WO2011070906A1 - ポリアミド樹脂組成物、該ポリアミド樹脂組成物の製造方法および該ポリアミド樹脂組成物から得られた成形体 - Google Patents
ポリアミド樹脂組成物、該ポリアミド樹脂組成物の製造方法および該ポリアミド樹脂組成物から得られた成形体 Download PDFInfo
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- WO2011070906A1 WO2011070906A1 PCT/JP2010/070762 JP2010070762W WO2011070906A1 WO 2011070906 A1 WO2011070906 A1 WO 2011070906A1 JP 2010070762 W JP2010070762 W JP 2010070762W WO 2011070906 A1 WO2011070906 A1 WO 2011070906A1
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- resin composition
- polyamide resin
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- weight reduction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
Definitions
- the present invention relates to a polyamide resin composition having improved strength (bending properties) using a fibrous clay mineral, a method for producing the polyamide resin, and a molded article formed from the polyamide resin composition.
- Polyamide resins are excellent in mechanical strength, heat resistance, chemical resistance, moldability, etc., and are therefore used in many fields such as the electronic / electric field, the automobile field, and the daily necessities field. And in order to further improve the mechanical strength, heat resistance, chemical resistance, moldability, etc. of polyamide resin, fiber such as glass fiber and carbon fiber and inorganic filler such as calcium carbonate are added to the polyamide resin as a reinforcing material.
- fiber such as glass fiber and carbon fiber and inorganic filler such as calcium carbonate are added to the polyamide resin as a reinforcing material.
- fiber such as glass fiber and carbon fiber and inorganic filler such as calcium carbonate are added to the polyamide resin as a reinforcing material.
- fiber such as glass fiber and carbon fiber and inorganic filler such as calcium carbonate
- inorganic fillers that are further improved in dispersibility in polyamide resin and have improved reinforcing (strengthening bending properties) have been studied. Furthermore, a method for producing a polyamide resin composition using the inorganic filler has been studied.
- JP62-74957A, JP2747019B, and JP2941159B describe that a swellable layered silicate is added during polymerization of a polyamide resin to obtain a polyamide resin composition having an enhanced reinforcing effect.
- JP63-251461A describes a resin composition in which a fibrous clay mineral is blended in a polyamide resin to improve the reinforcing effect.
- JP2-182758A describes a polyamide resin composition in which a reinforcing effect is improved by uniformly dispersing sepiolite, among fibrous clay minerals, in a polyamide resin.
- JP 6-84435B describes a method for producing a polyamide resin composition for further improving the reinforcing effect of the fibrous clay mineral dispersed in the polyamide resin.
- the reinforcing effect of the polyamide resin is insufficient. That is, the present situation is that the polyamide resin composition has not yet been widely used in various industrial fields.
- An object of the present invention is to provide a polyamide resin composition in which the bending properties of the polyamide resin are sufficiently strengthened and are lightweight. Furthermore, it aims at providing the manufacturing method of this polyamide resin composition, and the molded object formed by shape
- the inventors of the present invention are polyamide resin compositions in which fibrous clay minerals are dispersed in a polyamide resin, and the polyamide resin composition having a specific weight reduction rate is The inventors have found that the object can be achieved and have reached the present invention.
- the present invention it is possible to obtain a polyamide resin composition in which the bending properties of the polyamide resin are sufficiently enhanced and the weight is light. Furthermore, the manufacturing method of this polyamide resin composition and the molded object formed by shape
- the polyamide resin composition of the present invention comprises a polyamide resin (A) [hereinafter sometimes simply referred to as “component (A)”] and a fibrous clay mineral (B) [hereinafter simply referred to as “component (B)”. May be included].
- the component (A) in the present invention is a polymer having an amide bond in the main chain, with aminocarboxylic acid, lactam, or diamine and dicarboxylic acid as main raw materials.
- the relative viscosity of the component (A) is not particularly limited, but is preferably 1.5 to 3.5, and more preferably 2.0 to 3.5. If the relative viscosity is less than 1.5, the strength of the obtained resin composition may be lowered, which is not preferable. On the other hand, if it exceeds 3.5, the melt viscosity of the obtained resin composition becomes too high, and workability such as dispensing may be deteriorated.
- the relative viscosity is a value measured under conditions of a temperature of 25 ° C. and a concentration of 1 g / dl.
- the content of the component (A) needs to be 65 to 95% by mass in the resin composition, preferably 67 to 92% by mass, and more preferably 70 to 90% by mass.
- the content of the component (A) is less than 65% by mass, polymerization may be insufficient and a resin composition may not be obtained.
- content of a component (A) exceeds 95 mass, the weight reduction rate mentioned later becomes low and the reinforcement effect of a component (A) may become inadequate.
- the component (B) in the present invention is excellent in dispersibility as compared with other clay minerals. Therefore, the bending characteristics (flexural modulus) can be improved effectively. That is, it is preferable that the component (B) is well dispersed in the component (A).
- the resin composition of the present invention has a low density and excellent bending properties.
- Component (B) is preferably a fibrous hydrous magnesium silicate mineral.
- sepiolite and palygorskite are particularly preferably used from the viewpoint of easy dispersion in the component (A) and easy suppression of an increase in the melt viscosity of the obtained resin composition.
