WO2004009711A1 - Modified calcium carbonate, polymer composition containing the same and process for producing them - Google Patents

Abstract

A modified calcium carbonate comprising calcium carbonate as a raw material and, superimposed on the surface thereof, (i) a silica layer, (ii) an organic acid layer constituted of at least one member selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, resin acids, resin acid salts and resin acid esters and (iii) a layer of silane coupling agent; and a polymer composition comprising the modified calcium carbonate.

Description

 Specification

 Lucium, polymers containing it, and their technical fields

 TECHNICAL FIELD The present invention relates to ¾K-hard calcium, a polymer containing the same, and an ISt の method thereof, which is used for converting bows for polymers such as rubber and plastic. Background technology

 m White carbon (eg, silica) has been widely used as a reinforcement in polymer products that are escaping. However, since wet silica is acidic-filled, if it is blended with a polymer as it is, it is necessary to excite an active material such as polyethylene glycol. In addition, in terms of physical properties, for example, wet silica was blended with rubber: ^, and there was a defect that permanent elongation was poor. Further, silica has a problem in terms of processability and the like, because it causes the viscosity of uncured rubber to work.

 On the other hand, persimmons, which have been shelved as a transponder or auxiliary key for polymers, are W. basic, so that when blended into polymers, they lose their activity. Silica and ί: acidified, ^ 7 lime gives a polymer with excellent permanent elongation.

The Μλυ resin was used as the polymer bow t¾ ^: ^ is a polymer containing wet silica, which has a draw force, occupational food, toughness, sex, etc. I did not include giving

 In addition, persimum coated with a material such as mercaptanamine, which is an iSf compound, has a low mts force at low incorporation, but with wet silica !: Acid, tensile strength, and transeating There was a problem that physical properties such as heat resistance were poor.

 As a means of reducing such problems regarding polymer 櫥!, There are (i) anisotropy (high aspect ratio) of m \ particles, (ii) fine particles ^ (J particles, (i ii ) t

 The introduction of the reaction '1 $ ^ to the surface, such as coating with a silane coupling agent, has been observed.

According to the method of providing anisotropy to (i), the »j property of the polymer is hindered For this reason, 力 ®t, high modulus, etc. are applied. According to the method (ii) of shelving the delicate particles, the interaction between the polymer and the polymer or the interaction between the polymer II and the interaction between the polymer and the polymer is reduced, and the tensile strength and tensile strength are reduced. Be improved. In addition, according to the method (iii) of introducing the aa building functional group, chemistry is introduced between the trans-polymer and the polymer, so that the heat resistance and heat resistance can be improved. You.

 However, it is difficult to provide: ^, anisotropy, and especially: Τ¾ orientation of calcium carbonate. Therefore, the means of (i) is rarely applied, and the use of fine particles of (ii) or iii) Attempts have been made to improve the physical properties when blended with the polymer by means of introducing the trace 'ίkan ^ ¾' on the surface of the Jatari J grain.

 For example, a method of treating a calcium surface with a substance having a hydroxyl group such as a silica hydrosol (JP: No. 9107471), or using both a COOH group and an OH group ^ It is possible to climb together with the method of putting together a polymer (day: Φ kyu 2 7 4 5 0 3 3). However, substituting calcium in the sub-micron order with a silica hydrosol caused the silica hydrosol to strongly solidify the lime, causing silent particles to be generated, and the aggregated particles to be difficult to separate. In addition, the polymer that has both C〇〇H and 〇Η groups is thinned: ^ is the skeleton alk! / || covers the ΟΗ group, and the silane cap link ^! And not enough: there was a t. Disclosure of the invention

 The main object of the present invention is to provide a polymer ma exhibiting mechanical properties comparable to that of white carbon when blended with a polymer, and to further disperse a polymer having excellent polymer moldability. And

The inventor of the present invention has made it possible to provide (i) a silica layer, (ii) a fat Ji carrier, a fatty acid salt, a fat J! Fiber ester, separation, shelf test At least one kind of organic acid layer selected from fatty acid esters, and (ii i) silane cup link ^! It has been found that the physical properties of the polymer product thus obtained can be improved, and the present invention has been accomplished through further studies. That is, the present invention provides the following calcium carbonate, a polymer containing the calcium carbonate: m, these ^ t methods, lima ^ / を よ り «〖得 る 得 る 得 る. Item 1. On the surface of calcium carbonate, at least one selected from the group consisting of (i) silica layer, (ii) grease j «, grease JJ male salt, grease ester, m, shelf test ester And (iii) a silane cup link J layer provided with a ^^ ratio. Item 2. The calcium potion according to Item 1, wherein the calcium carbonate has a BETit efficiency of 5 to 120 m ² Zg. Item 3. BETl B®l ^ of modified calcium carbonate, 4 to: 賴 ^ 7 lucium according to Item 1, which is I1Om ^ g. Item 4. For calcium carbonate 10 OS *, 0.5 to 15 weight of silica layer is attached. 0.5 to 20 is added for organic mii and silane cup link ^! ! The observation system according to item 1, wherein the dimension of the layer is 0.05 to: 10M. Item 5. A step of (i) forming a silica layer on the surface of calcium carbonate by leaking a silica hydrosol into the calcium sulfate slurry.

 (2) The calcium carbonate slurry provided with the silica layer is supplemented with at least one selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, optionally, and bacterium oxalate. i 0 βϋ

 (3) the steps of: (i) slurried calcium carbonate slurry having a silica layer and (ii) an organic acid layer; and

 (4) A step of forming a silane coupling agent layer by surface-treating the obtained (i) calcium carbonate particles having a silicic acid layer and (ii) a shelf acid layer with a silane coupling agent.

