antioxidant may be added.

Further, the vinyl chloride resin composition containing the surface-treated heavy calcium carbonate of the present invention may be prepared, for example, by mixing the resin, the surface-treated heavy calcium carbonate of the present invention and the colloidal calcium carbonate with a super mixer or a ribbon blender. After mixing with a kneading machine, it is obtained by kneading with a single-screw or twin-screw extruder such as a Banbury mixer, a mixing roll, etc., granulating and molding, and further performing steps such as extrusion molding, injection molding and blow molding. After that, it is commercialized. The vinyl chloride resin composition obtained by using the surface-treated heavy calcium carbonate of the present invention is uniformly dispersed without agglomeration at the time of kneading with a resin, has excellent extrusion moldability, and has excellent extrusion moldability. The impact strength is also good.

The blending amount of the surface-treated heavy calcium carbonate of the present invention in the vinyl chloride resin varies depending on the type and application of the resin, but is 0.3-18% by weight based on the resin composition obtained.
It is preferable to mix within the range. If the content of the surface-treated heavy calcium carbonate of the present invention is less than 0.3% by weight with respect to the vinyl chloride resin composition, a sufficient impact resistance improving effect cannot be obtained, and if it exceeds 18% by weight, the impact resistance is not improved. Is reduced. Incidentally, the vinyl chloride resin composition of the present invention, as long as the effect of the present invention is not impaired, if necessary, additives generally used in the vinyl chloride resin composition, for example, a heat stabilizer,
Antioxidant, colorant, UV absorber, flame retardant, deodorant,
You may mix | blend a bactericidal agent, a light stabilizer, a neutralizer, a lubricant, an anti-clouding agent, an antiblocking agent, an antistatic agent, a slip agent, etc.

[0065]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these.

The surface treatment agents used in the following Examples and Comparative Examples are shown below. Stearic acid (Product name: TST: Miyoshi Oil & Fat Co., Ltd.) Palmitic acid (Product name: Palmitic acid 98: Miyoshi Oil & Fat Co., Ltd.) Oleic acid (Product name: NAA-34: Miyoshi Oil & Fat Co., Ltd.) Fatty acid ester (Product) Name: T-3050: Toei Chemical Co., Ltd. Lauric acid (Product name: Lauric acid 98: Miyoshi Yushi Co., Ltd.) Disproportionated rosin soap (Product name: Bandis T-25K: Harima Kasei Co., Ltd. Leveled rosin potassium soap Decylbenzene sulfonic acid (trade name: Teika Power L12)
0: Teika Co., Ltd.

Examples 1 to 11 and 17 Comparative Examples 1 to 5 100 kg of heavy calcium carbonate having a BET specific surface area Sw shown in Table 1 was repeated by crushing and classifying white sugar-crystallized limestone.
Then, steam corresponding to the energy E amount is applied for T seconds, charged into a Henschel mixer, and then heated and mixed with the surface treatment agent Z under the temperature condition of 120 ° C. for 15 to 20 minutes, and crushed by a coloplex to obtain a surface treatment weight. Quality calcium carbonate was obtained. However, in Comparative Example 4, 120 ° C. was changed to 130 ° C. Table 1 shows the BET specific surface area of the heavy calcium carbonate after application of energy, the change rate of physical properties before and after the energy application, the preparation conditions of the surface-treated heavy calcium carbonate, and various physical properties of the obtained surface-treated heavy calcium carbonate.

Examples 13 to 14 100 kg of heavy calcium carbonate having a BET specific surface area Sw shown in Table 1 was repeated by repeatedly crushing and classifying white sugar crystalline limestone.
To the Henschel mixer, the mixture is heated and mixed with the surface treatment agent Z for 17 minutes under the temperature condition of 120 ° C., and the mixture is crushed with a coloplex to obtain the surface treated heavy carbonic acid. I got calcium. Table 1 shows the BET specific surface area of the heavy calcium carbonate after application of energy, the change rate of physical properties before and after the energy application, the preparation conditions of the surface-treated heavy calcium carbonate, and various physical properties of the obtained surface-treated heavy calcium carbonate.