- Sepiolite is a natural mineral containing Mg 8 H 2 (SiO 4 O 11 ) ⁇ 3H 2 O as a main component.
- the palygorskite is a natural mineral containing Mg 8 Al 2 Si 8 O 20 (OH 2 ) ⁇ 8H 2 O as a main component.
- magnesium may be replaced with iron or aluminum.
- Component (B) has a three-layer structure in which an octahedral magnesium oxide layer is a central layer and a tetrahedral silicate layer is disposed on both sides thereof. Since this three-layer structure extends along the X-axis direction (fiber length direction), the component (B) crystals are fibrous (fibrous crystals). Moreover, a some fibrous crystal may aggregate along a fiber direction.
- the octahedral magnesium oxide layer becomes a discontinuous layer and forms zeolite pores in the fiber cross section.
- the component (B) has a large number of silanol groups (Si—OH groups) along the X-axis direction, a highly polar substance such as water is present in the gaps between the zeolite pores and the particles. It has the property of easily entering.
- the weight reduction ratio represented by the following formula (I) is required to be 22 to 40%, more preferably 24 to 40%, and more preferably 30 to 40%. Is more preferable.
- the weight reduction rate means that the strength (elastic modulus) of the resin composition is taken into consideration when the content and density of the filler in the resin composition are taken into account when the filler is contained to improve the strength of the resin composition. It has been evaluated. That is, a high weight reduction rate indicates that the elastic modulus of the resin composition is higher and the resin composition is lighter. A molded body obtained from such a resin composition has an advantage that it can be reduced in weight without impairing the elastic modulus.
- t represents the thickness of the material.
- the deformation amount Y is inversely proportional to the product of the elastic modulus (E) of the material and the cube of the thickness t of the material.
- the thickness t of the material is inversely proportional to the third power of the elastic modulus of the material. Furthermore, since the mass of the compact is proportional to the value obtained by multiplying the thickness t by the material density ⁇ , this index is defined as the weight reduction index and defined by the above formula (II).
- Comparative Example 1 polyamide 6 resin of JP63-251461A described above, the density is about 1.13 g / cm 3 . Since sepiolite has a density of 2.3 g / cm 3 , the density of the polyamide resin composition obtained in Example 1 is about 1.19 g / cm 3 .
- the elastic modulus of Comparative Example 1 is 1.7 ⁇ 10 3 (kg / mm 2 ), and the elastic modulus of Example 1 is 2.5 ⁇ 10 3 (kg / mm). 2 ).
- the method for producing a polyamide resin composition of the present invention needs to include the following steps (i), (ii), (iii) and (iv) in this order.
- (i) A step of mixing the monomer constituting the polyamide resin (A) and the acid (C) at a temperature T equal to or higher than the melting point of the monomer constituting the polyamide resin (A) to obtain a mixed solution.
- Step of polymerizing monomers constituting polyamide (A) by heating the mixture obtained in the above (iii) Step (i) will be described below.
- the acid (C) plays a role of acting as a catalyst when the monomer constituting the component (A) is polymerized in the step (iv) described later.
- the component (B) is the above-mentioned sepiolite or palygorskite
- the acid (C) reacts with the monomer constituting the component (A) in the later-described step (ii).
- the obtained reaction product has an advantage that the dispersibility of the component (B) can be promoted by entering the component (B) having a large number of silanol groups.
- the acid (C) may be either an inorganic acid or an organic acid as long as the pKa (25 ° C., value in water) is 6 or less.
- the inorganic acid include phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, nitric acid and the like.
- the organic acid include formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, benzoic acid, p-toluenesulfonic acid, N-formyl- ⁇ -aminocaproic acid and the like.
- phosphoric acid is preferable from the viewpoint of reactivity with the monomer constituting the component (A).
- the amount of the acid (C) used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the monomer constituting the component (A).
- the amount of the acid (C) used is less than 0.01 parts by mass, the effect of promoting the dispersion of the component (B) may not be sufficiently exhibited, and the polymerization rate of the component (A) in the step (iv) described later is high. May be slow.
- it exceeds 5 parts by mass a polyamide resin (A) having a high degree of polymerization cannot be obtained, and problems such as corrosion of the reaction vessel may occur.
- step (i) water was added in this step (i) to obtain a mixed solution, and then component (B) was blended in step (ii).
- component (B) was blended in step (ii).
- the compatibility of the monomer constituting component (A), water, and component (B) is too good, so that when water is used in step (i), rotation proceeds as the polymerization proceeds.
- the viscosity increased too much. Therefore, the compounding quantity of the component (B) cannot be increased, and it has been difficult to sufficiently exhibit the reinforcing improvement effect.
- a mixed solution obtained by mixing the acid (C) with the monomer constituting the component (A) at a temperature T equal to or higher than the melting point without using water in step (i) It is preferable to use as. Thereby, the raise of rotational viscosity can be suppressed and the compounding quantity of a component (B) can be increased. That is, the reinforcing effect of the component (A) can be sufficiently exhibited.
- the mixing method in the step (i) is a method in which the monomer constituting the component (A) and the acid (C) are first mixed and mixed at a temperature T equal to or higher than the melting point of the monomer constituting the component (A).
- the mixing time in step (i) is preferably 1 minute to 1 hour from the viewpoint of workability.