Modified calcium carbonate containing, in particular, ^ i of boat calcium carbonate according to item 1 above Method. Item 6. (a) At least one member selected from the group consisting of (i) silica layer, (ii) fatty acid, fatty acid salt, fatty acid ester, m. (Iii) a silane cup link, a broodless redress system with eyebrows, and

 (b) Polymer

Item 7. The polymer IK¾l according to Item 6, wherein the calcium carbonate has a BET specific surface area of 5 to 120 m ² Zg. Item 8. The polymer according to Item 6, wherein the modified calcium carbonate has a BET specific surface area of 4 to 110 m ² Zg. Item 9. In response to calcium carbonate 100, the sound layer has a thickness of 0.5 to 15 layers. Yes «with« * 0.5 to 20 and silane cup link ^! The polymer M¾J according to item 6, wherein «is 0 · 05 to: L 0 〜. Item 10. The polymer according to Item 6, comprising 5 to 150 parts by weight of the modified calcium carbonate based on 100 parts by weight of the polymer. Item 11, a silica layer on the surface of calcium carbonate, (Ii) an organic acid layer of at least one selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, metamorphic acids, and tannin esters; and (iii) silane cup links ^! The eyebrows are subjected to a process of energizing calcium carbonate into the polymer and then mixing.

Item 1 2. (i) Silica layer and (ii) Fats, fats, JI fiber salt, fats, ester, acid It has at least one suggestion selected from the group consisting of acid esters, and has the property that ¾Λ ¾Λ し ¾Λ ¾Λ ポ リ マ ー ポ リ マ ー ポ リ マ ー ポ リ マ ー ポ リ マ ー 次 い で 次 い で 次 い で 次 い で. Sg removal of the polymer according to item 6, which comprises a step of mixing after measuring the amount of the polymer in the polymer. Item 1 3. Add a silane coupling agent to the polymer, and then select from the group consisting of (i) silica layer and (ii) fatty veins, ginseng fiber salt, S umbrella ester, jujube, resin ^ At least one recommendation is made; "The calcium is encouraged to the polymer!], And then the mixing process is performed." 1 4. What can be obtained by molding the polymer thread described in Item 6? ^. Hereinafter, the present invention will be further described.

 In the present invention, the “layer” refers to all or ^^ of the surface of calcium or calcium salt having one or two of a calcium layer, a silica layer, and a silane coupling agent layer. If the job is to cover the surface, it is not particularly necessary to cover the entire surface with a continuous crane.

 In the permeation film of the present invention, the surface layer has (1) a silica layer, an organic acid layer, and a silane coupling agent layer in this order, and (2) a silica layer and a silane coupling layer. Part, and (3) silica layer, part in the order of organic wake,

(4) Silica layer, organic silane coupling, silane coupling It is estimated that the partial force (in a single layer) 眉 I contained in the eyebrows U is included.

 The thickness of the layers is not particularly limited, and the thickness of each layer is suitable for obtaining desired physical properties. Ganshi Lucium

 In the present invention, the persimmon which is used as a mat is particularly useful in the use of charcoal permeate and synthetic (precipitated limestone, etc.).

Heavy calcium carbonate is made from natural calcium carbonate ore, roller mill, high-speed mill (shoulder mill), pole mill, tumbler, awake pole mill, jet mill ル 用 い る 用 い る 湿 湿 湿 湿 湿 湿 湿. Can be prepared. Synthetic omrn lucium can be obtained by the method of lime milk-¾9s ^^ method, calcium chloride-soda ash Mis method, lime milk-soda ash trace concentration ^]. Milk of lime «、 ス ス ス ス 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 膨 、 、 膨 す る 膨 燃 膨 膨 コ ー コ ー 生 コ ー. By adding the fiber slurry to the fiber slurry and baking the traces of watts generated as an auxiliary to w, it is possible to generate the lubricated slurry. It is powerful to get the desired submission. In addition to this, the salt which becomes 7j <mi «by the force P7j ^> is pumped into the calcium sulfate slurry, and at the same time, the ¾¾'s is published to make the slurry more stable than the above calcium carbonate. A method for producing finer calcium carbonate can also be applied (Course No. 4101044). The raw material «calcium BETi {S}} in the present invention, especially the knee, is usually 5 to 12 Om ^ gS. A more preferred range is 20 to 110 m ² Zg @ ^ T, and a still more preferred range is 50 to; L0 Om ^ key.

 Here, the BET specific surface area can be calculated by detecting P and N of nitrogen gas to calcium carbonate based on a gas adsorption method.

コスト的な問題がある。 脂藤、 脂 腿塩、 脂赚エステル、 綳醵、 樹脂酸驗«鼸エステル〖湖 [^としての作用 もあるので、 ポリマーに対する補^ 果が損なわれるおそれがある。 Raw materials BET warmth of persimmon is too large: ^ is at least selected from the group consisting of citrus, citrus salt, citrus ester, exfoliation, and kichin

There is a cost problem. It also acts as a lipstick, a thigh salt, a fatty ester, a fatty acid ester, a resin acid, and the like, so that the effect on the polymer may be impaired.

 On the other hand, the BET ratio of calcium carbonate as a raw material is too small :! ^ May have a small effect on the polymer obtained by the fine particles, and it may be trapped by the polymer.

The particle size of calcium carbonate can be selected as M31 so as to obtain a desired effect. However, HIS has an age of ^^ electron microscopic fiber, and the raw material preferably has a primary particle diameter of 0.01 to 0.5 m, preferably 0.02 to 0.5. More preferably, it is 4 m @ ^. Silica layer

 In the present invention, the silica layer is a layer obtained by treating with a silica hydrosol. '

 As the silica hydrosol to be inverted in the present invention, those which are difficult by the following method can be used. For example, it is possible to use a silica hydrosol by acid scouring. In addition, add sodium silicate to the fiber acid such as leaks and difficulties, add aluminum, or add spirits such as «@ body, acryl, etc., and other acid f raw materials such as ^ m ^ In this case, an amorphous silica hydrosol can be used. Alternatively, a silica hydrosol which is formed by permeation through sodium silicate when it is awake can be used. It is also possible to use silica hydrosol generated by the ions used.

 Examples of the treatment of calcium carbonate with a silica hydrosol include, for example, adding an appropriate sodium gamate to a difficult calcium slurry, and adding an appropriate substance such as ^ < Silica hydrosols can be used to climb the surface of the rudium.

 The age at which the silica hydrosol prepared beforehand is used can be increased by adding silica hydrozole to the calcium carbonate slurry by adding π and strongly ».

