JP2004083656A - Resin composition having excellent moldability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polytrimethylene terephthalate resin composition which has a short molding cycle and extremely improved burrs. <P>SOLUTION: The polytrimethylene terephthalate resin composition comprises (A) 100 parts wt. of a polytrimethylene terephthalate resin and (B) 0.1-15 parts wt. of an ionomer resin. <P>COPYRIGHT: (C)2004,JPO

Description

【００２９】
【表２】

【００３０】
【発明の効果】
本発明の、アイオノマー樹脂を配合してなるポリトリメチレンテレフタレート樹脂組成物が、成形サイクルの短縮が可能と同時に、バリが大幅に抑制されることが判った。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a polytrimethylene terephthalate resin composition having a short molding cycle and greatly improved burrs.
[0002]
[Prior art]
Thermoplastic polyesters represented by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, heat resistance, chemical resistance, weather resistance, and electrical properties, and are used in a wide range of fields such as automotive materials and electric and electronic parts. . Further, with the expansion and diversification of applications, higher performance, easy moldability for complicated shapes, and the like are increasingly required.
Generally, when performing injection molding of a molded product having a long flow length or a molded product in which the appearance is emphasized, an operation of increasing the injection pressure is often performed. At that time, the phenomenon that the resin leaks into a part of the molding die (burr) becomes a problem, and a good product may not be obtained.
To solve the above problems, for example, a method of adding a nucleating agent to a thermoplastic polyester resin is disclosed in JP-A-11-54189, JP-A-11-286596, and the like.
[0003]
However, in these methods, it is difficult to control the crystallinity of polytrimethylene terephthalate, and the molding cycle is not sufficiently shortened, and molding burrs are hardly improved.
Japanese Patent Application Laid-Open No. H11-54189 describes ionomers in the text, but the purpose of the publication is to improve impact resistance, particularly hinge characteristics. Rather, it is merely a description and is not a technical disclosure.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and has as its object to provide a polytrimethylene terephthalate resin composition which does not have the above-mentioned problems, that is, has a short molding cycle and has greatly improved burrs.
[0005]
Means for Solving the Invention
The inventor of the present invention has conducted a sharp study to solve the above problems, and as a result, has found that a resin composition obtained by blending an ionomer resin with a polytrimethylene terephthalate resin has a short molding cycle and significantly improves burrs. The present invention has been reached.
That is, the present invention provides: (A) a polytrimethylene terephthalate resin composition obtained by mixing 0.1 to 15 parts by weight of an ionomer resin with respect to 100 parts by weight of a polytrimethylene terephthalate resin;
2. (B) The polytrimethylene terephthalate resin composition according to (1), wherein the ionomer resin of the component is one or more selected from ethylene / acrylic ionomer and ethylene / methacrylic ionomer. ,
3. (B) The polytrimethylene terephthalate resin composition according to (1) or (2) above, wherein the metal component in the ionomer of the component is Na and / or Zn.
4. (B) The polytrimethylene terephthalate resin composition according to any one of (1) to (3), wherein the compounding amount of the ionomer resin of the component is 0.3 to 5 parts by weight.
5. The polytrimethylene terephthalate resin according to any one of the above items 1 to 3, wherein the inorganic filler is further added as a component (C) in an amount of 5 to 150 parts by weight based on 100 parts by weight of the total of (A) and (B). A composition.
[0006]
Hereinafter, the present invention will be described specifically.
First, the polytrimethylene terephthalate polymer of the present invention will be described.
The polytrimethylene terephthalate (hereinafter sometimes abbreviated as “PTT”) in the present invention refers to a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component. In the present invention, the trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, and a mixture thereof. From the viewpoint of 1,3-propanediol is particularly preferred.
[0007]
In addition, as long as the object of the present invention is not impaired, as an acid component, an aromatic dicarboxylic acid other than terephthalic acid, for example, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, Diphenoxyethane dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, etc .; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; Oxydicarboxylic acids such as caproic acid, hydroxybenzoic acid and hydroxyethoxybenzoic acid are used as glycol components as ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, Glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, may be copolymerized with such a part hydroquinone.
[0008]
