JPH11100495A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition improved in molding processability while retaining the heat resistance inherent in PEN resin. SOLUTION: This resin composition comprises 100 pts.wt. of a polyester resin blend prepared by compounding (A) polyethylene-2,6- naphthalenedicarboxylate with (B) polytetramethylene-2,6- naphthalenedicarboxylate so as to be 50-80 wt.% in the proportion of the component A based on a total of 100 wt.% of the components A and B, (C) 1-10 pts.wt. of a polyalkylene glycol or a derivative thereof wherein at least one end thereof is a carboxylic ester and/or alkyl ether, (D) 5-60 pts.wt. of a fibrous reinforcing material, and (E) 0.01-10 pts.wt. of a crystal nucleating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition,
More specifically, it relates to a polyethylene-2,6-naphthalenedicarboxylate (hereinafter sometimes abbreviated as PEN) resin having excellent heat resistance, mechanical properties, and moldability.

[0002]

2. Description of the Related Art Polyethylene-2,6-naphthalenedicarboxylate is excellent in heat resistance and mechanical properties, and is widely used for packaging materials such as beverage bottles, films and sheets.

[0003] In the field of resin applications, automotive parts,
Due to miniaturization and high performance of electric and electronic components, materials having high heat resistance and mechanical properties are required. However, regarding the use of PEN as a resin, a typical polybutylene terephthalate (hereinafter referred to as P
In some cases, the rate of crystallization from a molten state is significantly slower than that of resins and the like, and the heat resistance of molded products is not sufficient even at high mold temperatures during injection molding. For this reason, it has not been used while having excellent heat resistance.

[0004] Similarly, a method for improving the injection moldability of polyethylene terephthalate (hereinafter sometimes abbreviated as PET) resin having a low crystallization rate has been studied as a resin. A method for obtaining a molded article having excellent heat resistance has been proposed. For example, a compound of a polyalkylene glycol compound having a terminal blocked is disclosed in JP-A-8-81972 and JP-A-04-19772.
363356), a method of blending a benzoic acid derivative (Japanese Patent Application Laid-Open No. 55-133444), and a method of blending various other compounds.

[0005] As for the PEN resin, attempts have been made to improve the moldability by blending a polyalkylene glycol compound. For example, there is Japanese Patent Application Laid-Open No. 01-268752. However, since the PEN resin is further inferior in crystallinity to the PET resin, the effect of the conventional method is insufficient, and it has been difficult to use it under a wide range of conditions.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has been developed in view of the above problems.
The point is to obtain a resin composition.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to improve the moldability of a PEN resin while maintaining the heat resistance and mechanical properties thereof. As a result, the PEN resin and polytetramethylene-2,6 -It has been found that a composition in which a specific amount of a specific compound is mixed in a specific ratio of a mixture of a naphthalene dicarboxylate (hereinafter sometimes abbreviated as PBN) resin meets the above-mentioned object, and the present invention has been achieved.

That is, the present invention relates to (A) polyethylene-
2,6-naphthalenedicarboxylate and (B) polytetramethylene-2,6-naphthalenedicarboxylate, wherein component (A) has a total amount of component (A) and component (B) of 1
100 parts by weight of the mixed polyester resin mixture at a ratio of 50 to 80% by weight based on 00% by weight, (C) a polyalkylene glycol having at least one terminal of a carboxylic acid ester and / or an alkyl ether or a derivative thereof 1 10 to 10 parts by weight, (D) fibrous reinforcing material
A resin composition comprising 5 to 60 parts by weight and 0.01 to 10 parts by weight of (E) a crystal nucleating agent.

Hereinafter, the present invention will be described in detail. The polyethylene-2,6-naphthalenedicarboxylate used as the component (A) in the present invention is a polyester comprising 2,6-naphthalenedicarboquinic acid as an acid component and diethylene glycol as a diol component. The polytetramethylene-2,6-naphthalenedicarboxylate used as the component (B) is a polyester containing 2,6-naphthalenedicarboic acid as an acid component and tetramethylene glycol as a diol component.