Example 15 100 kg of heavy calcium carbonate having a BET specific surface area Sw shown in Table 1 was prepared by repeating crushing and classification of white sugar-crystalline limestone.
To the Henschel mixer, the mixture is heated and mixed with the surface treatment agent Z for 17 minutes under the temperature condition of 120 ° C., and the mixture is crushed with a coloplex to obtain the surface treated heavy carbonic acid. I got calcium. Table 1 shows the BET specific surface area of heavy calcium carbonate after application of energy and its rate of change, the preparation conditions of the surface-treated heavy calcium carbonate and various physical properties of the obtained surface-treated heavy calcium carbonate.

Example 16 As a method of adding the surface treatment agent, the same operation as in Example 1 was carried out, and steam corresponding to the amount of energy E was ⅔ for T seconds.
When the temperature reached, the surface-treated heavy calcium carbonate was obtained.

Comparative Example 6 A surface-treated heavy calcium carbonate was obtained in the same manner as in Example 1 except that energy was not applied. Table 1 shows various physical properties of the obtained surface-treated heavy calcium carbonate.

[0072]

[Table 1]

[0073]

[Table 1] Continued 1

Examples 18 to 34, Comparative Examples 7 to 12 Using the surface-treated heavy calcium carbonates obtained in Examples 1 to 17 and Comparative Examples 1 to 6, a porous film was prepared according to the following ingredients and preparation method. The resulting porous film was evaluated for moisture permeability, air permeability, film thickness and uniformity, rigidity, tensile strength and stretching cut rotation speed by the following methods. The evaluation results are shown in Table 2.

(Ingredient) Linear low-density polyethylene 38% by weight (Mitsui Petrochemical Industry Co., Ltd., trade name: Ultzex 2021L Density: 0.920 g / cm ³ , MI: 2.1 g / 10 min.) Solvent Castor oil ( Ito Oil Co., Ltd. Product name: Rhombus Special A) 3% by weight Surface-treated heavy calcium carbonate Examples 1-14 Comparative examples 1-6 59% by weight

(Preparation Method) After mixing the above components with a tampler mixer, kneading was performed at 200 ° C. using a tandem type extruder to obtain pellets, and the pellets were used with an extruder equipped with a T-die to give 240 Melted and kneaded under the conditions of ℃, extruded, and after film formation at a take-up speed of 100 m / min.
The film was uniaxially stretched in the machine direction at a draw ratio of 2 times between the preheating roll and the stretching roll heated to the above to obtain a porous film.

(Test and Evaluation Method) 1. MI value (melt index (g / 10min.) Temperature 190 ℃, load according to ASTM D-1238-57T (E)
Measured under the condition of 2160g. 2. Moisture vapor transmission rate (g / m ² · 24hr) Measured at a temperature of 40 ° C and a relative humidity of 60% according to the regulations of ASTM-E96 (water method). The test time was 24 hours. 3. Air permeability (sec./100 ml) Measured according to JIS P-8117.

4. Number of stretch breaks (times / hr) The porous film was continuously produced for 8 hours, the number of stretch breaks of the film was counted, and the value converted into the number of rotations per hour was defined as the number of stretch breaks.

5. Film thickness (μm) Uniform film thickness Sample from porous film [longitudinal direction (hereinafter referred to as MD): 110 cm, transverse direction (hereinafter referred to as TD)
: 5 cm] are sampled, and a total of 300 measuring points are set on the MD at 1 cm intervals. Thickness is measured using a thickness meter (PEACOCK, model: UPRIGHTDIAL GUAGE NO.25), average thickness X, maximum thickness MAX, and minimum thickness MIN are calculated, and the obtained average thickness X is rounded off to the nearest whole number. The film thickness, and calculate [(MAX-MIN)] / X,
Let it be the uniformity of the film thickness. 6. Rigidity (mm) Measured according to the method (canterever method) specified in JIS L-1096. 7. Tensile strength (kg / 25mm) In accordance with JIS P-8113, a 25mm x 100mm test piece was subjected to a tensile test at a measuring temperature of 23 ° C and a pulling speed of 200m / min. Measure each.