 As the calcium carbonate slurry, those having a solid content mo. Of 5 to 20%, preferably:! To 15% © J are used. Sodium silicate aqueous solution is about 1 to 40%; ^ used. Charcoal »Damage of sodium gayate to solid content of calcium slurries I Pick up is 11.3% to 200%.

The silica in the silica hydrosol attaches to the calcium carbonate in a manner that is approximately ¾M. The silica hydrosol according to the present invention has a good adhesion to the calcium, particularly, the amount of silica obtained from the silica hydrosol attached to calcium is 100 parts by weight of the raw material calcium carbonate. And usually 5 to: L5 heavy movement | ^, more preferably 1 to 12 gg | ^, and still more preferably 2 to 10 m * g | 5fii¾. The amount of silica hydrosol to be deposited is adjusted according to the BET specific surface area of calcium carbonate, which is the sticking point of the silica hydrosol. Too little silica is obtained from the silylation hydrosol adhering to calcium carbonate: ^ is too small to supply silane coupling # 1, and the desired rubber properties may not be exhibited. On the other hand, at the age of too many sticks, the silica hydrosol used to attach to the surface of calcium will be included in the note, so that the silica hydrosol strongly solidifies the ^ 7 calcium and is difficult to grind. ¾ »: Particles increase. The reversible spill containing such dust particles may reduce the erosion of the polymer and the resistance to flex cracking. Yes

 In the present invention, the shelf is a layer obtained by performing at least one step selected from the group consisting of fatty acid, fatty acid salt, fatty acid ester, resinic acid, and water-soluble ester.

 According to the present invention, the fatspots to be stored in the present invention can be picked up from 24 to 24, especially from 10 to 20 or a silent J ^ JM mosquito.

 Saturated or unsaturated fatty veins of 6 to 24 carbon fibers include, for example, stearic acid, palmitic acid, lauric acid, behenic acid, oleic acid, eric acid, and Rino-J. Can be mentioned. In particular, stearic acid, palmitic acid, lauric acid, and oleic acid are preferred. These may be used in a mixture of 2 @ ¾.

Examples of the salt of fat proof include, for example, sodium salts of 6 to 24 carbon atoms, especially sodium salts and salt salts of saturated or unsatisfactory fatty acids having 10 to 20 carbon atoms. I can do it. As also esters of fatty acids, for example, the number of carbon atoms of 6 to 2 4 about a fat膽particularly 1 0-2 0 saturated or unsaturated,賺^, alcohol ₆ to _{1 8}纖, Fujisu especially 10 to 18 saturated fats and alcohol esters.

 As a method of buffing with greasy fat, grease and / or grease ester, for example, the following can be performed.

 First, the fatty acid is tested (converted to a metal salt such as Na salt or K salt) while heating in an alkali metal aqueous solution such as an NaOH aqueous solution or a K 水溶液 H aqueous solution to form a solution.

The amount of the aqueous metal solution is not particularly limited as long as it is necessary to convert fatty acids. The concentration of the aqueous alkali metal solution is about 1 to 40%, preferably about 1 to 20%. Then, an aqueous suspension of calcium carbonate on which a silica layer has been formed is previously heated to 30 to 50 t :, and the above-mentioned fatty acid stone 鹼 is added to this suspension and stirred. And mixing to form an organic acid layer containing fatty acids and Ζ or fatty acid salts. The proportion of the fatty acid stone added to the aqueous suspension of calcium carbonate is about 10 to 70%, preferably about 10 to 50%.

 As for ^^, where stones such as fatty thigh Na are to be shelf as they are, prepare a pre-heated water paste and treat it in the same manner as above.

 In addition, it is possible to perform the summarization without using the fat and tears. For example, by heating the permeate with the silica layer in the! ^ State while heating the 脈 $ Λ¾¾ ± of the fat veins, excite and read the fat, and mix it with the fat. A vein including a pulse can be formed.

 The resin acids used in the present invention include, for example, abietic acid such as abietic acid, dehydroabietic acid, and dihydroabietic acid or a polymer thereof # disproportionated rosin, hydrogenated rosin, polymerized rosin, and salts thereof (for example, Alkali ^^, alkali! ^ Genus ^) or ester (eg rosin pentaerythritol 'ester, rosin dalicerol ester, hydrogenated rosin methyl ester, τΚ added rosin triethylene glycol' ester, hydrogenated rosin penta Erythritol 'ester) Among these, abieticin and dehydroabietic acid are preferred.

 As a treatment method using a resin acid, a resin acid or a resin acid ester, the same method as that for the fatty acid, the fatty acid zombie Z or the fatty acid ester can be used. Specifically, the resin acid is heated in an aqueous solution of an alkaline metal such as an NaOH 7K solution or an aqueous KOH solution to be tested (converted to a metal salt such as an Na salt or a K salt) to form a solution. To

The amount of the aqueous metal solution is not particularly limited as long as there is an amount necessary for curing the resin acid. The concentration of the aqueous alkali metal solution is about 1 to 40%, preferably about 1 to 20%. Next, the aqueous suspension of calcium carbonate on which the silica layer has been formed is previously heated to 30 to 50 ° C., and the above-mentioned resin oxide in the form of a solution is added to this suspension, followed by stirring. Then, they are mixed to form an organic acid layer containing a tamper acid and Z or a resinate. The addition ratio of the resin acid stone to the water suspension of calcium carbonate is about 10 to 70%, preferably about 10 to 50%. When using stones such as resin acid Na as it is, prepare a pre-heated resin acid stone Mizunada, and perform step ① in the same manner as above.

 Further, the treatment can be carried out without using the resin acid. For example, the silica layer-formed lucium is in the state of 棚, and the 棚 is contained in the mixture by adding the 綳 to the mixture, mixing the »with the 以上, and mixing. «The ability to form g.

 The amount of Tanito, that is, at least one kind of basket selected from the group consisting of ginseng, ginseng fiber salt, ginseng ester, fibers, mm fl este, is particularly p kneeling. Normally, it is 0.5-20S * for the permeate 10 as a raw material. More preferably, 1 to: 15Μ¾0 | ^, and still more preferably, 2 to 12 Silane coupling

 The silane cup link layer in the present invention is a layer obtained by treating with a silane force link ^ !.

