JP4373386B2 - Inorganic filler for chlorine-containing polymers - Google Patents

Description

  The present invention relates to an inorganic filler for a chlorine-containing polymer blended with a chlorine-containing polymer such as a vinyl chloride resin.

  Chlorine-containing polymers typified by vinyl chloride resin are excellent in economic efficiency, moldability, and processability and are used in many applications. It is expected to be applied to building materials such as window frames formed by profile extrusion.

  However, as a matter of course, building materials such as window frames are required to have impact strength, bending strength, elastic modulus, and dimensional stability as basic characteristics. Chlorine-containing polymers such as vinyl chloride resin are Since the basic characteristics are unsatisfactory, the use is limited at present.

Various proposals have also been made to improve mechanical properties of vinyl chloride resins and the like. For example, Patent Document 1 discloses vinyl chloride resins, elastomer modifiers, specifically methyl methacrylate-butadiene. -A vinyl chloride resin composition containing a styrene copolymer, chlorinated polyethylene, an acrylic modifier, and the like has been proposed.
JP 2003-73518 A

  When an elastomer-based modifier is blended as in Patent Document 1, although the impact strength can be improved to some extent, the actual situation is that further improvement in impact strength is required. Further, with the improvement of impact strength, there is a problem that the bending strength and the elastic modulus are lowered, and the dimensional stability is lowered due to the reduction of these characteristics.

  In order to improve the dimensional stability, it is usually effective to mix various inorganic fillers such as silica and calcium carbonate, but the blending of these inorganic fillers leads to a reduction in impact strength. Eventually, a vinyl chloride resin composition that is improved in flexural strength and elastic modulus as well as impact strength and excellent in dimensional stability has not yet been provided.

Therefore, the object of the present invention is to improve the impact strength by using in combination with an elastomer-based modifier, and at the same time for a chlorine-containing polymer capable of improving the elastic modulus while maintaining the bending strength. It is to provide an inorganic filler.
Another object of the present invention is to provide a method for producing the above inorganic filler for chlorine-containing polymers and a chlorine-containing polymer composition containing the inorganic filler.

  As a result of various studies on the mechanical properties of chlorine-containing polymers typified by vinyl chloride resins, the present inventors have obtained a mixture of calcium carbonate and kaolin prepared by mixing under certain conditions. The present inventors have found a new finding that the above-mentioned problems can be achieved and have reached the present invention.

  According to the present invention, it comprises a pulverized product of calcium carbonate and kaolin prepared under a wet condition, and calcium carbonate (A) and kaolin (B) are mixed at a weight ratio of A: B = 9: 1 to 1: 9. An inorganic filler for a chlorine-containing polymer is provided, characterized in that it has an average particle size in the range of 0.1 to 1.0 μm as measured by a laser diffraction scattering method.

  According to the present invention, the calcium carbonate (A) and the kaolin (B) are mixed at a weight ratio of A: B = 9: 1 to 1: 9, and the mixture is pulverized under a wet condition and dried. A method for producing an inorganic filler for chlorine-containing polymers is provided.

  In the above production method, it is preferable to prepare an aqueous slurry by adding 200 to 1000 parts by weight of water per 100 parts by weight of a mixture of calcium carbonate and kaolin, and perform pulverization using the slurry.

  According to the present invention, the inorganic filler for chlorine-containing polymer is further blended in an amount of 1 to 30 parts by weight and the elastomer-based modifier is 2 to 20 parts by weight per 100 parts by weight of the chlorine-containing polymer. A chlorine-containing polymer composition is provided.

  The inorganic filler for a chlorine-containing polymer of the present invention is a fine mixed powder (average particle diameter is 0.1 to 1.0 μm) of calcium carbonate (A) and kaolin (B). A particularly important point is that it is mixed at a constant weight ratio (A: B = 9: 1 to 1: 9) by co-grinding under wet conditions. Thus, when blended with a chlorine-containing polymer, the impact strength is not lowered, but rather is greatly improved, and at the same time, the flexural modulus can be improved while maintaining the flexural strength.

  The reason why the properties of the chlorine-containing polymer are improved by the inorganic filler of the present invention is not clearly elucidated, but the present inventors presume as follows. That is, kaolin has a plate-like particle structure, but by co-grinding under wet conditions, calcium carbonate particles react mechanochemically on the surface of kaolin, and both behave as integral particles. It seems that it is caused by. For example, as shown in the SEM photograph of FIG. 1, in the inorganic filler of the present invention, calcium carbonate fine particles adhere to the surface of the plate-like kaolin particles, and in this state, the two particles are integrated. It can be seen that they are dispersed. As a result, these particles can be uniformly dispersed in the chlorine-containing polymer, reinforcing the impact strength improvement by the elastomer-based modifier, and increasing the flexural modulus while maintaining the flexural strength. And is believed to provide excellent dimensional stability (see Table 1 below).