These polyesters may be obtained by substituting a part of the above-mentioned acid and diol components with a copolymer component. As the copolymerization component, phthalic acid derivatives such as terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, and methyl isophthalic acid; naphthalenedicarboxylic acids such as 2,7-naphthalenedicarboxylic acid and 1,5-naphthalenedicarboxylic acid; Derivatives; diphenylcarboxylic acids such as 4,4'-diphenyldicarboxylic acid and 3,4'-diphenyldicarboxylic acid and derivatives thereof; 4,4'-
Aromatic dicarboxylic acids such as diphenoxymethane dicarboxylic acid and 4,4'-diphenoxyethane dicarboxylic acid; aliphatic or alicyclic aliphatic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, decane dicarboxylic acid, cyclohexane dicarboxylic acid Dicarboxylic acids; other aliphatic diols;
Alicyclic diols such as 4-cyclohexanedimethanol;
Dihydroxybenzene and its derivatives such as hydroquinone and resorcin; bisphenol compounds such as 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) sulfone; bisphenol compounds and glycols such as ethylene glycol; And aromatic diols such as ether diols obtained from oxydicarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid and hydroxyethoxybenzoic acid.

When these components are used as a copolymer component, the copolymerization ratio is 40 mol% or less, preferably 10 mol% or less.
Mol% or less.

Further, the above-mentioned polyester has a branching component,
For example, tricarballylic acid, trimesic acid, trimellitic acid and the like, an acid having an ester-forming ability of 3 or 4 per molecule,
Alternatively, an alcohol having an ability to form a trifunctional or tetrafunctional ester such as glycerin, trimethylolpropane, or pentaerythritol is used in an amount of 1.0 mol% or less, preferably 0.5 mol% or less.
You may copolymerize below mol%, More preferably, below 0.3 mol%.

The intrinsic viscosity of PEN and PBN used in the present invention is preferably in the range of 0.5 to 1.5 when measured at 35 ° C. using o-chlorophenol.
Further, those having 0.5 to 0.9 are more preferable.

The PEN and PBN used in the present invention can be produced by a usual production method, for example, a melt polycondensation reaction or a method combining this with a solid phase polycondensation reaction.

For example, a production example of PEN will be described. A catalyst comprising 2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof (eg, a lower alkyl ester such as dimethyl ester or monomethyl ester) and ethylene glycol or an ester-forming derivative thereof is used as a catalyst. Is reacted by heating in the presence of a polyethylene glycol by a method in which the resulting glycol ester of 2,6-naphthalenedicarboxylic acid is polymerized to a predetermined degree of polymerization in the presence of a catalyst.
A 2,6-naphthalenedicarboxylate resin can be produced.

The polyalkylene glycol having at least one terminal of a carboxylic acid ester and / or an alkyl ether of the component (C) used in the present invention or a derivative thereof may be a compound represented by the following general formula (I). preferable.

[0017]

Embedded image

[N is an integer of 3 to 30, R is an aliphatic hydrocarbon group having 2 to 6 carbon atoms, X is hydrogen and 1 carbon atom.
To 18, an alkyl group, an aryl group, an acyl group, or an aroyl group, and Y is hydrogen, an alkyl group, an aryl group, an acyl group, or an aroyl group having 1 to 18 carbon atoms, provided that at least one of X and Y is hydrogen. Other groups. ]

Preferred compounds as the component (C) are glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyneopentyl glycol, polyethylene glycol / polypropylene glycol copolymer, and polyethylene glycol / polytetramethylene glycol copolymer. At least one end of the compound is esterified with a carboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, palmitic acid, stearic acid, benzoic acid, the methyl ether of the glycol, ethyl Ether, butyl ether, lauryl ether and stearyl ether.

The molecular weight of the polyalkylene glycol as the component (C) is preferably from 200 to 1500. If the molecular weight is smaller than this, the generation of volatile gas during extrusion or molding is increased, and if the molecular weight is larger, the compatibility with PEN and PBN is undesirably reduced.

Conventionally, PEN has a very low crystallization rate from a molten state and is unsuitable for injection molding. When polyalkylene glycol or a derivative thereof is blended with PEN to improve its moldability, the effect is insufficient if the blending amount is within a range that maintains the extrudability and the workability during molding.

However, the resin component (A) PE
When a polyalkylene glycol or a derivative thereof as the component (C) is further added to a polyester resin mixture of N and (B) PBN, the molding processability is remarkably improved, and a molded article having sufficient heat resistance by injection molding. The inventor has found that is obtained.

The PEN and PBN used in the present invention are:
The PEN is mixed so that the ratio of PEN is 50 to 80% by weight based on the total amount of PEN and PBN of 100% by weight. PEN
If the ratio is less than 50% by weight, the heat resistance of the resulting composition is not sufficient, and if it is more than 80% by weight, the effect of improving the crystallization speed of the resin composition by the addition of PBN is not sufficiently exhibited.