Examples of the silane coupling according to the present invention include biertrichlorosilane, bieletrimethoxysilane, biertriethoxysilane, biertris (β-methoxyethoxy) silane, and β- (3,4-epoxycyclohexyl) ethyltrimethy Xysilane, α (2-aminoethyl) aminopropyltrimethoxysilane, αglycidoxypropyltrimethoxysilane, αglycidoxypropyltrimethyljetoxysilane, αglycidoxypropyltriethoxysilane, αmethacryloxy Propyl methyldimethoxysilane, α-methacryloxypropyl trimethoxysilane, α-methacryloxypropyl methyl ethoxysilane, α-methacryloxypropyl triethoxysilane, Ν- / 3 (aminoethyl) amino Propylmethyldimethoxysilane, Ν-β (aminoethyl) aminopropyltrimethoxysilane, Ν- / 3 (aminoethyl) aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, e-phenylaminopropyletrimethoxysilane, achloropropyltrimethoxysilane, amercaptopropyltrimethoxysilane, bis- (3- [triethoxysilyl J-re] prohirile) —Tetrasa ^ / Fan (TE S PT), bis- (3- [triethoxysilyl] -propyl) 1,: ^ Lupane, etc. can be mentioned.

 In particular, α- (2-aminoethyl) aminopropyl trimethoxysilane, 3-aminobutyrate pyrethleethoxysilane, Ν_] 3 (aminoethyl) aminopropyletrimethoxysilane, α-mercaptopropyltrimethoxysilane, Bis- (3- [triethoxysilyl] monopropyl) mono-tetrasulfan, bis- (3- [triethoxysilyl] -prohirile) Disalephane

 In the present invention, the method for treating calcium carbonate using the silane cup link ^! 1 is capable of exposing various surfaces known in the art without being particularly kneel. The age at which the permeate through the silica layer is leaky can be overcome, for example, by overcoming this permeate in the mix and spraying the silane cap with a spray or the like. It can be used to apply silane coupling to the surface of the rubber. this:! ^, If necessary, heating may be performed after surface treatment.

In addition, when the calcium carbonate that forms the silica layer and the acid layer is disturbed in the state of β-solution, this suspicious silane cup link is applied, and the silane cup link is placed on the surface of the permeate. The surface wall is formed by adsorption, and then the treated material is separated by filtration, followed by sintering, so that the lithium obtained by the silane cup link can be sitted. Also,

Alternatively, silane coupling may be added to this. For certain ages, wet mills such as i ^ im or bead mills or sand mills may be used to make the coating even. .

 The amount of the silane coupling agent that forms the silane coupling agent layer is not particularly limited, but is usually in the range of 0.05 to 10 baskets per 10 parts of the raw material. ^, Preferably 0.07-5S * g | ^ l, more preferably 0.1-3 weight%. The adhesion amount is adjusted according to BETl efficiency of the J-Resistance to which the silane coupling agent is attached.

カ ル シ ウ ム Calcium carbonate の The calcium carbonate of the present invention is obtained from (i) a silica layer, (ii) fat veins, fat salts, fat fat esters, resin acids, and shelf acid acid esters on the surface of difficult-to-make calcium as a raw material. And at least one organic acid layer selected from the group consisting of: (iii) a silane coupling layer.

 The watch in the present invention can be operated in the following manner.

 For example, (1) a step of forming a silica layer on a luster surface by adding a silica hydrosol to a permeate slurry to form a silica layer, and (2) adding a grease to the permeate slurry provided with the silica layer. «Ester,, mmp ^ at least one selected from the group consisting of acid esters, π to form a ^

(3) The process of slurping the coal slurries forming the silicide layer and t ^ WB, and (4) spheroidizing the obtained sulphide particles by silane coupling 1 to obtain a silane coupling. This is a method for forming a J layer.

 The modified calcium salt of the present invention is characterized by having (0) a silica layer, (ii) an organic acid layer, and (iii) a silane coupling layer on the surface of the desired calcium particles by the TO method. .

The BET specific surface area of the calcium carbonate obtained in the present invention is usually 4 to 110 m ² / g sq. A more preferred range is about 15 to 100 m ² g, and a still more preferred range is 40 to 90 m ² gS ^.

 The BET ratio can be calculated by detecting the absorption of the crane gas into the limestone based on the gas adsorption method.

 If the modified calcium carbonate has an excessively large BET ratio, the feeding of the modified bowel to the polymer may be impaired. On the other hand, if the BET ratio of the treated sorghum is too small, the effect obtained by the fine particles may be small, and the supplemental effect of the polymer blended may be reduced.

In addition, the vertical diameter of the modified potassium carbonate in the present invention can be adjusted for the purpose of obtaining a desired effect. The primary particle size is preferably from 0.01 to 0.6 ml, more preferably from 0.02 to 0.5 mgJt. Polymer WI;

 The polymer M / of the present invention can be obtained by blending the above-mentioned modified calcium carbonate of the present invention with a polymer such as rubber or plastic.

The blending amount of the modified calcium carbonate in the polymer is not particularly limited, but the polymer is usually 100 M¾, but usually 5 to 150Μ ^ | ^ Τ, preferably 3 ο to ι 2 o mm, more preferably 5 o-ii

 An excessively large amount of the modified calcium carbonate relative to the polymer is not preferable because the fluidity of the polymer is impaired. In particular, the rubber, which is a polymer, is lost, and workability is reduced. There is also a lack that it becomes too carrying. On the other hand, if the distribution is too small, it is not preferable because the bending efficiency of the polymer and the bowing boat are good. Particularly, the polymer is rubber; Is too small to achieve the desired physical properties.

 As the polymer in the cured polymer of the present invention, for example, a natural rubber, a synthetic rubber, a recommended fat, a thermoplastic elastomer, or the like can be used.

 Natural rubber is a high-quality rubber-like material obtained from products.

— As long as it has a 1,4-polyisoprene structure, the m tone is not particularly limited.

 Synthetic rubbers include, for example, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, fluoro rubber, cross-linked sulfonated polyethylene, Examples include picrohydrin rubber and polysulfide rubber.

