JP2003342553A - Additive for preventing slip, filler containing the same and resin composition formulating those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for prevention of slip capable of providing a composition excellent in slip resistance, particularly when compounded with acrylic plastisol and providing a composition having a viscous property, a thixotropic property and superior slip resistance when combinedly used with precipitated calcium carbonate surface-treated with an organic surface treating agent. <P>SOLUTION: The additive for preventing slip comprises particles in which at least the surface is composed of a calcium phosphate compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an anti-slip additive, a filler containing the anti-slip additive,
And a resin composition containing them. More specifically, for example, when it is used in a thermoplastic resin represented by plastisol for automobiles, the viscosity /
Without impairing the thixotropy / slump resistance imparting effect,
Further, the present invention relates to an anti-slip additive capable of imparting particularly excellent slip resistance, a filler containing the same, and a resin composition containing them.

[0002]

2. Description of the Related Art Plastisol is a coating film in which thermoplastic polymer particles having an adjusted particle size and particle size distribution are dispersed in a plasticizer together with a filler, and which has excellent processability, toughness and durability. It has been used in various industrial fields by taking advantage of its physical properties.

Particularly as a thermoplastic polymer particle for an automobile body, it has excellent rust prevention properties, and fills a gap in a joint well,
Further, a polyvinyl chloride-based material represented by a vinyl chloride polymer or a copolymer of vinyl chloride and vinyl acetate is often used because a relatively thick coating film can be formed.

In recent years, due to environmental problems, an acrylic plastisol in which acrylic polymer particles are dispersed in a plasticizer together with a filler has been developed in place of the polyvinyl chloride plastisol. Acrylic plastisols have been studied as an alternative material because they have the same morphology, workability, and processability as polyvinyl chloride compositions, and have coating strength and durability comparable to that of polyvinyl chloride plastisols. A film was obtained.

However, the acrylic polymer particles used in the acrylic plastisols have a weaker intermolecular force acting between the molecules than the vinyl chloride polymer particles, so that the plasticizer is easily incorporated between the molecules and is incorporated. The plasticizer thus produced bleeds out over time, and as a result, the plasticizer that bleeds out easily causes a slip during heating film formation. Therefore, there is a demand for an additive capable of solving this slip property, a filler having a good workability while having slip resistance, and a resin composition capable of solving them, but it is still in a satisfactory state. It is difficult to say that it is in Japan.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention has a particularly excellent effect of imparting viscosity and thixotropy when blended with a plastisol typified by an acrylic resin, but particularly excellent slip resistance. .Anti-slip additive that can impart slump resistance, filler containing the same,
And a resin composition containing the same.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using specific particles as an anti-slip additive. The invention was completed.

That is, the first aspect of the present invention relates to an anti-slip additive characterized in that at least the surface is composed of particles composed of a calcium phosphate compound.

A second aspect of the present invention is an anti-slip effect characterized by comprising the above-mentioned anti-slip additive (A) and precipitated calcium carbonate (B) surface-treated with an organic surface-treating agent. The content is the filler that it has.

A third aspect of the present invention relates to a resin composition characterized in that the above-mentioned anti-slip additive and / or the above-mentioned filler is blended with a resin.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. A first aspect of the present invention relates to an anti-slip additive characterized in that at least the surface is composed of particles composed of calcium phosphate.

The calcium phosphate-based compound used in the present invention is not particularly limited, but amorphous calcium phosphate (abbreviation ACP, chemical formula Ca ₃ (PO ₄ ) ₂ .nH)
₂ O), Fluorapatite (abbreviation FAP, chemical formula Ca ₁₀
(PO ₄ ) ₆ F ₂ ), chlorine apatite (abbreviation CAP, chemical formula Ca ₁₀ (PO ₄ ) ₆ Cl ₂ ), hydroxyapatite (abbreviation HAP, chemical formula Ca ₁₀ (PO ₄ ) ₆ (O
H) ₂ ), octacalcium phosphate (abbreviation OCP, chemical formula C
_{a 8 H 2 (PO 4)} 6 · 5H 2 O), tricalcium phosphate (abbreviation TCP, chemical formula _{Ca 3 (PO 4) 2)} , calcium hydrogen phosphate (abbreviation DCP, formula CaHPO _4),
Examples thereof include calcium hydrogen phosphate dihydrate (abbreviation DCPD, chemical formula CaHPO ₄ .2H ₂ O) and the like, and may be one kind or two or more kinds. Among them, hydroxyapatite and octacalcium phosphate are highly stable in composition. , Tricalcium phosphate and calcium hydrogen phosphate are preferable, and hydroxyapatite is particularly preferable. With respect to the content of hydroxyapatite, which has the highest stability, it is preferably 10% by weight or more, more preferably 50% by weight, and most preferably 90% by weight or more based on the total calcium phosphate compound.

C in the calcium phosphate-based compound particles
The atomic ratio of a / P is preferably 16.7 or less, and is 5.5 from the viewpoint that a more excellent slip improving effect can be obtained.
6 or less is preferable, 3.33 or less is more preferable,
Most preferably, it is 1.85 or less. The lower limit of the Ca / P atomic ratio is preferably about 1.60 from the viewpoint of maintaining the stability of the particles. In addition, all the calcium carbonate used as the core material was changed to a calcium phosphate-based compound, and the calcium carbonate as the core material did not exist in the particles.
There is no problem even if 00% (the atomic ratio of Ca / P is 1 to 1.67) is changed to the calcium phosphate compound.

The anti-slip additive of the present invention is a calcium phosphate-based compound in which particles whose surface is composed of calcium phosphate at least have a porous structure in which calcium carbonate is a core material, and the Ca / P atomic ratio is 16.7
It is preferable that the following are satisfied and the following expressions (a) to (e) are satisfied. (A) 0.2 ≦ dx1 ≦ 30 (μm) (b) 0.01 ≦ dx2 ≦ 1 (μm) (c) 50 ≦ Sw1 ≦ 300 (m ² / g) (d) 1 ≦ α ≦ 5 α = d50 / dx1 (e) 0 ≦ β ≦ 2 where β = (d90−d10) / d
50 However, dx1: average particle diameter (μm) of particles measured by an electron micrograph. dx2: In the mercury penetration method, the pore range is 0.001 to
In the pore distribution in the range of 1.0 μm, the average pore diameter (μm) Sw where the mercury intrusion increase amount (integrated pore volume increase amount / log average pore diameter) becomes the maximum value (Dys) Sw: by nitrogen adsorption method BET specific surface area (m ² / g) α: Dispersion coefficient d50: 50% average particle diameter (μm) of particles measured by Microtrac FRA laser type particle size distribution meter. β: Sharpness d90: Cumulative 90% particle diameter (μm) of particles passing through a sieve measured by Microtrac FRA laser type particle size distribution meter. d10: 10% cumulative total particle size on the sieve passage side of the particles measured by a Microtrac FRA laser type particle size distribution meter (μm).

The average particle diameter dx1 of the calcium phosphate-based compound particles is preferably 0.2 ≦ dx1 ≦ 30 (μm). If the average particle size is less than 0.2 μm, the particles may remarkably agglomerate and a sufficient slip improving effect may not be obtained. If the average particle size exceeds 30 μm, there is no problem with the slip property, but when blended with the resin. Viscosity and thixotropy may decrease. Therefore, more preferably 0.3 ≦ dx
1 ≦ 25 (μm), more preferably 0.4 ≦ dx1 ≦
20 (μm).