The amount of copolymerization in the case of copolymerization is not particularly limited as long as the object of the present invention is not impaired, but is usually preferably 20 mol% or less of the acid component or 20 mol% or less of the glycol component. .
Further, the above-mentioned polyester component may contain a branching component such as tricarballylic acid, trimesic acid, trimellitic acid, etc., or a trifunctional or tetrafunctional ester-forming acid or trifunctional such as glycerin, trimethylolpropane, pentaerythritol. Alternatively, alcohols having tetrafunctional ester-forming ability may be copolymerized, in which case they are 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0 mol% or less of the total dicarboxylic acid component. 0.3 mol% or less. Further, PTT may be used in combination of two or more of these copolymer components.
[0009]
The intrinsic viscosity [η] of the PTT of the present invention is preferably 0.60 or more from the viewpoint of mechanical properties, more preferably [η] is 0.70 or more, and [η] is 0.80 or more. It is most preferred that this is the case.
For the intrinsic viscosity [η], the specific viscosity ηsp in o-chlorophenol and the ratio ηsp / C of the concentration C (g / 100 ml) were extrapolated to a concentration of zero using an Ostwald viscometer at 35 ° C. You can ask.
[Η] = lim (ηsp / C) C → 0
[0010]
The method for producing PTT used in the present invention is not particularly limited, but is described in, for example, JP-A-51-140992, JP-A-5-262882, JP-A-8-31177, and the like. Terephthalic acid or an ester-forming derivative thereof (for example, a lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or an ester-forming derivative thereof are heated at a suitable temperature and time in the presence of a catalyst. And a method of subjecting the resulting glycol ester of terephthalic acid to a polycondensation reaction at a suitable temperature and time to a desired degree of polymerization in the presence of a catalyst.
[0011]
Next, the ionomer resin which is the component (B) of the present invention will be described.
The ionomer resin (B) refers to a copolymer containing (b1) an α-olefin and (b2) an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms as main components. It is neutralized with a valent metal ion. Here, specific examples of the α-olefin of the component (b1) include ethylene, propylene, and butene-1, and among them, ethylene is particularly preferable.
Specific examples of the α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms of the component (b2) include, for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, and maleic acid. Acrylic acid and methacrylic acid are preferably used.
[0012]
The copolymer of the component (B) of the present invention has the above-mentioned component (b1) and the component (b2) as main components, and further contains (b4) an acrylate and / or methacryl as optional components. A copolymer containing an acid ester as a main component can also be used.
Here, as the acrylate or methacrylate of the component (b4), specifically, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid Examples thereof include methyl, n-butyl methacrylate, and isobutyl methacrylate. Of these, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferably used.
[0013]
The copolymer of component (B) may contain α, β-unsaturated carboxylic acid in an amount of usually 0.2 mol, irrespective of whether or not it is a copolymer with optional component (b4). %, Especially 5 mol% or more, and as an upper limit 25 mol% or less, especially 15 mol% or less is recommended.
The (B) ionomer resin of the present invention is obtained by neutralizing the above copolymer with at least one of (b3) at least one of trivalent metal ions. Examples of the metal ion include ions of sodium, potassium, lithium, magnesium, calcium, zinc, aluminum, ferrous iron, ferric iron, and the like. Among them, sodium and zinc are particularly preferred.
[0014]
In order to introduce such a metal ion, a copolymer having the above-mentioned (b1), (b2) and the optional component (b4) as main components, and a hydroxide, methoxide and ethoxide of the above-mentioned 1-3 valent metal , Carbonates, nitrates, formates, acetates, oxides and the like. As for the degree of neutralization, it is preferable that at least 10 mol%, especially 30 mol%, 100 mol% or less, especially 90 mol% or less of the carboxylic acid groups in the copolymer are neutralized by metal ions.
The ionomer resin as the component (B) may be a single ionomer resin neutralized with one kind of metal ion, but may be used in combination of two or more ionomer resins neutralized with different metal ions. Is preferred.
One or more of these ionomer resins are added to 100 parts by weight of the PTT resin in an amount of 0.1 to 15 parts by weight from the viewpoint of the desired effect and the appearance and warpage of the molded product. Preferably, it is 0.2 to 10 parts by weight, more preferably 0.3 to 5 parts by weight.
[0015]