- the form when using the component (B) is not particularly limited as long as the dispersibility in the monomer constituting the component (A) can be improved. It is preferable because it is easy to make.
- the blending amount of component (B) is preferably 5 to 35% by mass in the resin composition, more preferably 8 to 33% by mass, and still more preferably 10 to 30% by mass.
- the weight reduction rate described later is lowered, and the reinforcing effect of the component (A) may be insufficient.
- it exceeds 35 mass% superposition
- the rotational viscosity of the stirring solution obtained in step (ii) is preferably 20 to 500 Pa ⁇ s, more preferably 25 to 500, as measured with a B-type viscometer at a temperature T equal to or higher than the melting point of the monomer. 400 Pa ⁇ s, particularly preferably 30 to 350 Pa ⁇ s. If the rotational viscosity exceeds 500 Pa ⁇ s, the fluidity of the stirring solution will be extremely reduced, and therefore it will be difficult for the mixture to cause a uniform reaction during the step (iv) described later, and the polymerization will be insufficient. There is a case. Furthermore, it is difficult to shift from step (ii) to step (iii) described later, which may lead to a decrease in productivity.
- the heating temperature T in the step (ii) is not particularly limited as long as the monomer constituting the component (A) is melted.
- the heating temperature is set to 69 ° C. or higher, and when a molar salt of hexamethylenediamine adipate is used, the heating temperature is set to 200 ° C. or higher to melt. It is preferable.
- the shape of the stirring blade, the number of rotations, and the like under the stirring conditions in step (ii) are not particularly limited.
- the stirring time in step (ii) is preferably 0.5 to 10 hours from the viewpoint of dispersibility of component (B) in component (A) and workability, and preferably 1 to 5 hours. Is more preferable.
- step (i) water was blended in step (i).
- step (iii) it is preferable to use water not in step (i) but in step (iii) from the viewpoint of increasing the amount of component (B).
- the weight reduction rate can be further improved, and it is possible to obtain a resin composition that is lightweight and exhibits a reinforcement improvement effect.
- step (iii) the amount of water blended in the stirring solution obtained in step (ii) is preferably 0 to 15% by mass, and more preferably 1 to 10% by mass in the stirring solution. If the amount of water exceeds 15% by mass, the polymerization time may be too long, causing problems in productivity and workability.
- step (iv) since a fibrous clay mineral is used as the filler, an increase in melt viscosity during step (iv) can be suppressed, and the melt viscosity can be controlled within a preferable range. Therefore, the compounding quantity of the component (B) to the component (A) can be increased, and the strength improvement effect can be sufficiently expressed.
- the polymerization temperature in step (iv) is preferably from the melting point of the polyamide to 340 ° C. from the viewpoint of the polymerizability of the polyamide.
- the polymerization time in step (iv) is preferably 0.5 to 10 hours from the viewpoint of productivity and polymerizability.
- ⁇ -caprolactam as a monomer constituting component (A). Even when aminocaproic acid or the like is used as the monomer constituting the component (A), a polyamide resin composition can be obtained. However, in such a case, since the component (B) cannot be well dispersed in the component (A), the strength improving effect may not be sufficiently exhibited.
- a heat stabilizer an antioxidant, a pigment, an anti-coloring agent, a weathering agent, a flame retardant, a plasticizer, a crystal nucleating agent, A mold release stabilizer or the like may be added.
- the resin composition obtained in the present invention can be blended with other polymers as necessary as long as the characteristics thereof are not significantly impaired.
- Such polymers include polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, chlorinated butyl rubber, elastomers such as chlorinated polyethylene, And acid-modified products thereof with maleic anhydride, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide , Polyethersulfone, phenoxy resin, polyphenylene ether, polymethyl methacrylate, polyether ketone, polyarylate, polycarbonate, polyt
- additives or blending of the polymer can be efficiently added or blended by mixing with the resin composition of the present invention and then melt-kneading using a twin screw extruder.
- the desired molded product can be produced by subjecting the resin composition obtained in the present invention to a normal molding method.
- the resin composition obtained in the present invention can be formed into a molded body using a hot melt molding method such as injection molding, extrusion molding, blow molding, or sintering molding.
- a hot melt molding method such as injection molding, extrusion molding, blow molding, or sintering molding.
- it can also be set as a thin film by melt
- the resin composition of the present invention exhibits a remarkable strength improvement effect as compared with a polyamide resin reinforced with conventional fibers. Therefore, it is suitably used in the electric / electronic equipment field, the automobile field, the machine field, and the like.
- Rotational viscosity (Pa ⁇ s) The rotational viscosity was measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions were 80 ° C. and 0.3 rpm when polyamide 6 resin was used. When polyamide 66 resin was used, the temperature was 200 ° C. and 0.3 rpm.
- (2) Content (% by mass) of component (B) in the resin composition The mass of the obtained polyamide resin composition was measured. Subsequently, this polyamide resin composition was heated at 500 degreeC for 3 hours, and the residue mass after a heating was measured. The content rate of the component (B) was calculated by the following formula.