The average pore diameter dx2 of the calcium phosphate compound particles is preferably 0.01 ≦ dx2 ≦ 1 (μm). When the average pore diameter is less than 0.01 μm, it is difficult to capture the liquid component inside the pores because the pore diameter is small.
Therefore, a sufficient slip improving effect may not be obtained, and when it exceeds 1 μm, the captured liquid component may be released again due to the large pore diameter, and thus a sufficient slip improving effect cannot be obtained. There are cases. Therefore, more preferably 0.02 ≦ dx2 ≦ 0.8 (μ
m), and more preferably 0.03 ≦ dx2 ≦ 0.6 (μ
m).

The BET specific surface area Sw1 of the calcium phosphate compound particles is preferably 50 ≦ Sw1 ≦ 300 (m ² / g). If Sw1 is less than 50 m ² / g, low capture efficiency of the liquid component, may not sufficiently slip effect is obtained, also Sw1 is 300 meters ² /
If it exceeds g, the liquid component may be trapped too much, which may cause an extreme increase in viscosity when blended with the resin. Therefore, more preferably 55 ≦ Sw1 ≦ 250 (m ² /
g), more preferably 60 ≦ Sw1 ≦ 200 (m ² /
g).

The coefficient α showing the dispersibility of the calcium phosphate compound particles and the sharpness β showing the uniformity of the particles are as follows:
It is preferable that 1 ≦ α ≦ 5 and 0 ≦ β ≦ 2, and more preferably 1 ≦ α ≦ 2 and 0 ≦ β ≦ 1. If α exceeds 5, the proportion of coarse aggregates may increase, which may cause a decrease in viscosity when blended with the resin. If α is less than 1, the proportion of fine particles increases and blended with the resin. It may cause an extreme increase in viscosity. Further, when β exceeds 2, the particle size is non-uniform, which may cause a decrease in thixotropy when compounded in the resin, resulting in deterioration in workability and slump property.

The method for preparing the calcium phosphate-based compound particles is not particularly limited. For example, in a water system in which calcium carbonate is dispersed, water-soluble phosphoric acid or a water-soluble phosphate is gradually reacted, It is prepared by forming a calcium phosphate compound on the surface of the core material.
Specifically, an aqueous suspension dispersion of calcium carbonate as a specific core material and a dilute aqueous solution of phosphoric acid and / or a specific aqueous suspension of calcium dihydrogen phosphate and / or a specific calcium hydrogen phosphate 2 After mixing the water suspension dispersion of hydrous salt in a specific ratio under a specific mixing condition and aging under a specific aging condition,
A method of drying is exemplified.

Among the calcium phosphate-based compounds,
A method for preparing a calcium phosphate-based compound containing a petal-like porous hydroxyapatite as a main component, which can be particularly preferably used, will be described more specifically. An aqueous suspension dispersion of calcium carbonate having a mean particle size of 0.1 to 5 μm measured with a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) and / or a dilute aqueous solution of phosphoric acid and / or a particle size distribution analyzer (Calcium dihydrogen phosphate aqueous suspension dispersion having an average particle diameter of 2 to 10 μm measured by Shimadzu SA-CP3) and / or a particle size distribution analyzer (Shimadzu SA -CP3), an aqueous suspension dispersion of calcium hydrogen phosphate dihydrate having an average particle size of 2 to 10 m has a Ca / P atomic ratio of 16.7 to.
After mixing in water at a ratio of 1.60 under the following mixing conditions,
Furthermore, aging under the following aging conditions, dehydration, washing with water,
It is dried in a dry atmosphere of 300 ° C. or less and crushed and finished.

[0021] Mixing conditions     Calcium carbonate water suspension dispersion solid concentration 1-15% by weight     Concentration of dilute aqueous solution of phosphoric acid 1 to 50% by weight     Peripheral speed of mixing and stirring blade 0.3 to 50 m / sec     Mixing time 0.1 to 150 hours     Mixed system water suspension temperature 0-80 ° C     Mixed system water suspension pH 5-9 Aging conditions     Aging system Ca concentration 0.4-5% by weight     Aging time 0.1 to 100 hours     Aging system water suspension temperature 20-80 ° C     Aging system water suspension pH 6-9     Peripheral speed of stirring blade 0.3 to 50 m / sec

The calcium phosphate compound particles may be subjected to a surface treatment by coating the surface of the particles with a surface treating agent, if necessary. It is possible to obtain sufficient slip resistance even without treatment, and in many cases, the resin composition is often surface-treated in order to add storage stability, dispersibility, stability of color tone and the like. Therefore, the surface treatment amount is not particularly limited, but is usually 50% by weight or less. When it exceeds 50% by weight, liberation to the resin component or the plastic component occurs due to an excessive amount of the surface treatment agent, which may cause a bleeding phenomenon and adversely affect the slip property and the viscosity stability of the resin composition. Therefore, it is more preferably 40% by weight or less, and further preferably 35% by weight or less.

The type of surface treatment agent is not particularly limited, and examples thereof include coupling agents such as silane coupling agents and titanate coupling agents, and organic acids such as α, such as fatty acids, resin acids and acrylic acids. , Β-monoethylenically unsaturated carboxylic acids and their esters, oxalic acid, organic acids such as citric acid, tartaric acid, inorganic acids such as hydrofluoric acid,
Surface treatment agents such as polymers and copolymers thereof, salts thereof, or esters thereof, saturated fatty acids typified by caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and alginic acid, oleic acid. , Elaidic acid, linoleic acid, unsaturated fatty acids typified by ricinoleic acid, alicyclic carboxylic acids typified by naphthenic acid, abietic acid, pimaric acid, parastolic acid, resin acids typified by neoabietic acid, and these Disproportionated rosin, hydrogenated rosin, dimer rosin, modified rosin typified by trimer rosin, sulfonic acids typified by alkylbenzene sulfonic acid, and their alkali metal salts, alkaline earth metal salts, ammonium salts, Amine salts, anionic, cationic and nonionic surfactants, sodium hexametaphosphate, pyro Phosphate, sodium pyrophosphate, tripolyphosphate, sodium tripolyphosphate, trimetaphosphate, condensed phosphoric acid and its salts such as Haiporirin acid are used. These surface treatment methods are not particularly limited, and the surface treatment may be performed by a wet method or a dry method according to a conventional method.

The effect of the anti-slip additive of the present invention can be more effectively exhibited by combining it with the precipitated calcium carbonate surface-treated with the organic surface treatment agent. That is, the second aspect of the present invention has an anti-slip effect, which is characterized by comprising the above-mentioned anti-slip additive (A) and the precipitated calcium carbonate (B) surface-treated with an organic surface treatment agent. It relates to the filler.

The precipitated calcium carbonate (B) surface-treated with an organic surface treatment agent preferably satisfies the following formulas (f) to (g). (F) 10 ≦ Sw2 ≦ 200 (m ² / g) (g) 0.5 ≦ As ≦ 7.5 (mg / m ² ) Sw2: BET specific surface area (m ² / g) As by nitrogen adsorption method As: Surface treatment amount (g / m ² ) per unit specific surface area calculated by the formula Surface treatment calcium carbonate at 200 ° C to 500 ° C 1
Thermal loss per gram (mg / g) / Sw (m ² / g)

The expression (f) relates to the BET specific surface area (Sw2) of the precipitated calcium carbonate (B) surface-treated with the organic surface treatment agent, and 10≤Sw2≤200.
It is preferably (m ² / g). Specific surface area is 10m
If it is less than ² / g, the viscosity and thixotropy when blended with the resin will deteriorate, and the slump property will deteriorate significantly, so the slip phenomenon itself may become difficult to occur due to this effect.
If it exceeds 0 m ² / g, it may cause an extreme increase in viscosity when kneaded into the resin. Therefore, it is more preferably 20 to 180 m ² / g, further preferably 30 to 1
It is 60 m ² / g.