8. Appearance of Film By visually observing the obtained film, the unevenness of stretching of the film was judged in four stages according to the following criteria. A: Almost no stretching unevenness is recognized. B: Some stretching unevenness is recognized. C: Uneven stretching is considerably observed. D: Uneven stretching is noticeable. 9. Comprehensive Evaluation From the above test contents, the comprehensive evaluation as a porous ethylene film was judged in the following four criteria. A: Very good. B: Good. C: Some deterioration of physical properties is recognized, but it does not affect practically. D: Physical properties are deteriorated, which is a problem in practical use.

[0081]

[Table 2]

[0082]

[Table 2] Continued 1

Examples 35 to 51, Comparative Examples 13 to 18 Using the surface-treated heavy calcium carbonates obtained in Examples 1 to 17 and Comparative Examples 1 to 6, a vinyl chloride resin was prepared according to the following compounding ingredients and preparation methods. Was prepared, and the strength of the obtained vinyl chloride resin was measured and evaluated. The evaluation results are shown in Table 3.

[0084] (Ingredients)   Vinyl chloride resin (average degree of polymerization 1030) 84.4% by weight   Dibasic lead phosphite 3.0% by weight   Dibasic lead stearate 1.3% by weight   Lead stearate 0.8% by weight   Calcium stearate 0.4% by weight   Fatty acid lubricant (trade name: Roxyol VPG1781, manufactured by Henkel Hakusui Co., Ltd.)                                                           0.8% by weight   Acrylic processing aid (trade name: METABLEN P55, manufactured by Mitsubishi Rayon Co., Ltd.)                                                           0.8% by weight   Acrylic impact modifier (trade name: METABLEN S2001, manufactured by Mitsubishi Rayon Co., Ltd.)                                                           4.2% by weight   Surface treated colloidal calcium carbonate (average particle size 0.04μm stearic acid treated product)   Surface-treated heavy calcium carbonate Examples 1-17 Comparative Examples 1-6 4.2% by weight

(Preparation Method) The above components were put into a Henschel mixer and mixed by high speed stirring to prepare a vinyl chloride resin composition.

(Test and Evaluation Method) From the obtained vinyl chloride resin composition, test pieces A and B were prepared according to the following method.
Were prepared, and each was subjected to a Charpy impact test (Kgf · cm / cm ² ) according to JIS K-711 and evaluated. The evaluation results are shown in Table 3. Preparation of test piece A: The obtained vinyl chloride resin composition was kneaded with a roll having a diameter of 9 inches at 170 ° C. for 6 minutes, and then 195
Press molding was performed at 5 ° C. for 5 minutes to obtain a 3 mm thick sheet, and a test piece A was prepared from this sheet. Preparation of test piece B: The obtained vinyl chloride resin composition was supplied to a single-screw extruder (full flight screw having a diameter of 40 mm), and C1: 150 ° C, C2: 170 ° C, C3: 190 ° C, D:
A 3 mm thick sheet was prepared under a temperature condition of 195 ° C., and a test piece B was prepared from this sheet.

Comprehensive Evaluation From the above test contents, a comprehensive evaluation as a vinyl chloride resin composition was judged according to the following criteria in four stages. A: Very good. B: Good. C: Some deterioration of physical properties is observed, but it does not affect practically. D: The physical properties are deteriorated and there is a practical problem.

[0088]

[Table 3]

[0089]

[Table 3] Continued 1

[0090]

As described above, the surface-treated heavy calcium carbonate of the present invention has improved dispersibility in a resin and improved affinity for the resin, and has excellent physical properties in a porous film and impact resistance. It is possible to provide an excellent resin composition. The surface-treated heavy calcium carbonate of the present invention can be obtained by increasing the reactivity between the surface of particles of heavy calcium carbonate and the surface-treating agent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09C 1/02 C09C 1/02 3/10 3/10 3/12 3/12 (72) Inventor Kiyomizu Shimizu F-Term, 1455, Nishioka, Uozumi-cho, Akashi-shi, Hyogo F-Term within Maruo Calcium Co., Ltd. (reference) CB10 CB21 CB23 CB26 CC03 CC28 DD05 DD07 DD13 DD27 EE02 EE28 FF03 FF15

Claims (7)