- [Content of component (B)] (residue mass) / (mass of polyamide resin composition before heating) ⁇ 100 (3)
- Flexural modulus (GPa) The molded body obtained by injection molding was measured for flexural modulus (GPa) according to ISO 178. In the present invention, a material having a pressure of 5.5 GPa or more can be practically used. In this embodiment, the elastic modulus is represented by the bending elastic modulus.
- Polyamide resin weight reduction index M0 The weight reduction index M0 shown by the component (A) before containing the component (B), that is, the polyamide resin, was calculated by the following equation.
- Weight reduction index M0 of polyamide resin (density of polyamide resin) / (elastic modulus of polyamide resin) 1/3
- the numerical values obtained in the above (3) and (4) were used for the density of the polyamide resin and the elastic modulus of the polyamide resin.
- Weight reduction index M1 of polyamide resin composition The weight reduction index M1 which the polyamide resin composition which consists of a component (A) and a component (B) shows was computed by following Formula.
- Weight reduction index of polyamide resin M1 (density of polyamide resin composition) / (elastic modulus of polyamide resin composition) 1/3
- the numerical value obtained by said (3) and (4) was used for the density of a polyamide resin composition, and the elasticity modulus of a polyamide resin composition.
- Weight reduction rate of polyamide resin composition It calculated from the following formula using M0 and M1 obtained in the above (5) and (6).
- [Weight reduction ratio of polyamide resin composition] ⁇ 1 ⁇ (weight reduction index M1 of polyamide resin composition) / (weight reduction index M0 of polyamide resin) ⁇ ⁇ 100
- (A-1) 10 kg, (C-1) 20 g, and 0.5 liter of water are placed in the same container, and stirred and mixed at 80 ° C. using a homomixer (trade name “MARKII20” manufactured by PRIMIX Co., Ltd.). The mixture was put into an autoclave, purged with nitrogen, and ⁇ -caprolactam was polymerized while stirring at 260 ° C. for 90 minutes.
- the obtained polymer was discharged in a strand form from the bottom drain valve of the autoclave, the polymer was cooled and solidified in a hot tub, and cut into pellets with a cutter.
- the obtained pellets were refined with hot water at 95 ° C. for 24 hours to remove unreacted monomers and oligomers remaining in the pellets. Then, it was dried at 80 ° C. for 24 hours, and further vacuum dried at 80 ° C. for 48 hours to obtain a polyamide resin.
- the obtained polyamide resin pellets were injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (trade name “EC-100” manufactured by Toshiba Machine Co., Ltd.) to produce a molded body. .
- the obtained molded product had a flexural modulus of 2.5 GPa, a density of 1.13 (g / cm 3 ), and M0 of 0.83.
- M0 weight reduction index obtained in Preparation Example 1
- the weight reduction ratios of Examples 1 to 7 and Comparative Examples 1 to 3, 5, and 6 described later were calculated.
- Example 1 10 kg of (A-1) and 20 g of (C-1) were put in the same container and mixed at 80 ° C. to prepare an ⁇ -caprolactam solution.
- ⁇ -caprolactam solution 1.14 kg of sepiolite (B-1) was blended, and the mixture was stirred at 80 ° C. for 4 hours using a homomixer (trade name “MARKII20” manufactured by Primics).
- the rotational viscosity of this stirred solution was 67 Pa ⁇ s.
- 0.5 liters of water was added to the resulting stirred solution and stirred to obtain a mixture.
- This mixture was put into an autoclave, and ⁇ -caprolactam was polymerized while stirring at 260 ° C. for 90 minutes.
- the obtained polyamide resin 6 composition pellets were injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (trade name “EC-100” manufactured by Toshiba Machine Co., Ltd.). Was made.
- the obtained molded product had a content of (B-1) of 10% by mass, a flexural modulus of 6.6 GPa, a density of 1.19 (g / cm 3 ), and M1 of 0.64.
- the weight reduction rate was 24%.
- Example 2 10 kg of (A-1) and 20 g of (C-1) were put in the same container and mixed at 80 ° C. to prepare an ⁇ -caprolactam solution. To this solution, 1.14 kg of (B-1) was blended and stirred at 80 ° C. for 2 hours using a homomixer. The rotational viscosity of this stirred solution was 25 Pa ⁇ s. Subsequent operations were performed in the same manner as in Example 1 and were evaluated. The obtained molded product had a content of (B-1) of 10% by mass, a flexural modulus of 6.2 GPa, a density of 1.19 (g / cm 3 ), and M1 of 0.65. The weight reduction rate was 22%.
- Example 4 10 kg of (A-1) and 20 g of (C-1) were put in the same container and mixed at 80 ° C. to prepare an ⁇ -caprolactam solution. To this solution, 3.35 kg of (B-1) was blended, and stirred at 80 ° C. for 3 hours using a homomixer. The rotational viscosity of this stirred solution was 340 Pa ⁇ s. Subsequent operations were performed in the same manner as in Example 1 and were evaluated. The obtained molded product had a content of (B-1) of 25% by mass, a flexural modulus of 12.5 GPa, a density of 1.29 (g / cm 3 ), and M1 of 0.56. The weight reduction rate was 33%.
- Example 5 Evaluation was performed in the same manner as in Example 1 except that (B-1) was changed to (B-2).
- the rotational viscosity of the stirring solution was 72 Pa ⁇ s.