The formula (g) is the amount (As) of the surface treatment agent per unit specific surface area of the precipitated calcium carbonate (B) surface-treated with the organic surface treatment agent of the present invention, and The system surface treatment amount As is 0.5 ≦ As ≦ 7.5.
It is preferably (mg / m ² ). 0.5 mg / m
If it is less than ^{2, the} viscosity and thixotropy may be abnormal due to insufficient treatment. On the other hand, if it exceeds 7.5 mg / m ² , the amount of surface treatment per unit area is too large and the surface treatment agent In some cases, release to the resin component or the plastic component may occur and slip performance may deteriorate. Therefore, the amount is more preferably 0.7 to 6.0 mg / m ² , and more preferably 1.0 to 5.0 mg / m ² .

The method for producing calcium carbonate before the surface treatment of the precipitated calcium carbonate (B) surface-treated with the organic surface treating agent of the present invention is not particularly limited,
For example, a conventional method of synthesizing calcium carbonate particles by blowing carbon dioxide gas into lime milk, or JP-A-1
As described in JP-A 0-72215, there is used a production method in which a complexing agent with calcium is added to lime milk to end the carbonation reaction, and then aging.

The preferable preparation conditions are shown below.                         (Reaction conditions) Milk milk concentration: 3.5-20.0% by weight Carbon dioxide gas flow rate: 200 to 2000 L / hr Gas concentration: 10-50% Complex-forming substance: 15% by weight or less                           (Aging condition) Calcium carbonate concentration: 2.4-20.0% by weight Aging time: within 6 to 240 hours                           (surface treatment) Surface treatment amount: appropriately selected within a range satisfying the expressions (f) and (g)

A preferred method for producing calcium carbonate used in the present invention will be specifically described. The lime milk concentration of (reaction condition) is preferably 3.5 to 20.0% by weight. When the lime milk concentration is less than 3.5%, the productivity is low and the cost is high, and even if the concentration is further decreased, it is difficult to contribute to the improvement of the dispersibility. 20.0% by weight
If it exceeds, aggregation of the primary particle size after the reaction becomes tight, and the average secondary particle size becomes higher than the average secondary particle size even after aging, and it is difficult to obtain desired viscosity physical properties. Therefore, more preferably 5.0 to
It is 12.0% by weight, most preferably 6.0 to 10.0% by weight.

The flow rate of carbon dioxide gas is usually 200 to 2000 L / hr per calcium hydroxide. If it is less than 200 L / hr, the primary particles after the reaction tend to be large, and if it exceeds 2000 L / hr, the cost becomes industrially high.

The gas concentration of 10 is preferably 10 to 50%. When the gas concentration is less than 10%, the primary particles after the reaction tend to be large, and when it exceeds 50%, the cost becomes industrially high.

Further, as described above, an arbitrary complex-forming substance may be added to lime milk before carbon dioxide gas is added. The addition amount of the complex-forming substance is preferably 15% by weight or less. Addition amount is 1
If it exceeds 5% by weight, the primary particles after the reaction are too fine, so that the dispersibility of the secondary particles decreases, and as a result, it is difficult to obtain the desired high viscosity. At the time of addition, it may be added before or during the carbonation reaction, or both before and during the reaction.

Examples of the complex-forming substance include hydroxycarboxylic acids such as citric acid, oxalic acid and malic acid and their alkali metal salts, alkaline earth metal salts and ammonium salts; polyhydroxycarboxylic acids such as gluconic acid and tartaric acid and their alkalis. Metal salts, alkaline earth metal salts and ammonium salts; aminopolycarboxylic acids such as iminodiacetic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid and their alkali metal salts, alkaline earth metal salts and ammonium salts; polyacetic acid such as hexametaphosphoric acid and tripolyphosphoric acid And its alkali metal salts, alkaline earth metal salts and ammonium salts; ketones such as aceracetone, methyl acetoacetate and allyl acetoacetate; sulfuric acid and its alkali metal salts, alkaline earth metal salts and ammonium salts, and the like. Use alone or in combination of two or more It is also possible to. Among them, hydroxycarboxylic acids have a high binding property with calcium, and citric acid can be particularly preferably used.

Regarding the calcium carbonate concentration of (aging conditions), 2.4 to 20.0% by weight is preferable. If it is less than 2.4% by weight, industrial productivity is low, and if it exceeds 20.0% by weight, the structural viscosity of the system increases when the dispersibility is improved by aging, and the system can be uniformly stirred. Becomes difficult,
The dispersibility of the secondary particles decreases, and as a result, it is difficult to obtain the desired high viscosity. Therefore, more preferably 4.0-1
The amount is 7.0% by weight, and more preferably 5.0 to 14.0% by weight. As described above, the aging concentration tends to be an important index for improving the dispersibility, so that it is more effective to make the concentration smaller in the preferable range for finer particles.

The ripening time is not particularly limited because the degree of dispersion varies depending on the target particle size due to the difference in cohesive force. Generally, the smaller the particle size, the stronger the cohesive force, and therefore the aging takes longer. Although there are differences depending on the target particle size, normally 6 to 240 hours are preferable. If the time is less than 6 hours, the dispersion of the secondary particles may be insufficient and the desired viscosity may not be obtained, and if the time exceeds 240 hours, the cost will be high in industrial production. Therefore, it is more preferably 9 to 200 hours, further preferably 12 to 1
80 hours.

Conditions other than the above-mentioned manufacturing conditions may be set in the conventional manner. For example, the synthesis temperature condition is in the range of 5 to 25 ° C, and the aging temperature condition is in the range of 30 to 70 ° C. Further, the stirring condition at the time of aging is sufficient if the stirring force is such that the entire liquid system can be uniformly stirred, but with the conventional stirring ability, it becomes necessary to dilute the concentration of the system and the cost increases. Prone. From the viewpoint of improving not only productivity but also dispersibility, it is preferable that the stirring ability is higher than in the past. As the stirring mechanism, a paddle, turbine, propeller, high speed impeller, etc. are generally used.

The precipitated calcium carbonate obtained by compounding and aging according to the above method is surface-treated with an organic surface-treating agent. The amount of the surface treatment depends on the specific surface area of the calcium carbonate dough. Therefore, Sw in the equation (f)
2 may be appropriately selected within a range that satisfies As of the expression (g) and 2).

The organic surface treatment agent used in the present invention is
Saturated fatty acids represented by caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and aragic acid, unsaturated fatty acids represented by oleic acid, elaidic acid, linoleic acid, ricinoleic acid, and fats represented by naphthenic acid. Resin acids typified by cyclic carboxylic acids, abietic acid, pimaric acid, parastolic acid, neoabietic acid, and disproportionated rosins, hydrogenated rosins, dimeric rosins, and modified rosins typified by trimer rosins , Sulfonic acids represented by alkylbenzene sulfonic acid and their alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and anionic, cationic and nonionic surfactants exemplified below. It is also possible to use two or more types in combination.