Further, when the resin composition of the present invention is further blended with 5 to 150 parts by weight of an inorganic filler as the component (C) based on 100 parts by weight of the total of (A) and (B), the composition further meets the purpose. A composition is obtained.
Specific examples of the inorganic filler include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, aluminum borate whisker, wollastonite, talc, glass flake, and glass beads. In particular, glass fiber is preferable, and the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber, and the like.
[0016]
In addition, for example, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] for the purpose of improving the thermal stability of PTT as long as the object of the present invention is not impaired. Heat stabilizers such as -4,4'-diylbisphosphonite and tris (2,4-di-t-butylphenyl) phosphite; ethylenebis (oxyethylene) bis [3- (5-t-butyl); -2-Hydroxy-m-tolyl) propionate], etc., and 2- (2H-benzotriazol-2-yl) -4-6-bis (1- Various ultraviolet absorptions such as methyl-1-phenylethyl) phenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and octabenzone Nucleating agents such as talc, kaolin and boron nitride, fatty acid metal salts (Ca montanic acid and Ca stearate), fatty acids (such as stearic acid), fatty acid esters and waxes for the purpose of improving the processability and compounding For example, blending of lubricants, etc., pigments such as carbon black and aluminum powder for coloring, blending of dyes such as phthalocyanine, halogen-based flame retardants such as brominated polystyrene for the purpose of imparting flame retardancy, Blending of non-halogen flame retardants such as melamine polyphosphate, thermoplastic resins such as polycarbonate resin and ABS resin, and elastomers such as polyester polyether elastomer for the purpose of improving impact resistance and heat resistance It can be performed. In particular, the combined use with a lubricant such as a fatty acid metal salt is more suitable for the purpose of the present invention.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to the examples and the like. The thermoplastic polyester used in the examples, main evaluation methods, and measured values were determined by the following methods.
(1) Thermoplastic polyester resin (A)
A: Polytrimethylene terephthalate having an intrinsic viscosity of 0.9.
(2) Crystal nucleating agent (B)
B-1: Ethylene / methacrylic acid ionomer Metal ion component Na (trade name “HIMILAN 1707” manufactured by Mitsui DuPont Polychemicals, Inc.)
B-2: Ethylene / methacrylic acid ionomer Metal ion component Na (trade name “HIMILAN 1706” manufactured by Mitsui DuPont Polychemicals, Inc.)
B-3: Talc (trade name "Micro Ace L-1" manufactured by Nippon Talc Co., Ltd.)
[0018]
(3) Inorganic filler (C)
D: Glass fiber (03T-187 / PL, manufactured by NEC Corporation)
(4) Measurement of burrs Using a molding machine (PS40E manufactured by Nissei Plastics Co., Ltd.) set under the following conditions, a flat test piece (with a film gate) of 100 × 100 mm (having a film gate) was injected with an injection pressure. When molding by changing the injection pressure, the injection pressure is gradually increased from the injection pressure (SSP) immediately before the resin is fully filled, and the injection pressure (BP) at which burrs are observed is measured. The range of the injection pressure from SSP to BP is determined. When the injection pressure range is wider, a good molded product can be obtained under a wide range of pressure conditions, and it can be judged that the moldability is easy.
Molding conditions: cylinder temperature 260 ° C., mold temperature 90 ° C., injection time 20 seconds, cooling time 20 seconds
(5) Molding cycle A molded article with a cylindrical bottom (outer diameter 40 mmφ, height 40 mm, average wall thickness 4 mm) is molded under the following conditions to obtain a molded article with good appearance without collapse of the molded article. The required time (seconds) at the limit of the molding cycle at which the molding was possible was determined. The lower the numerical value, the better the high cycle formability.
Molding conditions: cylinder temperature 260 ° C, injection pressure: 1400 kg / cm ² , mold temperature 90 ° C
Molding cycle: The cooling time was determined while keeping the injection holding pressure time constant.
[0020]
Embodiment 1
4 parts by weight of ethylene / methacrylic acid ionomer (trade name “Himilan 1707” manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) and 100 parts by weight of PTT pellets, and 0.2 part by weight of IRGAFOS P-EPQ as a stabilizer And 0.1 parts by weight of calcium montanate as a lubricant, a twin-screw extruder equipped with a vent having a screw diameter of 25 mm and L / D = 45 (ZSK-25 manufactured by Warner & Friedler Co., Ltd.) Supplied. As the kneading conditions, the mixture was melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletized. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 1 shows the results.
[0021]
Embodiment 2