- the obtained molded product had a content of (B-2) of 10% by mass, a flexural modulus of 6.5 GPa, a density of 1.19 (g / cm 3 ), and M1 of 0.64.
- the weight reduction rate was 23%.
- Example 6 Evaluation was performed in the same manner as in Example 1 except that the blend of (B ⁇ ⁇ BR> P) was changed to 5.38 kg.
- the rotational viscosity of the stirring solution was 400 Pa ⁇ s.
- the obtained molded product had a content of (B-1) of 35% by mass, a flexural modulus of 16.5 GPa, a density of 1.37 (g / cm 3 ), and M1 of 0.52.
- the weight reduction rate was 35%.
- Example 8 10 kg of (A-3) and 20 g of (C-1) were put in the same container and mixed at 200 ° C. to prepare an adipic acid hexamethylenediamine salt solution.
- adipic acid hexamethylenediamine salt solution 10 kg of (A-3) and 20 g of (C-1) were put in the same container and mixed at 200 ° C. to prepare an adipic acid hexamethylenediamine salt solution.
- B-1 sepiolite
- the rotational viscosity of this stirred solution was 52 Pa ⁇ s.
- 0.5 liters of water was added to the obtained stirring solution and stirred to obtain a mixture.
- This mixture was put into an autoclave, and hexamethylenediamine adipate was polymerized while stirring at 270 ° C. for 90 minutes. .
- the obtained polymer was discharged in a strand form from the bottom drain valve of the autoclave, the polymer was cooled and solidified in a hot tub, and cut into pellets with a cutter. Then, it was dried at 80 ° C. for 24 hours, and further vacuum dried at 80 ° C. for 48 hours to obtain a polyamide 66 resin composition.
- the obtained pellets of the polyamide resin 66 composition were injection molded at a cylinder temperature of 285 ° C. and a mold temperature of 80 ° C. using an injection molding machine (trade name “EC-100” manufactured by Toshiba Machine Co., Ltd.). Was made.
- the obtained molded product had a content of (B-1) of 10% by mass, a flexural modulus of 7.2 GPa, a density of 1.20 (g / cm 3 ), and M1 of 0.62.
- the weight reduction rate was 22%.
- Example 9 10 kg of (A-3) and 20 g of (C-1) were put in the same container and mixed at 200 ° C. to prepare an adipic acid hexamethylenediamine salt solution. To this solution, 3.35 kg of (B-1) was blended and stirred at 200 ° C. for 3 hours using a homomixer. The rotational viscosity of this stirred solution was 365 Pa ⁇ s. Subsequent operations were performed in the same manner as in Example 1 and were evaluated. The obtained molded product had a content of (B-1) of 25% by mass, a flexural modulus of 13.8 GPa, a density of 1.30 (g / cm 3 ), and M1 of 0.54. The weight reduction rate was 32%.
- Table 1 summarizes the evaluation results of the polyamide resins obtained in Preparation Examples 1 and 2, the compositions and evaluation results of the polyamide resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 6.