Examples of the anionic surfactant include alkyl ether sulfuric acid exemplified by polyoxyethylene alkyl ether sulfuric acid and the like, alkyl ether phosphoric acid exemplified by polyoxyethylene alkyl ether phosphoric acid and the like, polyoxyethylene alkylphenyl ether sulfuric acid and the like. Examples of alkyl aryl ether sulfuric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, etc., alkyl aryl ether phosphoric acid, polyoxyalkyl sulfuric acid ester, etc. Alkyl aryl sulfates exemplified by alkyl phosphates, polyoxyalkylphenyl sulfates, etc. Alkyl aryl phosphates exemplified by polyoxyalkylphenyl phosphates, etc. Alkylamido sulfuric acid ester exemplified by sulfuric acid ester of fatty acid alkylolamide, alkyl sulfonic acid exemplified by polyoxyethylene alkyl sulfonic acid, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, sulfosuccinic acid, dialkyl sulfosuccinic acid ester, etc. Anionic surfactants such as sulfosuccinic acid ester, α-olefin sulfonic acid, N-acyl sulfonic acid and / or their alkali metal, alkaline earth metal salt, amine salt, ammonium salt, α, β unsaturated Monocarboxylic acid, α, β unsaturated dicarboxylic acid, methacrylic acid alkyl ester, (meth) acrylic ether having an alkoxy group, (meth) acrylate having a cyclohexyl group, α, β monoethylenically unsaturated hydroxy ester, poly Alkylene glycol mono (meth) acrylate, vinyl ester,
Vinyl aromatic, unsaturated nitrile, unsaturated dicarboxylic acid ester, vinyl ether, conjugated diene, chain olefin, cyclic olefin, anionic polymer dispersant exemplified by a copolymer of sulfo group-containing monomers and the like, and Examples thereof include salts partially or completely neutralized with alkali metals, alkaline earth metals, ammonium and the like.

Further, as the cationic surfactant,
Aliphatic amine salts such as stearylamine acetate and stearylamine hydrochloride, aliphatic quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride, aromatic quaternary ammonium salts such as alkylbenzyldimethylammonium chloride, heterocycle 4 Cationic surfactants such as quaternary ammonium compounds, polar groups such as amino groups (primary amine groups), imino groups (secondary amine groups), tertiary amine groups, quaternary ammonium groups, hydrazino groups, etc. Molecular dispersants, monomers copolymerizable with those having polar groups, such as α, β unsaturated monocarboxylic acids, α, β
Unsaturated dicarboxylic acid, methacrylic acid alkyl ester, (meth) acrylic ether having an alkoxy group,
A (meth) acrylate having a cyclohexyl group, α,
β monoethylenically unsaturated hydroxy ester, polyalkylene glycol mono (meth) acrylate, vinyl ester, vinyl aromatic, unsaturated nitrile, unsaturated dicarboxylic acid ester, vinyl ether, conjugated diene, chain olefin, cyclic olefin, sulfo group Examples thereof include copolymers with monomers such as contained monomers, and salts thereof partially or completely neutralized with alkali metals, alkaline earth metals, ammonium and the like.

Furthermore, examples of the nonionic surfactant include polyoxyethylene and its derivatives, betaine exemplified by carboxybetaine, sulfobetaine and the like, aminocarboxylic acid and imidazoline derivatives.

Of these, saturated fatty acids, unsaturated fatty acids and salts thereof, resin acids and salts thereof are particularly preferable in view of workability, easiness of handling and cost.

In the filler of the present invention, the slip preventing additive (A) and the precipitated calcium carbonate (B) surface-treated with an organic surface treating agent are in a weight ratio (Awt / Bwt).
It is preferable that 0.005 ≦ Awt / Bwt ≦ 2. However, Awt represents the number of parts by weight of the slip prevention additive (A), and Bwt represents the number of parts by weight of the precipitated calcium carbonate (B) surface-treated with the organic surface treatment agent. A
If wt / Bwt is less than 0.005, the ratio of the slip prevention additive (A) may be too low and a sufficient slip improving effect may not be obtained. If Awt / Bwt exceeds 2, the resin may not be added. The viscosity when compounded may be extremely high. Therefore, more preferably 0.01 ≦ Awt /
Bwt ≦ 1.5, more preferably 0.02 ≦ Awt /
Bwt ≦ 1.

In the filler of the present invention, (A) and (B)
The method of mixing both components is not particularly limited. For example, after the aging step of the precipitated calcium carbonate, after the surface treatment step of the precipitated calcium carbonate, dehydrated cake state,
After drying and after pulverization, they may be mixed at any stage such as when blending with a resin.

Further, the method of mixing both components (A) and (B) is not particularly limited. For example, in the case of mixing the slurries as described in (1) to (3), mixing and stirring may be performed with a paddle, an SG mill, a disper, a turbine, a propeller, a high speed impeller, or the like. When the dehydrated cakes are mixed with each other as described above, or when the slurry is added to the dehydrated cakes, they may be mixed with a kneader, a Henschel mixer, a screw mixer, a paddle kneader, or the like. Further, when the powders are mixed with each other as in the following, any means such as a blender, a screw mixer, a paddle kneader, a planetary mixer, a Henschel mixer, or manual mixing may be used, and the final filling is performed. It suffices if the materials are blended uniformly. As described above, in the case of mixing at the time of blending with the resin, it may be added at the stage of adding the powder in the usual blending process. In addition, at that time, the charging may be performed at different stages, instead of the simultaneous charging.

As described above, the slip preventing additive of the present invention and the filler containing the slip preventing additive are
For example, it is blended with a resin for plastisols to obtain a resin composition having excellent properties and physical properties. That is, the third aspect of the present invention
Relates to a resin composition comprising the above-mentioned slip preventing additive and / or the above-mentioned filler mixed with a resin.

The resin to which the anti-slip additive of the present invention and / or the filler of the present invention is blended is not particularly limited, but it is particularly preferably applied to a resin having a problem in slip resistance, for example, It is most effectively applied to thermoplastic plastisols, especially acrylic plastisols.
It should be noted that, rather than directly blending the antislip additive of the present invention with a resin, it is more viscous and thixotropic and more excellent slump resistance is obtained by blending the filler of the present invention containing the antislip additive. It is preferable in that the composition can be provided.

The acrylic plastisol of the present invention is composed of acrylic polymer particles, a plasticizer, a filler and an antislip agent, but a block type urethane resin and a curing agent can also be blended. Other conventionally known additives such as colorants, antioxidants, foaming agents, diluents, and ultraviolet absorbers can be added.

As the acrylic polymer particles constituting the acrylic plastisol of the present invention, any acrylic polymer particles usually used as a composition of acrylic plastisols can be used. For example, a homopolymer or a copolymer of a monomer selected from acrylic acid alkyl ester, methacrylic acid alkyl ester and the like can be used. Specific examples of these monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl. Methacrylate, octyl methacrylate, decyl methacrylate, hydroxymethaethyl acrylate, hydroxypropyl methacrylate, etc. are mentioned, and these are used 1 type or in combination of 2 or more types. Among them, polymer particles having a core / shell structure are preferably used because of storage stability and easy adjustment of gel speed. For example, the core portion is a homopolymer of alkyl acrylate, hydroxy acrylate, alkyl methacrylate or hydroxy methacrylate, a copolymer thereof, and further, acrylic acid, methacrylic acid, maleic acid, itaconic acid, styrene, etc. It is formed compatible with the plasticizer from the copolymer, and the shell part is methyl methacrylate homopolymer, methyl methacrylate and alkyl acrylate, hydroxy acrylate, alkyl methacrylate, hydroxy methacrylate, acrylic acid, methacrylic acid, maleic acid. , Itaconic acid, a copolymer formed with styrene or the like, which is incompatible with the plasticizer.