  Thus, the combined use of the inorganic filler of the present invention and the elastomer-based modifier improves the impact strength and the flexural modulus while maintaining the flexural strength of the chlorine-containing polymer such as vinyl chloride resin, and Since the dimensional stability can be enhanced, the chlorine-containing polymer composition in which such an inorganic filler or the like is blended can be particularly suitably used for a building material such as a window frame.

  In the inorganic filler of the present invention, the calcium carbonate is not particularly limited, and for example, any of heavy calcium carbonate and precipitated calcium carbonate can be used.

The kaolin used for co-grinding with calcium carbonate is a plate-like crystal aluminum silicate salt mineral. For example, the X-ray diffraction image has a peak intensity at the following interplanar spacing (dx).
Spacing (dx) 相 対 Relative strength (%)
7.17 100
4.366 60
3.579 80

That is, kaolin is a two-octahedral 1: 1 layered silicate, ideally containing only Si as a tetrahedral cation and only Al as an octahedral cation, and a 1: 1 layer composition. Is represented by Al ₂ Si ₂ O _5. (OH) ₄ . Examples of such kaolins include kaolin clay minerals such as kaolinite, decaite, and halloysite. The composition of kaolin used in the present invention on the basis of oxide is as follows, for example, when kaolinite is taken as an example.
SiO ₂ : 40 to 55% by weight
Al ₂ O ₃ : 35 to 50% by weight
H ₂ O: 10 to 20% by weight
Other oxides such as TiO ₂ : 10% by weight or less

  In the present invention, calcium carbonate (A) and kaolin (B) are used in a weight ratio of A: B = 9: 1 to 1: 9, particularly 8: 2 to 2: 8. Provided. When the amount of calcium carbonate is small (or only kaolin is used), the bending strength and the bending elastic modulus can be improved, but the impact strength cannot be greatly improved. Also, when the amount of kaolin is small (or using only calcium carbonate), the impact strength cannot be greatly improved. Therefore, in the present invention, it is necessary to use calcium carbonate (A) and kaolin (B) in such a quantity balance as described above.

  The co-grinding of calcium carbonate and kaolin is carried out under a wet condition after mixing them in the above-mentioned ratio, for example, 200 to 1000 parts by weight, particularly 400 to Water is mixed in an amount of 600 parts by weight to prepare an aqueous slurry and co-grinding is performed. When the amount of water is small, there is a risk that the grinding medium (spherulite, etc.) and the slurry will co-rotate due to an increase in the viscosity of the slurry, making it difficult to grind. Moreover, when water is present in a larger amount than necessary, the pulverization efficiency is remarkably reduced, and there is a possibility that the pulverization takes a long time or fine pulverization becomes difficult.

  Co-grinding can be performed using a mixing and grinding machine such as a ball mill, a tube mill, or a dyno mill.

The co-pulverization is performed until the average particle size (D ₅₀ ) of the co-pulverized product by laser diffraction scattering method is in the range of 0.1 to 1.0 μm, particularly 0.3 to 0.7 μm. When co-pulverization is performed until the average particle size becomes finer than necessary, particles in which kaolin and calcium carbonate are adhered and integrated tend to aggregate, and as a result, the bending strength and bending elastic modulus are improved to some extent. Although it can be ensured, the improvement in impact strength by the elastomer-based modifier cannot be reinforced. Further, when the average particle size is larger than the above range, the uniform dispersibility of the particles in which kaolin and calcium carbonate are adhered and integrated is greatly impaired, and any characteristics such as impact strength, bending strength, bending elastic modulus, etc. It becomes difficult to improve.

  By crushing the dried product after co-grinding as described above with a sample mill or the like, the inorganic filler of the present invention containing calcium carbonate and kaolin in a predetermined quantitative ratio and having a predetermined particle size is obtained. .

  The inorganic filler of the present invention described above is kneaded with a chlorine-containing polymer together with an elastomer-based modifier to obtain a chlorine-containing polymer composition, thereby improving the characteristics of the chlorine-containing polymer.