- the polyamide resin composition of the present invention is useful in the electrical / electronic equipment field, the automobile field, the machine field and the like because its bending characteristics are sufficiently strengthened and light weight.
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Abstract
Description
(1)ポリアミド樹脂(A)と繊維状粘土鉱物(B)からなるポリアミド樹脂組成物であって、ポリアミド樹脂組成物100質量%中、繊維状粘土鉱物(B)の含有量が5~35質量%であり、下記式(I)で示される軽量化率が22~40%であることを特徴とするポリアミド樹脂組成物。
(I):[1-{ポリアミド樹脂(A)と繊維状粘土鉱物(B)からなるポリアミド樹脂組成物が示す軽量化指数}/{繊維状粘土鉱物(B)を含有する前のポリアミド樹脂(A)が示す軽量化指数}]×100
なお、上記式(I)において、軽量化指数は下記式(II)で示される。
(II):(樹脂、または樹脂組成物の密度)/(樹脂、または樹脂組成物の弾性率)1/3
(2)(1)のポリアミド樹脂組成物を製造する方法であって、以下の(i)~(iv)の工程を、この順で含むことを特徴とするポリアミド樹脂組成物の製造方法。
(i)ポリアミド樹脂(A)を構成するモノマーの融点以上の温度Tで、ポリアミド樹脂(A)を構成するモノマーと酸(C)とを混合し混合溶液を得る工程
(ii)上記(i)で得られた混合溶液に繊維状粘土鉱物(B)を配合し、攪拌し攪拌溶液を得る工程
(iii)上記(ii)で得られた攪拌溶液に水を配合し混合物を得る工程
(iv)上記(iii)で得られた混合物を加熱しポリアミド(A)を構成するモノマーを重合する工程
(3)上記工程(ii)で得られた攪拌溶液において、前記モノマーの融点以上の温度TにおけるB型粘度計で測定した回転粘度が20~500Pa・sとなるように攪拌することを特徴とする(2)の樹脂組成物の製造方法。
(4)(1)の樹脂組成物を成形してなることを特徴とする成形体。
(以下、成分(A)と成分(B)からなるポリアミド樹脂組成物が示す軽量化指数をM1、成分(B)を含有する前の成分(A)が示す軽量化指数をM0と記載する場合がある。)
上記式(I)において、軽量化指数は下記式(II)で示される。
(II):(樹脂、または樹脂組成物の密度)/(樹脂、または樹脂組成物の弾性率)1/3
なお、上記式(II)において、樹脂または樹脂組成物の密度(単位:g/cm3、以下「ρ」と記載する)、および、樹脂または樹脂組成物の弾性率(単位:GPa、以下「E」と記載する)は、絶乾時にISO178に従って測定されたものである。
上記式(III)において、Xは、Lを材料における力のかかる支点間距離、bを材料における力のかかる幅として、X=L3/4bで算出される。L、bともに定数であるため、Xも定数である。
従って、tとEとには、下記式(V)の関係が成り立つ。
ここで、同じ応力(F)を加えたときに、同じ変形量(Y)を示すように設計したときのEとtには下記式(VI)の関係が成り立つ。
ここで、K=(X×F/Y)1/3であるため、Kは定数である。
上記軽量化指数の一例として、JP63-251461Aに記載された、実施例1および比較例1の軽量化指数を計算する。
(比較例1の軽量化指数M0):1.13×(1.7×103)1/3=0.947
(実施例1の軽量化指数M1):1.19×(2.5×103)1/3=0.878
上記の軽量化指数により軽量化率を計算すると、下記の通りである。
軽量化率=1-0.878/0.947×100=7.3(%)
従って、JP63-251461Aの実施例1で示されるポリアミド樹脂組成物の軽量化率は、7.3%である。
(i)上述のポリアミド樹脂(A)を構成するモノマーの融点以上の温度Tで、ポリアミド樹脂(A)を構成するモノマーと、酸(C)とを混合し混合溶液を得る工程
(ii)上記(i)で得られた混合溶液に上述の繊維状粘土鉱物(B)を配合し、攪拌し攪拌溶液を得る工程
(iii)上記(ii)で得られた攪拌溶液に水を配合し混合物を得る工程
(iv)上記(iii)で得られた混合物を加熱しポリアミド(A)を構成するモノマーを重合する工程
工程(i)について、以下に説明する。
1.原料
(1)成分(A)を構成するモノマー
A-1:ε-カプロラクタム(宇部興産社製)(融点:69℃)
A-2:6-アミノカプロン酸(ナカライテスク社製)(融点:205℃)
A-3:アジピン酸ヘキサメチレンジアミン等モル塩(BASF社製、AH塩)(融点:185℃)
(2)成分(B)
B-1:セピオライト(TOLSA社製、商品名「PANGEL HV」) 平均粒径:5μm
B-2:パリゴルスカイト(昭和KDE社製、商品名「POLEISY」) 平均粒径:50μm
B-3:モンモリロナイト(クニミネ工業社製、商品名「クニピアF」)平均粒径:40μm
(3)酸(C)
C-1:リン酸(ナカライテスク社製)
C-2:塩酸(ナカライテスク社製)
以下に実施例および比較例で用いた評価方法を以下に示す。
2.試験方法
(1)回転粘度(Pa・s)
B型粘度計(東機産業社製)を用いて回転粘度を測定した。なお、測定条件としては、ポリアミド6樹脂を用いた場合には80℃、0.3rpmとした。また、ポリアミド66樹脂を用いた場合には200℃、0.3rpmとした。
(2)樹脂組成物中の成分(B)の含有率(質量%)
得られたポリアミド樹脂組成物の質量を測定した。次いで、該ポリアミド樹脂組成物を500℃で3時間加熱し、加熱後の残渣質量を測定した。以下の式により、成分(B)の含有率を算出した。
[成分(B)の含有率]=(残渣質量)/(加熱前のポリアミド樹脂組成物の質量)×100
(3)曲げ弾性率(GPa)
射出成形により得られた成形体について、ISO 178に従って、曲げ弾性率(GPa)を測定した。本発明においては、5.5GPa以上であるものを実用に耐えうるものとした。なお、本実施例においては、弾性率を曲げ弾性率で代表する。
(4)密度(g/cm3)
ISO 1183に従い密度を求めた。
(5)ポリアミド樹脂の軽量化指数M0
成分(B)を含有する前の成分(A)、すなわちポリアミド樹脂が示す軽量化指数M0を次式により算出した。