As the compound bell resin, both a thermoplastic resin and a gadget can be used. Examples of the thermoplastic resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, audio polyethylene, ultra-high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate. Copolymer (EEA), ethylene-propylene copolymer # propylene homopolymer, ethylene-propylene rubber, polybutene, butyl rubber, high impact polystyrene (HIPS), polystyrene (P S), ABS, Shiridani Pinyl Resin, Methacryl J-Res J3, Methyl Methacrylate (MMA)-Styrene Copolymer Polyamides such as polyamide 6, polyamide 66, polyamide 6 10, polyamide 12, polyamide 46 Polyester such as resin, polycarbonate, polyacetal, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyaryl ether ketone, polyamideimide, polyimide, polyethery Examples include mide, polysulfone, polyestersulfone, fluororesin, polyurethane, ionomer, polyvinylidene chloride, polyethylene, polydicyclopentadiene, methylpentene resin, and polyacrylonitrile. Power to do. Examples of the sacrificial resin include phenolic resin, bisphenol A type epoxy resin, cresol nopolak type epoxy resin, f resin, phenol nopolak type epoxy resin, fat, bisphenyl type epoxy resin, fat, naphthale epoxy resin, Allyl phenolic novolak type epoxy resin, if fat, epoxy resin, #fat, ^^^: epoxy resin such as epoxy resin and their halogenated compounds, polyurethane (for products), furan resin, fubo n polyester, Examples thereof include melamine resin, m, aryl resin (DAP), polyimide, and gay resin (thermosetting b).

 Examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers, polypropylene-based thermoplastic elastomers, polygen-based thermoplastic elastomers, thermoplastic thermoplastic elastomers, and engineering plastics-based elastomers. I can do it.

The polymer containing the modified calcium carbonate of the present invention includes, for example, (1) (i) a silica layer,) fatty acid, fatty acid salt, fatty acid ester, sm, and transic acid. A method of adding $ βt by blending at least one organic β selected from the group consisting of esters and (iii) ^ calcium of the present invention forming a silane coupling agent layer with the polymer, or 2) The part before the silane cup link ^ ij is applied to the ¾κ charcoal m¾sium, that is, (i) silica layer and (ii) grease, grease fiber salt, grease ester, shelf, test acid At least one organic compound selected from the group consisting of esters can be obtained by a method in which calcium and silane coupling agent J are mixed into a polymer and mixed with B. In the method (2), specifically, the portion where the ω-silica layer and the () -short acid layer are formed is prepared by adding calcium to the polymer, further adding silane coupling to the polymer, and then mixing. I can do it. Alternatively, the silane coupling pin ij is urged to the polymer, and then (i) the partially modified layer of the organic layer and (ii) the organic acid layer is leaked into the polymer, and then mixed and observed. You can climb.

 As mentioned above, the ω-silica layer and the organic calcium carbonate and the silane cup link ^! 1 should be mixed with each other after plowing each of them. As a result, (i) a silica layer, (ii) a partially modified coal having organic MS »silane coupling is adsorbed on the surface of the lithium, and (i) a silica layer, (ii) an organic acid layer, and (iii) Silane Cup Link Coal calcium is formed in the three layers of the eyebrows, and it is a polymer blended with high molecular calcium.

 (i) Silica layer and (ii) Calcium and silane cutlet ^! J are plowed into polymer in S-paint ITT: ^, (i) Silica layer, (ii) Yes and (iii) Silane The amount of the silane coupling agent used for forming the calcium salt is from 0.05 to 10 weights per 100 weight of the raw material calcium carbonate.

 It is preferably 0.07 to 5 times * g | ^, more preferably 0.1 to 3 times. The polymer pirates of the present invention may further contain, if necessary, a compounding agent. For example, other materials such as silica, clay, and aluminum can be used in combination. Further, an additive π agent such as process oil, antioxidant, aging preventive, stearic acid, mi, wax, etc., and a raw material such as vulcanization, etc. can be blended as required.

 The polymer product of the present invention can be obtained by subjecting the polymer, the modified calcium carbonate and, if necessary, the above-mentioned compounding agent to Ori-ori, hot extrusion and heating.

There are no particular restrictions on the conditions of the loach east, and the conditions of ¾λ 碰 to the ori east, rotor rotation, ram pressure, etc. «M according to There is no particular limitation on the kneading device, and any of closed type or open type can be used. For example, 織 woven butterfly device, specifically, bread pal mixer-quotient ^), intermix (^ Quotient, kneader, lori] ^ it can.

 Heating conditions are not particularly limited. Heating ^^ Heating: During s #, jiim can be performed depending on the purpose of xn m. As the heat input device, for example, a spleen such as a roll machine is used.

 The conditions for the extrusion are not particularly limited, and the extrusion time, the extrusion, the extrusion device, and the extruder temperature can be adjusted according to the purpose. As an extruder, for example, an extruder used for extruding rubber for tires / is used.

The molded article of the present invention can be obtained by applying the modified calcium carbonate-containing polymer of the present invention by various known methods.

 Examples of the molding method used in the present invention include, for example, calendering, extrusion, and the like for rubber products, and injection «, jBi molding, transfer molding, extrusion«, and professional molding for Resin®a. Molding, calendering, etc.

 For example, in the case of a resin, a film or sheet-like body can be obtained by subjecting the polymer of the present invention to force rendering or extrusion molding. By applying the shape, it is possible to obtain heat ^^ For example, by dissolving an unfavorable 3 polymer into pellets to obtain pellets, and then subjecting the obtained pellets to injection molding or blow molding, Injection moldings or hollows can be obtained respectively.

 In the case of rubber, after the above-mentioned molding, vulcanized rubber can be obtained by molding vulcanization, shouting, direct or indirect steam vulcanization, or high-frequency propulsion fiber. The device for performing the heating and the m-stripe can be tailored to the particular purpose.

The grown ginseng of the present invention contains the calcium carbonate of the present invention, so that it is excellent in mechanical properties, wear resistance, and humility of permanent elongation. It can be converted for use as a tube. Best Mode for $ ¾ · τ Invention

 Hereinafter, the present invention will be described with practical difficult examples and examples, but the present invention is not limited to these examples.