  When blended into the chlorine-containing polymer, if necessary, the hydrophobicity can be increased by surface treatment with a fatty acid, silicone oil, silane coupling agent, titanate coupling agent, phosphate ester, etc. Foaming when blended with a chlorine-containing polymer can be effectively suppressed. Such a surface treating agent is usually about 0.1 to 5 parts by weight per 100 parts by weight of the inorganic filler of the present invention.

  As the elastomer-based modifier, those known per se can be used. For example, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), polybutadiene (BR), poly Isoprene (IR), butyl rubber, natural rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), polyurethane rubber, silicone rubber, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene- Styrene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers and the like can be used alone or in combination of two or more. In the present invention, an acrylic rubber containing a diene unit such as butadiene or a styrene unit in a (meth) acrylic unit such as (meth) acrylic acid ester is particularly preferably used from the viewpoint of an impact strength improving effect. .

  In addition, as the chlorine-containing polymer in which the above inorganic filler or elastomer-based modifier is blended, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, or the like is used.

  In addition, in the chlorine-containing polymer composition containing the inorganic filler and elastomer modifier as described above, from the viewpoint of impact strength, bending strength, bending elastic modulus, the inorganic filler of the present invention, The elastomer modifier is blended in an amount of 1 to 30 parts by weight, particularly 3 to 20 parts by weight per 100 parts by weight of the chlorine-containing polymer, and the elastomeric modifier is 2 to 20 parts by weight, especially 100 parts by weight of the chlorine-containing polymer. It is preferably blended in an amount of 5 to 15 parts by weight.

  In addition, such a chlorine-containing polymer composition is appropriately mixed with a stabilizer for suppressing the elimination of chlorine, for example, a lead-based or non-lead-based stabilizer. Lubricants, processing aids, ultraviolet absorbers, other inorganic fillers, and the like can be appropriately blended in such an amount that the effect of improving properties by the inorganic filler is not impaired.

  Such a chlorine-containing polymer composition has a high flexural modulus and flexural strength as well as impact strength, and can be very effectively applied to the use of profile extrusion products such as building materials represented by window frames. .

  The superior effects of the present invention are illustrated in the following examples. In addition, the measurement method of the test performed in the Example is as follows.

(1) Particle size measurement Using a Particle Size Analyzer Model LS13 320 manufactured by Coulter, the particle size was measured by a laser scattering method.

(2) Preparation of test piece A test piece was prepared by the following composition and method.
Basic formulation parts by weight Vinyl chloride resin (degree of polymerization = 1050) 100.0
Elastomer modifier (acrylic reinforcing agent) 8.0
Lead-free stabilizer 4.0
Surface treatment calcium carbonate 3.0
Lubricant 0.8
SUPERMIXER SM V-20 manufactured by Kawada Manufacturing Co., Ltd. was used, and the inorganic filler powder was blended into the basic blend and mixed at 1500 rpm for 5 minutes at room temperature to prepare a vinyl chloride resin mixture.
Next, the above-mentioned vinyl chloride resin mixture was fed into the extruder main body MEDIA RECOVERY HAAKE RHEOCORD 90, the mixer part HAAKE RHEOMEX CTW 100 THERMO HAAKE TYP 557-2204, the mixture supply part HAAKE BUMETER INSTRUME INSTRUME INSTRUME INSTRUME INSTRUME INSTRUME INSTRUME INSTRUM Was used to produce an extrusion test piece having a width of 20 to 27 mm and a thickness of 1.5 to 2.5 mm at a resin temperature of 200 to 210 ° C.
Furthermore, SF-70 manufactured by Shindo Metal Industries Co., Ltd. was used for the above extrusion molded test piece, preheated at 220 ° C. and a pressure of 10 kg / cm ² for 3 minutes, and then heated and molded at a pressure of 150 kg / cm ² for 5 minutes, and a pressure of 150 kg Water cooling was performed at / cm ² for 2 minutes to produce a press sheet of an extrusion molded specimen having a thickness of 4 mm.
The bending property test piece used was a DUTMBEL CUTING MASHINE SDAP1200FBBR2TRP, and a press sheet of the extrusion test piece produced above was produced according to JIS K7203.
The Charpy impact test piece was cut and produced in the same manner as the bending property test piece, and then a test piece with a Charpy edgewise impact single notch was produced in accordance with JIS K7111, using a cutting machine.

(3) Bending characteristic test It was carried out in accordance with JIS K7203 using TENSILON / UTM-III-500 manufactured by TOYO BALDWIN.

(4) Charpy impact test The Charpy impact test was conducted in accordance with JIS K7111, using IMPACT TESTER manufactured by Nippon Rigaku Corporation.