[ポリアミド樹脂の軽量化指数M0]=(ポリアミド樹脂の密度)/(ポリアミド樹脂の弾性率)1/3
なお、ポリアミド樹脂の密度、およびポリアミド樹脂の弾性率は、上記(3)、(4)で得られた数値を用いた。
(6)ポリアミド樹脂組成物の軽量化指数M1
成分(A)と成分(B)とからなるポリアミド樹脂組成物が示す軽量化指数M1を次式により算出した。
[ポリアミド樹脂の軽量化指数M1]=(ポリアミド樹脂組成物の密度)/(ポリアミド樹脂組成物の弾性率)1/3
なお、ポリアミド樹脂組成物の密度、およびポリアミド樹脂組成物の弾性率は、上記(3)、(4)で得られた数値を用いた。
(7)ポリアミド樹脂組成物の軽量化率
上記(5)、(6)で得られたM0、M1を用いて次式より算出した。
[ポリアミド樹脂組成物の軽量化率]={1-(ポリアミド樹脂組成物の軽量化指数M1)/(ポリアミド樹脂の軽量化指数M0)}×100
(調製例1)
(A-1)10kg、(C-1)20g、水0.5リットルを同一容器に入れ、ホモミキサー(プライミクス社製、商品名「MARKII20」)を用いて、80℃で攪拌混合し、次いで、オートクレーブに投入し、窒素置換後、260℃で90分間攪拌しながら、ε-カプロラクタムを重合させた。
(A-2)を用いた以外は、調製例1と同様の操作を行ってポリアミド樹脂を得た後、射出成形し、成形体を作製した。得られた成形体の曲げ弾性率は2.5GPa、密度は1.13(g/cm3)、M0は0.83であった。調製例2で求められた軽量化指数M0を用いて、後述の比較例4の軽量化率を算出した。
(調整例3)
(A-3)を用い、重合条件を270℃で90分間攪拌とした以外は、調整例1と同様の操作を行ってポリアミド樹脂を得た後、射出成形し、成形体を作製した。得られた成形体の曲げ弾性率は3.0GPa、密度は1.14(g/cm3)、M0は0.79であった。調製例3で求められた軽量化指数M0を用いて、実施例8、9および比較例7の軽量化率を算出した。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、セピオライト(B-1)1.14kgを配合し、ホモミキサー(プライミクス社製、商品名「MARKII20」)を用いて、80℃で4時間攪拌した。この攪拌溶液の回転粘度は67Pa・sであった。次いで、得られた攪拌溶液に水0.5リットルを配合し攪拌して混合物を得、この混合物をオートクレーブに投入し、260℃で90分間攪拌しながら、ε-カプロラクタムを重合させた。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)1.14kgを配合し、ホモミキサーを用いて、80℃で2時間攪拌した。この攪拌溶液の回転粘度は25Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は10質量%、曲げ弾性率は6.2GPa、密度は1.19(g/cm3)、M1は0.65であった。軽量化率は22%であった。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)0.98kgを配合し、ホモミキサーを用いて、80℃で10時間攪拌した。この攪拌溶液の回転粘度は32Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は7質量%、曲げ弾性率は5.8GPa、密度は1.16(g/cm3)、M1は0.65であった。軽量化率は22%であった。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)3.35kgを配合し、ホモミキサーを用いて、80℃で3時間攪拌した。この攪拌溶液の回転粘度は340Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は25質量%、曲げ弾性率は12.5GPa、密度は1.29(g/cm3)、M1は0.56であった。軽量化率は33%であった。
(B-1)を(B-2)に変えた以外は、実施例1と同様に行い評価に付した。攪拌溶液の回転粘度は72Pa・sであった。得られた成形体の(B-2)の含有率は10質量%、曲げ弾性率は6.5GPa、密度は1.19(g/cm3)、M1は0.64であった。軽量化率は23%であった。
(B-・BR>P)の配合を5.38kgとした以外は、実施例1と同様に行い評価に付した。攪拌溶液の回転粘度は400Pa・sであった。得られた成形体の(B-1)の含有率は35質量%、曲げ弾性率は16.5GPa、密度は1.37(g/cm3)、M1は0.52であった。軽量化率は35%であった。
(C-1)を(C-2)に変えた以外は、実施例1と同様に行い評価に付した。攪拌溶液の回転粘度は70Pa・sであった。得られた成形体の(B-1)の含有率は10質量%、曲げ弾性率は6.6GPa、密度は1.19(g/cm3)、M1は0.64であった。軽量化率は24%であった。
(A-3)10kg、(C-1)20gを同一容器に入れ、200℃にて混合し、アジピン酸ヘキサメチレンジアミン塩溶液を調製した。この溶液に、セピオライト(B-1)1.14kgを配合し、ホモミキサー(プライミクス社製、商品名「MARKII20」)を用いて、200℃で4時間攪拌した。この攪拌溶液の回転粘度は52Pa・sであった。次いで、得られた攪拌溶液に水0.5リットルを配合し攪拌して混合物を得、この混合物をオートクレーブに投入し、270℃で90分間攪拌しながら、アジピン酸ヘキサメチレンジアミン塩を重合させた。
(A-3)10kg、(C-1)20gを同一容器に入れ、200℃にて混合し、アジピン酸ヘキサメチレンジアミン塩溶液を調製した。この溶液に、(B-1)3.35kgを配合し、ホモミキサーを用いて、200℃で3時間攪拌した。この攪拌溶液の回転粘度は365Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は25質量%、曲げ弾性率は13.8GPa、密度は1.30(g/cm3)、M1は0.54であった。軽量化率は32%であった。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)1.14kgを配合し、ホモミキサーを用いて、80℃で0.5時間攪拌した。この攪拌溶液の回転粘度は15Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は10質量%、曲げ弾性率は5.0GPa、密度は1.19(g/cm3)、M1は0.70であった。軽量化率は16%であった。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)0.01kgを配合し、ホモミキサーを用いて、80℃で4時間攪拌した。この攪拌溶液の回転粘度は0.3Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は3質量%、曲げ弾性率は3.8GPa、密度は1.15(g/cm3)、M1は0.74であった。軽量化率は11%であった。