 In the following difficult examples and I: 瞧, the silica hydrosol was prepared by adding an acidic substance to a sodium silicate solution (warm ^^, 193-08185).

 Ji The JMs include fats and oils containing oleic acid, stearic acid, and palmitic acid (sum) ^ ¾ », oleic acid (159-00246), stearic acid (199-10995), and palmitic acid (165- 00102)) was used.

 As the idiot, abietic acid ^^ m, 017-00011) was used.

 As the silane coupling agent, 3-aminopropyltriethoxysilane

(S-330, manufactured by Chisso Corporation) was used.

 In the following examples and comparisons, “%” indicates unless otherwise specified.麵 Example 1 '-

ΕΊ¾¾ Synthesis of 80πι ² / ^ ¾ Calcium slurry (solid content: 8%) was heated to 40 ° C while being sprayed well. At room temperature, 10% OM ^ B of the slurry is treated at room temperature with 3% sodium gayate aqueous solution as silica for 7S and 3.5% for 7 days with sodium silicate. And a silica layer was applied to the surface of the water.

 Next, sodium hydroxide was added, the mixture was stirred at 90, and the mixture was oxidized, and the mixture was converted to sodium bristles by 5≤ * g. Using 80 micron conditions, the obtained was subjected to micron milling using a micrometer mill (Super Micron Mill, Supermicron Mill) to produce a key calcium powder having a silica layer and ^ Ml.

While mixing this calcium carbonate powder with a mixer, an amount of 3-aminopropyltriethoxysilane (manufactured by Chisso Corporation, S-330 ), And after stirring for 10 minutes, 100. CX was heated for 60 minutes to prepare the calcium of the present invention. Table 1 shows the amounts of silica layer, organic acid layer and silane coupling agent layer in the obtained modified calcium carbonate per 100 mM of raw material.

 To the synthetic rubber (styrene butadiene rubber (SBR), 1502), the face-resistant calcium obtained by the above-mentioned method was added to the rubber 10 Og * g in an amount of 10 0 This roll was subjected to IH bonding under the conditions of T40 to 50 ° C to prepare the polymer of the present invention. Difficult case 2

In Difficult Example 1, a BET specific surface advisor of 0 m ² Zg was used, and a slurry of 3% sodium silicate was used as silica, and 5M¾, and the amount of mixed oil was used as 2.5. Of the present invention I got Lucium. Table 1 shows the amounts of the silica layer, the organic acid layer, and the silane coupling agent layer in the modified calcium carbonate obtained, per 100 parts by weight of the I material.

 Synthetic rubber (Styrene-butadiene rubber (SBR), 1502) To 100 kumbe, 35 quality resin 10 OS ^ obtained by himself was compounded in the same manner as in Example 1 to obtain a polymer. It was created. Difficult case 3

 4 o while removing the synthetic calcium carbonate slurry (solid content: 8%) with a BET specific surface area of 8 Om ^. Heated to c. At room temperature, 10% of the total calcium in the slurry was added with 7% silica at room temperature and 3% sodium silicate was added to the mixture, and 3.5% of sodium silicate was added in bulk to form a mixture of sodium gayate. By introducing the silica layer, a silica layer was formed on the surface of the ruthenium. After 5 minutes of oil J3 «^ ¾ was added to the obtained ^ 7 lime slurry having the silica layer, and the same as in Difficult Example 1, the soil was applied and calcium carbonate having a silica layer and A powder was made.

 The synthetic rubber (SBR1502) was treated with the silica layer obtained by the above-mentioned method and the silica gel having the reversibility, and the rubber 1 mm was described in Example 1 with difficulty; It was blended in a similar manner.

Then, 3-aminopropyltriethoxysilane (produced by Chisso Corporation, S-330) was directly polymerized in an amount of 1. IM ^ to the raw coal, calcium 10 osa ^. Then, the mixture was mixed to prepare a polymer composition of the present invention containing the face of the present invention.

 Table 1 shows sticks per 100 parts of the raw material of the silica layer, the shelf acid layer and the silane coupling agent layer in the obtained calcium carbonate. Difficult case 4

 In Difficult Example 1, a resin and a polymer were obtained in the same manner as described above except that the resin acid was used in place of the fatty acid.

 Table 1 shows the amounts of the silica layer, the organic acid layer and the silane coupling agent layer in the obtained modified calcium carbonate per 100 parts by weight of IT material. Ratio shelf 1

BET specific surface area 80m ² Zg Calcium phosphate slurry (solids concentration 8%), 5% * of fat and oil for 100% ≤ * part of the slurry in this slurry. In the same manner as in Example 1, s½7 m was added to the mixture to prepare an organic leakage curette.

 、 In the same manner as in Example 1, the synthetic rubber (SBR1502) was modified with the above-mentioned bridging mechanism by adding a part-modified part of ル / lucium to 100 parts by weight of the rubber. The polymer was created according to the weight sound. Comparison

A synthetic calcium carbonate slurry (solid content: 8%) having a BET specific surface area of 80 m ² / g was heated to 40 with good ». To 100 parts by weight of this total slurry in the slurry, 7 parts by weight of a 3% aqueous solution of sodium silicate as silica was added at room temperature, and 3. was added to neutralize sodium silicate. To form a silica layer on the calcium carbonate surface. ■

In the same manner as in Difficult Example 1, the synthetic rubber (SB1502) is coated with the above-mentioned silica layer containing partially modified carbon resin, and the rubber 100 The mixture was mixed to make Polymer W¾l. While mixing the fatty acid prepared in the comparison l with calcium chloride, 3-aminopropyltriethoxysilane (S-330, manufactured by Chisso Corp.) was added to the raw material ^ 7 r.d. 1. The mixture was exfoliated in an amount of 1 part, heated for 10 minutes, and then heated and dried at 100 ° C. for 60 minutes to prepare a partial resin having an organic acid layer and a silane coupling agent layer.

 部分 In the same manner as in Example 1, a synthetic rubber (SBR 1502) is blended with the above-mentioned material and a partially sulphide having a silane coupling agent layer in a manner to remove 10% of the rubber from 10% of the rubber. "created.