[Claims] 1. A heavy calcium carbonate satisfying the following formulas (1) to (5), a fatty acid / alicyclic carboxylic acid / aromatic carboxylic acid, an aliphatic / alicyclic / aromatic sulfonic acid, and a resin acid. A surface treatment with at least one surface treatment agent selected from metal salts / amine salts / esters thereof, coupling agents, silicone oils, and paraffin, wherein the surface-treated heavy calcium carbonate is represented by the following formula (6): Surface-treated heavy calcium carbonate characterized by satisfying (16). 0.1 ≤ D50 A ≤ 40 (1) 0.2 ≤ Sw ≤ 30 (2) 60 ≤ L ₁ ≤ 99.9 (3) -3 ≤ a ₁ ≤ 1 (4) -1.5 ≤ b ₁ ≤ 2.5 (5) 0.15 ≤ D50 ≤ 30 (6) 0.25 ≤ Sw1 ≤ 20 (7) 8 ≤ α ≤ 10 (8) 5 ≤ Sc ≤ 300 (9) 60.5 ≤ L ₂ ≤ 99.5 (10) -2.9 ≤ a ₂ ≤ 0.9 (11) -1.4 ≤ b ₂ ≤ 2.4 (12) 0 ≤ ΔL ≤ 2 (13) 0 ≤ Δa ≤ 1 (14) 0 ≤ Δb ≤ 2 (15) 0.050 ≤ W / Sw ≤ 0.700 (16) However, D50A: Microtrack FRA laser type particle size 50% average particle size [μm] Sw of heavy calcium carbonate measured with a distribution meter: BET specific surface area [m ² / of heavy calcium carbonate]
g] L ₁ : L value of heavy calcium carbonate obtained by color difference meter [-] a ₁ : a value of heavy calcium carbonate obtained by color difference meter [-] b ₁ : heavy calcium carbonate obtained by color difference meter B value of [-] D50: 50% average particle size of surface-treated heavy calcium carbonate measured by Microtrac FRA laser particle size distribution meter
[μm] Sw 1: BET specific surface area of surface-treated heavy calcium carbonate
[m ² / g] α: pH of surface-treated surface-treated heavy calcium carbonate
[−] Sc: Electric conductivity of surface-treated heavy calcium carbonate [μS
/ Cm] L _2: the surface treatment heavy calcium carbonate obtained by the color difference meter L
Value [-] a _2: a surface treatment heavy calcium carbonate obtained by the color difference meter
Value [−] b ₂ : b of surface-treated heavy calcium carbonate obtained by color difference meter
Value [−] ΔL: L value difference of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes [−] Δa: a value of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes Difference [−] Δb: b value difference of surface-treated heavy calcium carbonate before and after heat resistance test at 250 ° C. for 15 minutes [−] W: amount of surface treatment agent to heavy calcium carbonate [% by weight] W / Sw: heavy Amount of surface treatment agent per 1 m ^{2 of} calcium carbonate [wt% · g / m ² ] 2. The energy E [kJ / m ² ] represented by the following formula (17) per unit area of the heavy calcium carbonate particles.
Then, fatty acid / alicyclic carboxylic acid / aromatic carboxylic acid, aliphatic / alicyclic / aromatic sulfonic acid, resin acid, metal salt / amine salt / ester thereof, coupling agent, silicone oil A method for producing surface-treated heavy calcium carbonate, which comprises surface-treating with at least one surface-treating agent selected from paraffin. 10 ≤ E ≤ 1000 (17) 3. The energy E [k] of heavy calcium carbonate
The time T [sec.] For giving J / m ² ] is within the range of the following formula (18), and the method for producing surface-treated heavy calcium carbonate according to claim 2. 30 ≤ T ≤ 3600 (18) 4. The BET specific surface area S of heavy calcium carbonate
A method for producing surface-treated heavy calcium carbonate, characterized in that the ratio of w [m ² / g] to the BET specific surface area Sw1 of the surface-treated heavy calcium carbonate is within the range of the following formula (19). 0.8 ≦ Sw1 / Sw ≦ 1 (19) 5. A resin composition comprising the surface-treated heavy calcium carbonate according to claim 1 blended with a resin. 6. The resin composition according to claim 5, wherein the resin is a polyolefin resin. 7. The resin composition according to claim 5, wherein the resin is a vinyl chloride resin.