As the plasticizer constituting the acrylic plastisol of the present invention, known plasticizers such as phthalic acid ester, phosphoric acid ester, adipic acid ester and sebacic acid ester plasticizer can be used. As a phthalate ester-based plasticizer, dimethyl phthalate (DM
P), diethyl phthalate (DEP), dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), diisodecyl phthalate (DIDP), butylbenzyl phthalate (BBP), diisononyl phthalate (DINP),
Examples of phosphoric acid ester plasticizers such as dinonyl phthalate (DNP) include tricresyl phosphate (TCP),
Triphenyl phosphate (TPP), trixylylene phosphate (TXP) and the like, adipic ester plasticizers such as dioctyl adipate (DOA) and diisodecyl adipate (DIDA), and sebacic acid ester plasticizers such as dibutyl sebacate ( DBS), dioctyl sebacate (DOS), etc., and one or more kinds of these, such as epoxy plasticizers such as epoxidized soybean oil, benzoic acid plasticizers, polyester plasticizers, etc. Although it can be used, a phthalic acid-based plasticizer is particularly preferable.

As the filler, in addition to the filler of the present invention, common fillers such as precipitated calcium carbonate, ground calcium carbonate, colloidal silica, talc, kaolin, zeolite, resin balloons and glass balloons. You may use together.

The acrylic plastisol of the present invention is preferably blended with a block type urethane resin. Examples of the block type urethane resin include polyols such as polyether polyol and polyester polyol, diphenylmethane diisocyanate, tolylene diisocyanate,
A urethane resin obtained by reacting with an isocyanate such as hexamethylene diisocyanate, xylene diisocyanate, 1,3-biscyclohexane diisocyanate, tetramethylxylylene diisocyanate, m-isopropenyldimethylbenzyl isocyanate, etc., is a blocking agent such as oxime or amine. 1 such as urethane resin blocked by using, a oxybenzoic ester or alkylphenol block of a diisocyanate polymer, a nurate ring forming body of a diisocyanate polymer, etc.
One kind or a combination of two or more kinds is preferably used.

As the colorant, for example, titanium dioxide,
Inorganic pigments such as carbon black and organic pigments such as azo type and phthalocyanine type can be used. As the antioxidant, for example, a phenol-based or amine-based antioxidant can be used. As the foaming agent, a foaming agent of a type that generates gas upon heating can be used, and for example, an azo foaming agent such as azodicarbunamide or azobisformamide can be used. As the diluent, for example, a solvent such as xylene or mineral terpene can be reduced. A benzotriazole type etc. can be used as an ultraviolet absorber.

The blending ratio of these resins with the slip preventing additive and / or the filler consisting of the slip preventing additive and the precipitated calcium carbonate surface-treated with the organic surface treating agent is not particularly limited. It may be appropriately determined depending on the kind and use of the resin and the desired physical properties, and it goes without saying that various other additives such as the above-mentioned fillers, plasticizers, stabilizers and the like may be added. is there. For example, in the case of acrylic plastisols, the number of parts by weight of the anti-slip additive is usually 0.
01 to 50 parts by weight, preferably 0.05 to 40 parts by weight,
More preferably, it is about 0.1 to 30 parts by weight.

The reason why the slip-preventing additive of the present invention improves the slip property is not clear, but by using calcium phosphate at least on the surface, the affinity with the resin is improved, and the surface has a porous structure. It is considered that by taking the above, it is easy to capture the plasticizer in the formulation and bleeding to the interface is prevented, so that the slip effect is improved.

[0057]

EXAMPLES The present invention will be described in more detail below with reference to synthetic examples and examples, but the present invention is not limited to these as long as the gist thereof is not exceeded. In the following description,% and parts mean% by weight and parts by weight, respectively, unless otherwise specified. Moreover, the measurement of each physical property value was performed with the following equipment and conditions.

Dx1: Average particle diameter (μm) by electron micrograph A sample was put in a small amount in methanol, stirred by hand, and placed on a sample stand for vapor deposition. The sample thus obtained was observed in a field of view of 10000 times of Hitachi Scanning Electron Microscope S-2360N (manufactured by Hitachi), the primary particle diameter was measured at 10 points with a ruler, and the average value was taken.

Dx2: average pore diameter (μm) A sample was weighed to about 0.10 g, and a porosimeter 952 was used.
Measured with type 0 (manufactured by Shimadzu Corporation). The measurement conditions are as follows. Mercury purity = 99.99 (%) Mercury surface tension = 480 (dyns / cm) Mercury contact angle = 135 ° C Cell constant = 10.79 (μl / pF)

Sw: BET specific surface area (m ² / g) 0.3 g of a sample was weighed into a glass pellet cell having an effective volume of 0.45 cc, dried under nitrogen atmosphere at 180 ° C. for 1 hour, and then NOVA 2000 (Yuaasaai). Measured by the one-point method by Onyx Inc.).

Α, β (d50, d90, d10):
Particle size measured by particle size distribution meter 100 g of methanol and 1 g of sample were put into a 140 ml mayonnaise bottle, and after preliminary stirring with a stainless spoon,
A sample preliminarily dispersed by an ultrasonic disperser was used as a sample, which was measured with a Microtrac FRA laser particle size distribution meter (manufactured by Nikkiso) in a methanol system. d50, d90, d10 are
50% weight accumulation calculated from the small particle side, 9
The average particle diameter (μm) of 0% and 10% is indicated. As the ultrasonic disperser, US-300T (manufactured by Nippon Seiki Seisakusho Co., Ltd.) was used for preliminary dispersion under constant conditions of 100 μA-60 seconds.

As: 200 to 500 ° C. heat loss / Sw 0.15 g of a sample was weighed into an aluminum cell having an outer diameter of 5.2 mm and a height of 2.5 mm, and was measured at 15 ° C./min with TAS-100 (manufactured by Rigaku). 510 from room temperature at a heating rate of
Measure the heat loss in the range of 200-500 ° C when the temperature is raised to ℃. The obtained numerical value was divided by the BET specific surface area to calculate the surface treatment amount As per unit area.

(1) "Synthesis Example of Calcium Phosphate Compound" First, a method for preparing aqueous suspension dispersions a and b of calcium carbonate to be used will be described, and then at least the dispersions a and b will be used. Synthesis Examples 1 to 8 of particles whose surface is composed of a calcium phosphate compound will be described.

Aqueous Suspension Dispersion of Calcium Carbonate a Heavy calcium carbonate made by Maruo Calcium "Super SS"
S ”(1.2 m ² / g) was added and mixed with water, and then stirred and dispersed with a TK homomixer (5000 rpm, 15 minutes) to obtain a particle size of 3 μm with an average particle size measured from an electron micrograph with a solid concentration of 25%. Distribution measuring instrument (S, manufactured by Shimadzu Corporation)
Aqueous suspension dispersion a of calcium carbonate having an average particle size measured by A-CP3) of 3.4 μm was prepared.

Calcium carbonate aqueous suspension dispersion b 7,000 liters of lime milk (aqueous suspension of calcium hydroxide) having a specific gravity of 1.055 and a temperature of 8 ° C. and a carbon dioxide concentration of 27
A wt% furnace gas was passed at a flow rate of 24 m ³ to carry out a carbonation reaction up to pH 9, and then aged with stirring at 40 to 50 ° C. for 5 hours to elute the alkali between the particles to pH 1.
The average particle size measured by an electron micrograph was 0.05 μm, and the average particle size measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) was 0.8.
An aqueous suspension dispersion b of calcium carbonate having a diameter of 48 μm was prepared.