J: Kan 4

 To the calcium carbonate prepared in Comparative Example 2, 3-aminopropyltriethoxysilane (manufactured by Chisso Corp., S-330) was added to calcium carbonate, which is 1.1 parts by weight based on the material lOOSS ^. The resulting mixture was stirred in 10 minutes and heated at 100 ° C. for 60 minutes to produce a silica layer and a silane coupling layer (J) layer.

 ^ In the same manner as in Example 1, the synthetic rubber (SBR 1502) was partially married with the partially modified curdium having the above silica layer and silane coupling agent layer to 100 ≤ * Created. Comparative Example 5

BE Ti ¾®¾4m ² / g total calcium slurry, 1% calcium 100S¾ ^, 3% sodium gayate water as silica 2 fiber lottery A silica layer was formed on the surface of the permeate. While stirring this lucium with a mixer, 0.3S * ^ of 3-aminobutyl piltriethoxysilane was urged against the calcium carbonate 100 weight * 5 used as a raw material, and after winning for 10 minutes, 100 Heating and drying for 60 minutes were performed to produce partially modified calcium carbonate having a silica layer and a silane coupling agent layer. In the same manner as in Example 1, the partially modified calcium carbonate having the silica layer and the silane coupling agent layer was added to the synthetic rubber (SBR1502) by 100 weight per 100 weight of the rubber. Then, a polymer was prepared. Comparison

As a translation, we used wet silica (Nippon Silica Dish Nip Seal VN 3) with a BET specific surface area of 175 m ² / g.

 The above wet silica was combined with rubber (SBR1502) 10OOSM ^ at 40g ^ | ffi to prepare a polymer. In the polymer, the reason why the composition of the filler whose base is persium is different from that of the silica is to match the composition of the vulcanized rubber. In addition to the polymer prepared in Examples and Comparatives ^ !, 5 parts of ¾ 、, stearic acid singlet * ¾, vulcanizing agent DM (Dibenzothiazyl disulfide) 1.2 parts by weight, vulcanization TS (tetramethyl thiuram monosulfide) 0.2 parts by weight, sulfur double:: ^^: by mouth ^ | east to obtain a compounded rubber. J WJ6 wet silica alone also added jettyrene recall in addition to these.

 The obtained unvulcanized rubber was subjected to an oscillating disk rheometer: t c (90) between mouth and mouth was calculated, and press-crosslinking was performed at this time to obtain a press vulcanized sheet.

 The following methods were used for the physical properties of each polymer IWt; and press sheet.讓

 1. Tensile test

 The following test items were measured in 23 using the shopper tensile strength に 従 っ て according to the male specified in JIS K 6251.

3 0 0% modulus M _∞:引彌own at the time of 3 0 0% I monkey length

500% modulus M: 500% ί tensile strength at length Tensile strength T _B : Value obtained by dividing the finish of cutting by trial Elongation Ε _Β : Elongation of cutting

2. Hardness

 According to the method specified in JISΚ6253, 碰 ^ 13 (Type A) at 23 ° was measured.

3. Fiber

 According to the method set forth in JISK 6252, the measurement was performed at 23 using a Shopper tensile test. ¾l is a Kunt type.

4. Resistance to heat

 According to the method prescribed in JISK 6264, using Akron ^^ M manufactured by Shimadzu Corporation, under the conditions of a load of 6 1 b and an angle of 15 °, preliminary rubbing 200 times, rubbing 1 0 0 0 I checked ^^ «at times.

5. Flex crack resistance

 In accordance with the method specified in JIS K62060, the number of bends (cycles) was measured using a Ueshima Seisakusho's Demachia Flex until the flex at the time of flexure became 10 mm. The l-thickness used was 6.3 mm and the flexion was 300 times. The cut-off fiber is 5 5 7, the sword: 隱 is 75 5.

6. Practice elasticity

 According to the fineness specified in JIS K 6255, the value at 23 ° C. was measured using a Lupke fiber optic device. Try! The thickness of 1 was 12.5 mm and the diameter was 29 mm.

7. Permanent elongation

The shape of the dumbbell was 1 and the marked line was 40 mm. Cut at tension Elongated 50% of the instantaneous elongation and worked in this female for 30 minutes. After 30 ^ ¾i, external force was removed and the sample was left still for 30 minutes, and the residual elongation at this time was measured. As a result, the residual elongation with respect to the original length (40 mm) is expressed as a percentage.

8. Roll workability

 The roll calorie property was inferred from the ease of winding the polymer ffi ^ ti around the roll at the time of rubber weaving. ^ ¾ ^^: The larger the roll, the harder it is. On the consultation side, the degree of winding of the polymer at the time of satisfaction was evaluated.

A: Very 舰

B: mochi

C: Somewhat good

D: Bad

E: Very poor results are shown in Table 1.

A L

 it! father shelf 1 M A

w ^l \ m] Ty'J I w \

Coking coal

面積 Area [m ² / g] 80 40 80 80 80 80 80 100 4

Wet silica [m ² / g] 175

【Layer structure】

 , Rika "Lightning ¾Ί 7 / \ 7 ι 7 l 7/7 /

Fatty acids "Heavy ϋ

Resin acid lightning ¾¾1 J R

ΆKatsutsu. ¹ agent Γ "¾¾β1 1 1 1 1 1 1 1 1 1 .1 1 1.11

Rekoko trwjiij

 «300% Monhus LMPaj 4,2 5.4 6.4 4.4 1.2 1.4 2.4 6.1 2.4 2.2

¾UU% Monhus L Paj 9.6 11.9 14.3 9,9 2.1 2,4 5.4 10.7 3.5 4.1

 `` MPa1 171 J7 lO.f IO.O i IOQ.fU) IU.U Q 7 Ι .0 O.o M, ά Elongation [%] 680 610 550 670 900 880 690 540 740 740 860

 65 64 69 66 59 60 61 73 64 67 Bow 1 tear strength [N / mm] 37.4 32.8 36.4 41.9 18 20 23.6 50.1 17.1 41.5 Hair resistance [cc / leakage] 0.40 0.37 0.60 0.42 0.60 0.50 0.51 0.40 0.95 0.43 Flexibility «resistance [Kc 2 → 10] 1.0 1.0 1.5 1.2 1.5 1.2 1.5 3.3 <1 3.4 Rebound resilience [%] 46 51 46 46 45 45 46 40 55 49 Permanent elongation [%] 5.6 2.5 5.1 4.9 11.8 9.0 5.9 15.0 9.8 21.7

[Roll processing 14] ABAAAEAEAE As shown in the results in Table 1, the polymer blended with 匿 S calcium carbonate shown in Example 14 shows that the white curl of physical properties such as tensile strength and key I had a | Z5¾T It was also excellent in permanent elongation and roll workability, which are the lack of white carbon.