Example 1
A 15 L pot mill containing 13 kg of alumina balls having a diameter of 3 mm and 4 kg of water was charged with 700 g of calcium carbonate and 300 g of kaolin, and wet pulverized for 20 hours. The resulting slurry was transferred to a stainless steel vat and evaporated to dryness at 130 ° C. overnight. The dried product was pulverized with a sample mill to obtain a co-ground fine powder of calcium carbonate and kaolin.
The particle size of the obtained co-ground fine powder of calcium carbonate and kaolin was measured.
Next, the obtained powder was blended to prepare each test piece, and the physical properties were measured. The results are shown in Table 1. Moreover, the SEM photograph (magnification: 5000 times) of fine powder is shown in FIG.

(Example 2)
Using 1 kg of a mixture of 600 g of calcium carbonate and 400 g of kaolin as a raw material, a co-ground fine powder was obtained in the same manner as in Example 1, and the particle size was measured.
Next, the obtained powder was blended, each test piece was produced in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

(Example 3)
Using 1 kg of a mixture of 500 g of calcium carbonate and 500 g of kaolin as a raw material, a co-ground fine powder was obtained in the same manner as in Example 1, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

(Example 4)
Using 1 kg of a mixture of 200 g of calcium carbonate and 800 g of kaolin as a raw material, a co-ground fine powder was obtained in the same manner as in Example 1, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

(Example 5)
Using 1 kg of a mixture of 600 g of calcium carbonate and 400 g of kaolin as a raw material, the wet pulverization time was set to 3 hours, and the others were obtained in the same manner as in Example 1 to obtain a co-ground fine powder, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

(Example 6)
A 15 L pot mill containing 13 kg of alumina balls having a diameter of 3 mm and 4 kg of water was charged with 1000 g of calcium carbonate and wet pulverized for 20 hours. The resulting slurry was transferred to a stainless steel vat and evaporated to dryness at 130 ° C. overnight. The dried product was pulverized with a sample mill to obtain a fine powder of calcium carbonate.
Kaolin was similarly performed to obtain kaolin fine powder.
The particle sizes of the obtained fine powders of calcium carbonate and kaolin were measured.
Next, the obtained calcium carbonate and kaolin were blended at a weight ratio of 6: 4 to prepare each test piece, and the physical properties were measured. The results are shown in Table 2.

(Comparative Example 1)
Each test piece was prepared by the same method as in Example 1 with only the basic composition, and the physical properties were measured. The results are shown in Table 3.

(Comparative Example 2)
SUPERMIXER SM V-10 manufactured by Kawada Mfg. Co., Ltd. 1050 g of calcium carbonate and 450 g of kaolin were charged and mixed for 5 minutes at about 900 rpm, and dry milling only with a PJM-100SP jet mill manufactured by Nippon Pneumatic Co., Ltd. To obtain a pulverized fine powder, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 3.

(Comparative Example 3)
Using only 1 kg of calcium carbonate as a raw material, pulverized fine powder was obtained in the same manner as in Example 1, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 3.

(Comparative Example 4)
Using only 1 kg of kaolin as a raw material, a pulverized fine powder was obtained in the same manner as in Example 1, and the particle size was measured.
Next, the obtained powder was blended into the basic blend, each test piece was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 3.

It is a figure which shows the SEM photograph (magnification: 5000 times) of the inorganic filler for chlorine containing polymers obtained in Example 1. FIG.

Claims (4)

  A pulverized product of calcium carbonate and kaolin prepared under wet conditions, containing calcium carbonate (A) and kaolin (B) in a weight ratio of A: B = 9: 1 to 1: 9, and laser diffraction scattering An inorganic filler for chlorine-containing polymers, characterized in that the average particle diameter in the method is in the range of 0.1 to 1.0 μm.   A chlorine-containing polymer, wherein calcium carbonate (A) and kaolin (B) are mixed at a weight ratio of A: B = 9: 1 to 1: 9, and the mixture is pulverized under a wet condition and dried. Method for manufacturing inorganic filler.   The production method according to claim 2, wherein an aqueous slurry is prepared by adding 200 to 1000 parts by weight of water per 100 parts by weight of the mixture, and pulverization is performed using the slurry.   The inorganic filler for a chlorine-containing polymer according to claim 1 is blended in an amount of 1 to 30 parts by weight and the elastomer modifier is 2 to 20 parts by weight per 100 parts by weight of the chlorine-containing polymer. A chlorine-containing polymer composition.

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