Synthetic Example 1 One turbine blade having a diameter of 0.6 m and 0.4 with a stirrer
m ³ stainless steel tank (with baffle plate), solid content 8%,
400 kg of the above calcium carbonate aqueous suspension a adjusted to a temperature of 40 ° C. was added, and the Ca / P atomic ratio was adjusted to 3.33 while stirring at a stirring blade peripheral speed of 6 m / S.
% Aqueous solution of phosphoric acid diluted with water was added dropwise for 2.5 hours. The pH of the aqueous suspension during the reaction was 6.5-7. After completion of the reaction, stirring and aging were carried out for 12 hours at a temperature of 40 ° C. and a stirring blade peripheral speed of 6 m / s. After aging, adjust the solid concentration to 8%,
Porous calcium phosphate, which is a calcium phosphate-based compound having a petal-like porous structure with calcium carbonate as a core material, was prepared by spray-drying. Synthesis example 1
Table 1 shows the production conditions and the respective physical properties.

Synthetic Example 2 A petal-like porous material containing calcium carbonate as a core material was prepared in the same manner as in Synthetic Example 1 except that the phosphoric acid aqueous solution was adjusted so that the atomic ratio of Ca / P was 12.0. Porous calcium phosphate, which is a calcium phosphate-based compound having a structure, was prepared. Table 1 shows the production conditions and physical properties of Synthesis Example 2.

Synthesis Example 3 A petal-like porous structure having calcium carbonate as a core material was prepared in the same formulation as in Synthesis Example 1 except that the stirring blade peripheral speed at the time of reaction and aging was set to 1.5 m / s. Porous calcium phosphate, which is a calcium phosphate-based compound, was prepared. Table 1 shows the production conditions and physical properties of Synthesis Example 3.

Synthesis Example 4 To the calcium phosphate aqueous solution synthesized under the conditions of Synthesis Example 1, after completion of aging, 10% of sodium stearate which was heat-dissolved in heat was added to the porous calcium phosphate solid content.
0% was added and the surface treatment agent was sufficiently adsorbed on the calcium carbonate surface by vigorous stirring, and then spray-dried in the same manner as in Synthesis Example 1 to form a petal-like porous structure using calcium carbonate as a core material. Porous calcium phosphate which is a calcium phosphate-based compound having was prepared. Synthesis example 4
Table 1 shows the adjustment method and the respective physical properties.

Synthetic Example 5 The same formulation as in Synthetic Example 1 was used except that the above calcium carbonate aqueous suspension b was used and the phosphoric acid aqueous solution was adjusted so that the Ca / P atomic ratio was 1.67. Porous calcium phosphate, which is a calcium phosphate-based compound having a petal-like porous structure with calcium carbonate as a core material, was prepared. Table 1 shows the production conditions and physical properties of Synthesis Example 5.

Synthetic Example 6 A calcium phosphate-based compound having a petal-like porous structure using calcium carbonate as a core material and having the same formulation as in Synthetic Example 5 except that the stirring blade peripheral speed was set to 1.5 m / s. Porous calcium phosphate was prepared. Table 1 shows the production conditions and respective physical property values of Synthesis Example 6. In addition, electron micrograph (10 showing the particle structure of the obtained porous calcium phosphate)
(× 000) is shown in FIG.

Synthesis Example 7 The temperature during the reaction and aging was 27 ° C., and the peripheral speed of the stirring blade was 0.
Porous calcium phosphate, which is a calcium phosphate-based compound having a petal-like porous structure with calcium carbonate as a core material, was prepared in the same formulation as in Synthesis Example 1 except that the rate was 3 m / s. Table 1 shows the production conditions and physical properties of Synthesis Example 7.

Synthetic Example 8 A petal-like porous material having calcium carbonate as a core material was prepared in the same manner as in Synthetic Example 1 except that the phosphoric acid aqueous solution was adjusted so that the atomic ratio of Ca / P was 20.0. Porous calcium phosphate, which is a calcium phosphate-based compound having a structure, was prepared. Table 1 shows the production conditions and physical properties of Synthesis Example 8.

[0074]

[Table 1]

(2) "Synthesis Example of Calcium Carbonate Surface-Treated with Organic Surface Treatment Agent" A synthesis example of the surface-treated calcium carbonate used in the following Examples and Comparative Examples will be described.

Synthesis Example 9 Lime milk adjusted to a temperature of 12 ° C. and a concentration of 15.0% was added with 1700 L / hr of 20% C per 1 kg of calcium hydroxide.
O ₂ gas was introduced to produce calcium carbonate. Next, the calcium carbonate slurry was subjected to stirring aging at a temperature of 45 to 50 ° C. for 96 hours. To the calcium carbonate slurry, 10% sodium stearate heat-dissolved in warm water was added by 4% to the calcium carbonate solid content, and the mixture was stirred to allow the surface treatment agent to be sufficiently adsorbed on the calcium carbonate surface, followed by dehydration, Calcium carbonate obtained by drying and pulverizing and surface-treating an organic surface treating agent was synthesized. Table 2 shows the production conditions and physical properties of Synthesis Example 9.

Synthesis Example 10 1700 L / hr of 20% C per 1 kg of calcium hydroxide was added to lime milk adjusted to a temperature of 12 ° C. and a concentration of 12.0%.
O ₂ gas was introduced to produce calcium carbonate. Next, the calcium carbonate slurry was stirred and aged at a temperature of 45 to 50 ° C. for 12 hours. To the calcium carbonate slurry, 10% sodium stearate heat-dissolved in warm water was added 7% to the calcium carbonate solid content, and the mixture was stirred to allow the surface treatment agent to be sufficiently adsorbed on the calcium carbonate surface, followed by dehydration, Precipitable calcium carbonate obtained by drying, pulverizing and surface-treating an organic surface treating agent was synthesized.
Table 2 shows the production conditions and physical properties of Synthesis Example 10.

Synthesis Example 11 In lime milk adjusted to a temperature of 12 ° C. and a concentration of 8.0%, citric acid as a complex-forming substance was added to calcium hydroxide in an amount of 1.5.
%, And 1700 L / hr of 20% CO ₂ gas per kg of calcium hydroxide was introduced into the slurry to produce calcium carbonate. Next, the calcium carbonate slurry was adjusted to a concentration of 10% and aged with stirring at a temperature of 45 to 50 ° C. for 48 hours. To the calcium carbonate slurry, 15% of 10% sodium stearate dissolved in hot water was added to the calcium carbonate solid content, and the mixture was stirred to sufficiently adsorb the surface treatment agent onto the calcium carbonate surface, followed by dehydration, Precipitable calcium carbonate obtained by drying, pulverizing and surface-treating an organic surface treating agent was synthesized. Table 2 shows the production conditions and physical properties of Synthesis Example 11.

Synthesis Example 12 In lime milk adjusted to a temperature of 12 ° C. and a concentration of 5.0%, citric acid as a complex-forming substance was added to calcium hydroxide in an amount of 10%.
Add 1 per kg of calcium hydroxide to the slurry
700 L / hr of 20% CO ₂ gas was introduced to produce calcium carbonate. Next, the calcium carbonate slurry was adjusted to a concentration of 3%, and aged with stirring at a temperature of 45 to 50 ° C. for 144 hours. To the calcium carbonate slurry, 10% sodium stearate that was dissolved in hot water was added 30% to the calcium carbonate solid content, and the mixture was stirred to allow the surface treatment agent to be sufficiently adsorbed on the calcium carbonate surface, followed by dehydration, Precipitable calcium carbonate obtained by drying, pulverizing and surface-treating an organic surface treating agent was synthesized. Synthesis example 1
Table 2 shows the production conditions and physical properties of No. 2.