 On the other hand, only the fatty limestone layer shown in Comparative Stitch 1: Polymer containing calcium carbonate, which does not have sufficient physical properties in terms of modulus, ¾s, bow 1 Was.

Polymer containing calcium carbonate with only a silica layer as shown in Comparative Relative 2! § «| could not be sufficiently degraded in terms of physical properties such as modulus, strength, and tensile strength. Also, Rori's winding condition was bad. In the polymer containing calcium carbonate having only the fatty acid layer and the silane coupling agent layer shown in Comparative Example 3, satisfactory results were obtained in terms of the mimic properties such as modulus, transport, and tensile strength. It was easy.

 The polymer iwti containing calcium carbonate having only the silica layer and the silane coupling agent layer shown in Comparative Example 4 had insufficient physical properties with respect to mechanical growth such as 7 elongation. In addition, the wrapping around the roll was poor and the roll workability was poor. As shown in Fig. 5, the polymer containing BETit surface crane M, silica layer and silane coupling agent layer containing only calcium has low strength such as penetration, bending resistance, and anti-seizure properties. Les r Enough physical properties Shame was good.

 In addition, polymer pirate, including the white ri-bon, which is shown in Fig. 6, was humiliated enough in terms of modulus, permanent elongation, and other powers. Further, the roll workability was sufficient.

^ i: Availability

 The calcium in the present invention has at least one member selected from the group consisting of (i) a silica layer on the surface thereof, and (ii) a fat ester, a fat salt, a fat ester, a transester, or a jujutsu test confirmation ester. It has a functional organic layer, and further has a (source) silane cup link ^ I ”layer.

 For this reason, the polymer containing calcium carbonate of the present invention exhibits high strength and high elongation as compared with the polymer containing white carbon, and also has excellent permanent elongation and roll processability. Also, since the drying of coal and calcium is suppressed, there are few difficult coarse particles.

 The modified calcium carbonate of the present invention ## having such excellent properties and the polymer containing the same can be usefully used for applications such as tires and tires.

Claims

The scope of the claims 1. On the surface of calcium carbonate, (0 silica layer, (ii) at least one organic ^^ selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, ) Silane Cup Link A scheme that has eyebrows. 2. B ET ratio Table calcium carbonate, 5~1 ² 0 m 2 calcium Zhong mounting serial to claim 1 which is Zg. 3. modified charcoal »Rushiumu of ΒΕΤί: ® ^ 4~; Rushiumu according to claim 1, wherein the L 1 0m ² / g. 4. Calcium carbonate 10 OSM ^, the silica layer with M is 0.5-part, the M with M is 0.5 ~ 2 Q≤ * part, and the silane cup link ^ J layer is with The oscilloscope according to claim 1, wherein L is 0.05 to L OSagP. 5. (1) A step of forming an ω silica layer on the surface of calcium carbonate by leaking silica hydrosol into the calcium carbonate slurry,  (2) The calcium carbonate slurry provided with the ω-silica layer is added to at least one selected from the group consisting of butcher, fatty acid salt, fatty acid ester, resin acid, shelf acid; Adding a seed, (ii) forming an organic acid layer,  (3) a step of dehydrating and thighening the calcium carbonate slurry provided with (i) a silica layer and (ii) an organic acid layer, and  (4) A step of forming a silane coupling agent layer by subjecting the obtained (i) silica layer and (ii) calcium carbonate particles having an organic acid layer to a surface treatment with a silane coupling agent. Envelop the curricularism ^ t ^ method. 6. (a) On the surface of calcium carbonate (i) Silica layer, (ii) Fat JW, Fat «salt, Fat ester, Hide! ^ At least one member selected from the group consisting of unrecognized esters, and (iii) ¾M calcium carbonate having a silane coupling layer, and (b) Polymer # "Including polymer!« 1. 7.

7. The polymer according to claim 6, wherein the amount is 5 to 120 mg. 8. The polymer according to claim 6, wherein the modified calcium carbonate BETJt¾®¾ is 4 to 110 m ² Zg. 9. For 100 parts by weight of calcium carbonate, the amount of silica layer attached is 0.5 to 15 baskets, and the amount of attached is 0.5 to 20 SM¾ and silane cup link ^! The stick of the handle 0.05 to: The polymer according to claim 6, which is a L0S part. 100. The polymer according to claim β, wherein the polymer contains 5 to 150 parts by weight of the modified calcium carbonate based on 100 parts by weight of the polymer. 1 1. On the surface of calcium carbonate as a raw material, at least one selected from (i) silica layer, (ii) fatty acid, fatty acid salt, fatty acid ester, sequestration, tree fl A step of extruding the polymer with a modified carbonic acid solution having one kind of organic acid layer and (iii) a silane coupling agent layer, and then mixing the polymer. 1 2. (i) silica layer and (ii) at least one organic compound selected from the group consisting of fatty acid, fatty acid J, transport salt, fatty acid ester, resin acid, acetic acid, and isolated ester. Modification of calcium into polymer, then silane coupling agent into polymer 7. The @itm of the polymer yarn fiber according to claim 6, wherein a mixing step is performed after the inversion.  1 3. Add silane cup link ¾J to the polymer, and then add (i) silica layer and (ii) fat wisteria, fat J «^, fatty acid ester, butteric acid, and fine polyester. 7. The method according to claim 6, wherein a step of adding a mixture of at least one selected organic compound to the polymer and then mixing the mixture is performed. 1 4. A condition obtainable by molding the polymer according to claim 6