4 parts by weight of ethylene / methacrylic acid ionomer (trade name “Himilan 1707” manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.), 100 parts by weight of PTT pellets, 0.2 parts by weight of IRGAFOS P-EPQ as a stabilizer, 0.1 parts by weight of Ca montanate was blended as a lubricant, and a twin-screw extruder with a screw diameter of 25 mm and L / D = 45 (ZSK-25 manufactured by Warner & Friedler Co., Ltd.) was used. Supplied. Further, 45 parts by weight of glass fiber was supplied from a side arm installed just before the vent with respect to 100 parts by weight of the PTT pellet. As the kneading conditions, melt kneading was performed at a cylinder set temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletization was performed. Table 1 shows the results.
[0022]
Embodiments 3 to 5
Except that the amount and type of the ionomer resin were changed as shown in Table 1, the same operation as in Example 2 was performed, and the mixture was melt-kneaded and pelletized. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 1 shows the results.
[0023]
Embodiment 6
The same operation was performed as in Example 2, except that 10 parts by weight of brominated polystyrene was further added. Table 1 shows the results.
[0024]
[Comparative Example 1]
0.2 parts by weight of IRGAFOS P-EPQ as a stabilizer and 0.1 parts by weight of Ca montanate as a lubricant were added to 100 parts by weight of PTT pellets, and a vent having a screw diameter of 25 mm and L / D = 45 was used. And supplied to a twin screw extruder (ZSK-25 manufactured by Warner & Friedler Co., Ltd.). As the kneading conditions, the mixture was melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletized. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 2 shows the results.
[0025]
[Comparative Example 2]
0.2 parts by weight of talc as a nucleating agent, 0.2 parts by weight of IRGAFOS P-EPQ as a stabilizer and 0.2 parts by weight of PTT as a lubricant, and 0.1 parts by weight of Ca montanate as a lubricant with respect to 100 parts by weight of PTT pellets. And supplied to a twin-screw extruder with a screw diameter of 25 mm and L / D = 45 (ZSK-25 manufactured by Warner & Friedler Co., Ltd.). As the kneading conditions, the mixture was melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletized. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 2 shows the results.
[0026]
[Comparative Example 3]
0.2 parts by weight of IRGAFOS P-EPQ as a stabilizer and 0.1 parts by weight of Ca montanate as a lubricant were added to 100 parts by weight of PTT pellets, and a vent having a screw diameter of 25 mm and L / D = 45 was used. And supplied to a twin screw extruder (ZSK-25 manufactured by Warner & Friedler Co., Ltd.). Further, 45 parts by weight of glass fiber was supplied from a side arm installed just before the vent with respect to 100 parts by weight of the PTT pellet. As the kneading conditions, melt kneading was performed at a cylinder set temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletization was performed. Table 2 shows the results.
[0027]
[Comparative Example 4]
With respect to 100 parts by weight of the PTT pellet, 4 parts by weight of talc as a nucleating agent, 0.2 parts by weight of IRGAFOS P-EPQ as a stabilizer, and 0.1 parts by weight of Ca montanate as a lubricant. The mixture was supplied to a twin-screw extruder with a screw diameter of 25 mm and L / D = 45 (ZSK-25 manufactured by Warner & Friedler Co., Ltd.). Further, 45 parts by weight of glass fiber was supplied from a side arm installed just before the vent with respect to 100 parts by weight of the PTT pellet. As the kneading conditions, melt kneading was performed at a cylinder set temperature of 260 ° C. and a screw rotation speed of 300 rpm, and pelletization was performed. Table 2 shows the results.
[0028]
[Table 1]

[0029]
[Table 2]

[0030]
【The invention's effect】
It has been found that the polytrimethylene terephthalate resin composition of the present invention, which contains an ionomer resin, can shorten the molding cycle and at the same time greatly reduce the burr.

Claims (5)

A polytrimethylene terephthalate resin composition comprising a polytrimethylene terephthalate resin and an ionomer resin, wherein (A) 0.1 to 15 parts by weight of an ionomer resin is blended with 100 parts by weight of the polytrimethylene terephthalate resin. A polytrimethylene terephthalate resin composition comprising: The polytrimethylene terephthalate resin composition according to claim 1, wherein the ionomer resin of the component (B) is one or more selected from ethylene / acrylic acid ionomer and ethylene / methacrylic ionomer. object. The polytrimethylene terephthalate resin composition according to claim 1 or 2, wherein the metal component in the ionomer resin (B) is Na and / or Zn. The polytrimethylene terephthalate resin composition according to any one of claims 1 to 3, wherein the amount of the ionomer resin (B) is from 0.3 to 5 parts by weight. 5. The polytrimethylene terephthalate according to claim 1, wherein the component (C) further comprises 5 to 150 parts by weight of an inorganic filler based on 100 parts by weight of the total of (A) and (B). 6. Resin composition.