Synthesis Example 13 Lime milk adjusted to a temperature of 12 ° C. and a concentration of 17.0% was added with 1700 L / hr of 20% C per kg of calcium hydroxide.
O ₂ gas was introduced to produce calcium carbonate. Next, the calcium carbonate slurry was stirred and aged at a temperature of 45 to 50 ° C. for 240 hours. To the calcium carbonate slurry, 10% sodium stearate heat-dissolved in warm water was added by 4% to the calcium carbonate solid content, and the mixture was stirred to allow the surface treatment agent to be sufficiently adsorbed on the calcium carbonate surface, followed by dehydration, Precipitable calcium carbonate obtained by drying, pulverizing and surface-treating an organic surface treating agent was synthesized. Table 2 shows the production conditions and physical properties of Synthesis Example 13.

Synthesis Example 14 In lime milk adjusted to a temperature of 12 ° C. and a concentration of 8.0%, citric acid as a complex-forming substance was added to calcium hydroxide in an amount of 1.5.
%, And 1700 L / hr of 20% CO ₂ gas per kg of calcium hydroxide was introduced into the slurry to produce calcium carbonate. Next, the calcium carbonate slurry was adjusted to a concentration of 10% and aged with stirring at a temperature of 45 to 50 ° C. for 48 hours. To the calcium carbonate slurry, 1.5% of 10% sodium stearate dissolved in hot water was added to the calcium carbonate solid content, and the mixture was stirred to sufficiently adsorb the surface treatment agent onto the calcium carbonate surface. Precipitable calcium carbonate was synthesized by dehydration, drying, pulverization and surface treatment with an organic surface treatment agent. Table 2 shows the production conditions and physical properties of Synthesis Example 14.

Synthetic Example 15 In lime milk adjusted to a temperature of 12 ° C. and a concentration of 8.0%, citric acid as a complex-forming substance was added to calcium hydroxide in an amount of 1.5.
%, And 1700 L / hr of 20% CO ₂ gas per kg of calcium hydroxide was introduced into the slurry to produce calcium carbonate. Next, the calcium carbonate slurry was adjusted to a concentration of 10% and aged with stirring at a temperature of 45 to 50 ° C. for 48 hours. To the calcium carbonate slurry, 10% sodium stearate dissolved in hot water was added 40% to the calcium carbonate solid content, and the mixture was stirred to allow the surface treatment agent to be sufficiently adsorbed on the calcium carbonate surface, followed by dehydration, Precipitable calcium carbonate obtained by drying, pulverizing and surface-treating an organic surface treating agent was synthesized. Table 2 shows the production conditions and physical properties of Synthesis Example 15.

Synthesis Example 16 Heavy calcium carbonate having a BET specific surface area of 1.5 m ² / g was charged into a Henschel mixer (Kawata: 20 L),
After heating to a temperature of 100 ° C., 1% of stearic acid was added to the calcium carbonate solid content, and the mixture was stirred and mixed for 15 minutes.
Heavy calcium carbonate obtained by surface-treating an organic surface treating agent was obtained. Table 2 shows the respective physical properties of Synthesis Example 16.

[0084]

[Table 2]

(3) "Preparation of filler made of a mixture of anti-slip additive (A) and precipitated calcium carbonate (B) obtained by surface-treating an organic surface-treating agent"

Synthesis Example 17 A calcium phosphate slurry having a petal-like porous structure containing calcium carbonate prepared by the formulation of Synthesis Example 1 as a core material, with respect to the surface-treated calcium carbonate slurry prepared by the formulation of Synthesis Example 11. A slurry of the compound porous calcium phosphate after aging was added so that the solid content ratio was 20 parts with respect to 80 parts of calcium carbonate, and the mixture was sufficiently stirred and mixed. Then, dehydration, drying, and powdering were performed to obtain a filler composed of an anti-slip additive (A) made of calcium phosphate and a precipitated calcium carbonate (B) obtained by surface-treating an organic surface treatment agent. Table 3 shows the physical properties of Synthesis Example 17.

Synthetic Example 18 The surface-treated calcium carbonate slurry prepared by the formulation of Synthetic Example 11 was dehydrated by a filter press, and then the petal-like porous material containing calcium carbonate prepared by the formulation of Synthetic Example 1 as a core material. The aged slurry of porous calcium phosphate, which is a calcium phosphate-based compound having a quality structure, was dehydrated with a centrifugal dehydrator, and then each cake was measured so that the solid content ratio was 20 parts with respect to 80 parts of calcium carbonate. A kneader (manufactured by Kurimoto) was kneaded at a temperature of 80 ° C., followed by drying and pulverization to obtain a combined filler of calcium carbonate obtained by surface-treating calcium phosphate particles and an organic surface treating agent. Table 3 shows the respective physical property values of Synthesis Example 18.
Shown in

Synthesis Example 19 Calcium carbonate powder obtained by surface-treating an organic surface treating agent prepared by the formulation of Synthesis Example 11 was charged into a Henschel mixer (Kawata: 20 L), and the formulation of Synthesis Example 1 was added thereto. Porous calcium phosphate powder, which is a calcium phosphate-based compound having a petal-like porous structure with calcium carbonate as the core material, was prepared by adding calcium carbonate at a solid content ratio of 80%.
20 parts by weight relative to parts by weight, sufficiently stirred and mixed, and an anti-slip additive (A) made of calcium phosphate and a precipitated calcium carbonate (B) obtained by surface-treating an organic surface treatment agent. A filling material consisting of Table 3 shows each physical property value of Synthesis Example 19.

[0089]

[Table 3]

(4) Examples, Comparative Examples Anti-slip additives obtained in the above Synthetic Examples 1 to 8, calcium carbonate surface-treated with the organic surface treating agents obtained in the Synthetic Examples 9 to 16, and A resin composition was prepared based on the following composition and the composition shown in Table 4 by using the filler composed of the mixture of both obtained in Synthesis Examples 17 to 19.

[Compounding] Acrylic resin Zeon Acrylic resin F345 (manufactured by Shin-Daiichi Vinyl Industry Co., Ltd.) 250 parts Urethane block polymer (manufactured by Mitsui Takeda Chemical Co., Ltd.) 120 parts Urethane curing agent (manufactured by Mitsui Takeda Chemical Co., Ltd.) 70 parts DINP 500 parts Turpen 80 parts Sample 400 parts Each of the compounding ingredients was kneaded with a 5 L universal stirrer (manufactured by Dalton Co., Ltd.) at room temperature until no bumps were present, to prepare an acrylic sol.

<Viscosity / Thixotropy> The viscosity of the acrylic sol was measured at 2 rpm and 20 rpm using a BH type viscometer, and 2 rpm viscosity / 20 rpm viscosity was expressed as thixotropy.