(A-1)10kg、(C-1)20gを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)5.13kgを配合し、ホモミキサーを用いて、80℃で2時間攪拌した。(B-1)の含有率は45質量%であった。この攪拌溶液の回転粘度は720Pa・sであった。この攪拌溶液は回転粘度が高いため、その後の重合が不十分となり、ポリアミド樹脂組成物を得ることができなかった。
(A-2)10kg、(B-1)1.14kgを混合し、オートクレーブに投入して、220℃に加熱し、1時間攪拌しこれらを混合した。その後、260℃で80分間攪拌しながら、(A-2)を重合させた。重合終了後は実施例1と同様に行い、評価に付した。工程(i)~工程(iii)を経ないでポリアミド樹脂組成物を得たため、攪拌溶液の回転粘度は測定できなかった。得られた成形体の(B-1)の含有率は10質量%、曲げ弾性率は3.6GPa、密度は1.19(g/cm3)、M1は0.78であった。軽量化率は6.7%であった。
(B-1)を(B-3)に変えた以外は、実施例1と同様に行い評価に付した。攪拌溶液の回転粘度は41Pa・sであった。繊維状粘土鉱物を用いないで、繊維状ではない粘土鉱物を用いたため、工程(iv)におけるポリマーの溶融粘度が高くなりすぎ、重合を完了させることができず、ポリアミド樹脂組成物は得られなかった。
(A-1)10kg、(C-1)20g、水0.5リットルを同一容器に入れ、80℃にて混合し、ε-カプロラクタム溶液を調製した。この溶液に、(B-1)1.14kgを配合し、ホモミキサーを用いて、80℃で3時間攪拌した。この攪拌溶液の回転粘度は750Pa・sであった。回転粘度が高すぎ、工程(iii)に進めず、ポリアミド樹脂組成物は得られなかった。
(A-3)10kg、(C-1)20gを同一容器に入れ、200℃にて混合し、アジピン酸ヘキサメチレンジアミン塩溶液を調製した。この溶液に、(B-1)0.01kgを配合し、ホモミキサーを用いて、200℃で4時間攪拌した。この攪拌溶液の回転粘度は0.5Pa・sであった。その後の操作は、実施例1と同様に行い、評価に付した。得られた成形体の(B-1)の含有率は3質量%、曲げ弾性率は4.0GPa、密度は1.16(g/cm3)、M1は0.73であった。軽量化率は7.6%であった。
Claims (4)
- ポリアミド樹脂(A)と繊維状粘土鉱物(B)からなるポリアミド樹脂組成物であって、ポリアミド樹脂組成物100質量%中、繊維状粘土鉱物(B)の含有量が5~35質量%であり、下記式(I)で示される軽量化率が22~40%であることを特徴とするポリアミド樹脂組成物。
(I):[1-{ポリアミド樹脂(A)と繊維状粘土鉱物(B)からなるポリアミド樹脂組成物が示す軽量化指数}/{繊維状粘土鉱物(B)を含有する前のポリアミド樹脂(A)が示す軽量化指数}]×100
なお、上記式(I)において、軽量化指数は下記式(II)で示される。
(II):(樹脂、または樹脂組成物の密度)/(樹脂、または樹脂組成物の弾性率)1/3 - 請求項1に記載のポリアミド樹脂組成物を製造する方法であって、以下の(i)~(iv)の工程を、この順で含むことを特徴とするポリアミド樹脂組成物の製造方法。
(i)ポリアミド樹脂(A)を構成するモノマーの融点以上の温度Tで、ポリアミド樹脂(A)を構成するモノマーと酸(C)とを混合し混合溶液を得る工程
(ii)上記(i)で得られた混合溶液に繊維状粘土鉱物(B)を配合し、攪拌し攪拌溶液を得る工程
(iii)上記(ii)で得られた攪拌溶液に水を配合し混合物を得る工程
(iv)上記(iii)で得られた混合物を加熱しポリアミド(A)を構成するモノマーを重合する工程 - 上記工程(ii)で得られた攪拌溶液において、前記モノマーの融点以上の温度TにおけるB型粘度計で測定した回転粘度が20~500Pa・sとなるように攪拌することを特徴とする請求項2に記載の樹脂組成物の製造方法。
- 請求項1に記載の樹脂組成物を成形してなることを特徴とする成形体。
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| JP2010254992A (ja) * | 2009-03-31 | 2010-11-11 | Unitika Ltd | 繊維強化ポリアミド樹脂組成物 |
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| JPS6264827A (ja) * | 1985-09-17 | 1987-03-23 | Toyota Central Res & Dev Lab Inc | ラクタム重合触媒 |
| JPS6272723A (ja) * | 1985-09-26 | 1987-04-03 | Toyota Central Res & Dev Lab Inc | ラクタム重合触媒 |
| JPS63251461A (ja) * | 1987-04-08 | 1988-10-18 | Toyota Central Res & Dev Lab Inc | ナイロン複合材料およびその製造方法 |
| JP2010254992A (ja) * | 2009-03-31 | 2010-11-11 | Unitika Ltd | 繊維強化ポリアミド樹脂組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011070906A1 (ja) | 2013-04-22 |
| CN102612545A (zh) | 2012-07-25 |
| TW201129609A (en) | 2011-09-01 |
| CN102612545B (zh) | 2014-07-09 |
| JP5791519B2 (ja) | 2015-10-07 |
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