<Slip resistance and slump resistance> After thoroughly defoaming and mixing the acrylic sol, using a semi-circle beat plate of φ10 mm on a sufficiently polished electrodeposition coated plate, pull it to a length of 50 mm, and vertically It was left standing at 100 ° C. for 10 minutes. The slip value is from the bottom of the first applied sample,
It is expressed by the distance (mm) to the lowered tip. For the slump property, the sagging increase rate from the initial 50 mm was evaluated according to the following criteria. Slump resistance ◎: 0 to 10% increase ○: Over 10% to 20% △: Over 20% to 40% ×: Over 40% increase

Examples 1 to 8 and Comparative Examples 1 to 8 Acrylic sol resin compositions were obtained according to the formulations shown in Tables 4 and 5. Synthetic Example 1 as an additive for slip prevention
The one synthesized in 1. was used. The above-mentioned tests were conducted on the resin composition, and the viscosity, thixotropy, slip resistance and slump resistance were evaluated. The results are shown in Table 6. It is confirmed that the slip resistance is remarkably improved by the addition of the slip prevention additive. It is also confirmed that when used in combination with a precipitated calcium carbonate surface-treated with a specific organic surface-treating agent, good viscosity, thixotropy and slump resistance are imparted.

Examples 9 to 15 By the formulation shown in Table 4, acrylic sol resin compositions were obtained. As the precipitated calcium carbonate surface-treated with the organic surface treatment agent, the one synthesized in Synthesis Example 11 was used. The resin composition was subjected to the above tests to evaluate the viscosity, thixotropy, slip resistance and slump resistance. The results are shown in Table 7. It is confirmed that the slip resistance is significantly improved by the addition of the slip prevention additive. Further, the effect can be further enhanced by using it together with the precipitated calcium carbonate which is surface-treated with a specific organic surface-treating agent. For convenience of comparison, the test results of Example 3 and Comparative Example 3 are also shown.

Examples 16 to 19 Acrylic sol resin compositions were obtained according to the formulations shown in Table 4. The anti-slip additive used was the one synthesized in Synthesis Example 1, and the precipitated calcium carbonate surface-treated with the organic surface treatment agent was the one synthesized in Synthesis Example 11. The above-mentioned tests were conducted on the resin composition, and the viscosity, thixotropy, slip resistance and slump resistance were evaluated. The results are shown in Table 8. It is confirmed that the slip resistance is significantly improved by the addition of the slip prevention additive. It is also confirmed that when the amount of the anti-slip additive is small, the effect is slightly lowered, and when the amount is large, it is difficult to obtain a good sol composition.

Examples 20 to 22 An acrylic sol resin composition was obtained according to the formulation shown in Table 4. The fillers synthesized in Synthesis Examples 17 to 19 were used as the fillers made of a mixture of the slip prevention additive and the precipitated calcium carbonate surface-treated with the organic surface treatment agent. The above test is performed on the resin composition,
The viscosity, thixotropy, slip resistance, and slump resistance were evaluated. The results are shown in Table 9. It can be confirmed that the slip resistance is remarkably improved by the addition of the slip prevention additive. It is confirmed that the slip evaluation additive and the precipitating calcium carbonate surface-treated with the organic surface treatment agent have almost no effect on the final evaluation, regardless of the method used in combination.

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

[0103]

[Table 9]

[0104]

As described above, the additive for preventing slip of the present invention, when added to an acrylic plastisol composition, gives a composition excellent in slip resistance, and is further treated with an organic surface treatment agent. When used in combination with treated precipitated calcium carbonate, it is possible to provide a composition having viscosity and thixotropy and more excellent slump resistance.

[Brief description of drawings]

FIG. 1 is an electron micrograph (10000 times) showing the particle structure of porous calcium phosphate obtained in Synthesis Example 6.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C01F 11/18 C01F 11/18 J (72) Inventor Shigeo Takiyama 1455 Nishioka, Uozumi-cho, Akashi-shi, Hyogo Maruo Calcium Co., Ltd. F term (reference) 4G076 AA15 BF05 BF06 CA05 DA30 4J002 BG001 CD163 CF003 CH052 DD016 DE236 DH037 DH047 EF036 EF046 EF056 EF066 EH098 EH148 EV246 EW048 FD029 FD083 FD090 FD023 FD023 FD0903

Claims (9)

[Claims] 1. An anti-slip additive, characterized in that at least the surface thereof comprises particles composed of a calcium phosphate-based compound. 2. The particles, at least the surface of which is composed of a calcium phosphate-based compound, are calcium phosphate-based compounds having a porous structure with calcium carbonate as a core material, and the atomic ratio of Ca / P is 16.7 or less, And satisfying the following formulas (a) to (e):
The antislip additive as described. (A) 0.2 ≦ dx1 ≦ 30 (μm) (b) 0.01 ≦ dx2 ≦ 1 (μm) (c) 50 ≦ Sw1 ≦ 300 (m ² / g) (d) 1 ≦ α ≦ 5 α = d50 / dx1 (e) 0 ≦ β ≦ 2 where β = (d90−d10) / d
50 However, dx1: average particle diameter (μm) of particles measured by an electron micrograph. dx2: In the mercury penetration method, the pore range is 0.001 to
In the pore distribution in the range of 1.0 μm, the average pore diameter (μm) at which the mercury intrusion increase amount (integrated pore volume increase amount / log average pore diameter) becomes the maximum value (Dys) Sw1: by nitrogen adsorption method BET specific surface area (m ² / g) α: Dispersion coefficient d50: 50% average particle diameter (μm) of particles measured by Microtrac FRA laser type particle size distribution meter. β: Sharpness d90: Cumulative 90% particle diameter (μm) of particles passing through a sieve measured by Microtrac FRA laser type particle size distribution meter. d10: 10% cumulative total particle size on the sieve passage side of the particles measured by a Microtrac FRA laser type particle size distribution meter (μm). 3. An anti-slip agent comprising the anti-slip additive (A) according to claim 1 or 2 and a precipitated calcium carbonate (B) surface-treated with an organic surface-treating agent. Filler with effect. 4. The organic surface treatment agent is a saturated fatty acid, unsaturated fatty acid, resin acid, sulfonic acid, alkali metal salt, alkaline earth metal salt, ammonium salt, amine salt thereof,
The filler having an anti-slip effect according to claim 3, which is at least one selected from a cationic surfactant, an anionic surfactant, and a nonionic surfactant. 5. The slip according to claim 3, wherein the precipitated calcium carbonate (B) surface-treated with an organic surface treatment agent satisfies the following formulas (f) to (g). Filler with effect. (F) 10 ≦ Sw2 ≦ 200 (m ² / g) (g) 0.5 ≦ As ≦ 7.5 (mg / m ² ) Sw2: BET specific surface area (m ² / g) As by nitrogen adsorption method As: Surface treatment amount per unit specific surface area calculated by the formula (g / m ² ) Surface-treated calcium carbonate at 200 ° C to 500 ° C 1
Thermal loss per gram (mg / g) / Sw (m ² / g) 6. Precipitable calcium carbonate (B) surface-treated with an anti-slip additive (A) and an organic surface treatment agent.
And satisfy the weight ratio of the following formula (h), the filler having an anti-slip effect according to any one of claims 3 to 5. (H) 0.005 ≦ Awt / Bwt ≦ 2 Awt: Number of parts by weight of the slip prevention additive (A) Bwt: Number of parts by weight of precipitated calcium carbonate (B) surface-treated with an organic surface treatment agent 7. A resin composition comprising a resin for blending the additive for slip prevention according to claim 1 or 2 and / or the filler according to any one of claims 3 to 6. object. 8. The resin composition according to claim 7, wherein the resin is a resin for acrylic plastisols. 9. The compounding amount of the slip preventing additive and / or the filler is 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin for acrylic plastisol. The resin composition according to item 8.