The compounding amount of the polyalkylene glycol or the derivative thereof as the component (C) is 1 to 10 parts by weight per 100 parts by weight of the polyester resin mixture of the components (A) and (B). If the amount is less than 1 part by weight, the effect of improving the moldability of the composition is small, and if the amount is too large, decomposition during extrusion or molding becomes significant.

Examples of the fibrous reinforcing material (D) used in the present invention include glass fiber, aramid fiber, carbon fiber, steel fiber, asbestos, ceramic fiber, potassium titanate whisker, boron whisker and the like. May be used in combination.

Among these fibrous reinforcing materials, reinforcement by glass fiber is preferable, and the glass fiber is not particularly limited as long as it is generally used for reinforcing resin. For example, it can be selected from long fiber type (glass roving), short fiber chopped strand, milled fiber and the like.

The fibrous reinforcing material such as glass fiber is treated with a sizing agent (eg, polyvinyl acetate, polyester sizing agent, etc.), a coupling agent (eg, silane compound, borane compound, titanium compound, etc.), and other surface treatment agents. It may be.

Usually, a long fiber type glass fiber is used after being cut into a desired length before or after blending with a resin, and this use form is also useful in the present invention.

The amount of the fibrous reinforcing material (D) is 5 to 60 parts by weight based on 100 parts by weight of the polyester resin mixture. If the amount is less than 5 parts by weight, the effect of improving the mechanical strength and heat resistance of the molded product is not sufficient, and if it exceeds 60 parts by weight, the fluidity of the composition in the molten state is extremely poor. As a result, a molded article having a good appearance cannot be obtained, and the strength also reaches saturation, which is not preferable.

When a glass fiber is used, a glass fiber having a length of 0.2 mm or more at the main portion in the composition is preferably used.

The nucleating agent of component (E) used in the present invention is a known compound generally used as a nucleating agent for polyester resin.

For example, talc, silica, graphite,
Inorganic fine particles such as carbon powder, pyroferrite, gypsum, and neutral clay; metal oxides such as magnesium oxide, aluminum oxide, and titanium dioxide; sulfates, phosphates, silicates, oxalates, stearates, and benzoic acid Acid salt, salicylate, tartrate, sulfonate, montan wax salt, montan wax ester salt, terephthalate, benzoate, carboxylate, α-olefin and α, β-unsaturated carboxylate And ionic copolymers.

Among the compounds used as the nucleating agent, talc having an average particle size of not more than 20 μm is particularly effective.

The amount of the crystal nucleating agent (E) is 0.01 to 10 parts by weight based on 100 parts by weight of the polyester resin mixture.
Parts by weight. When the amount is less than 0.01 part by weight, the effect as a nucleating agent is not sufficient.
If the amount exceeds 0 parts by weight, the fluidity of the composition in a molten state and the mechanical properties of the composition become extremely poor, which is not preferable.

To the resin composition of the present invention, a pigment or other compounding agent may be added if necessary. Such ingredients include fillers such as kaolin, clay,
Wollastonite, talc, mica, calcium carbonate,
Examples thereof include powdery, granular and plate-like inorganic fillers such as barium sulfate and glass bead glass flakes.

[0036] Flame retardants such as brominated polystyrene,
Brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated acrylic resin, brominated bisphenol-A-diglycidyl ether and its oligomer, polycarbonate oligomer produced from brominated bisphenol-A, brominated biphenyl ether, Halogen-containing compounds such as brominated diphthalimide compounds and dimers of chlorinated hexapentadiene; phosphorus compounds such as red phosphorus and triphenyl phosphate; phosphorus-nitrogen compounds such as phosphonic amides; melamine, melam, melem, melon, cyanur. Triazine compounds such as acid and melamine cyanurate; flame-retardant assistants used alone or in combination with metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, and dihydrated stone or the above-mentioned halogen-containing compounds. Antimony trioxide, antimony compounds such as sodium antimonate, boron oxide, it is possible to blend the metal oxides such as iron oxide.

In order to further enhance the effects of these flame retardants,
You may mix | blend the compound which suppresses the dripping of the molten particle at the time of combustion. Known compounds that exhibit such effects include polytetrafluoroethylene and fumed colloidal silica produced by emulsion polymerization.

Further, an antioxidant such as a hindered phenol compound, an aromatic amine compound, an organic phosphorus compound and a sulfur compound or a heat stabilizer can be added for the purpose of improving heat resistance.

For the purpose of improving the melt viscosity stability and the hydrolysis resistance, various epoxy compounds, oxazoline compounds and the like may be added. Examples of the epoxy compound include bisphenol-A type epoxy compounds obtained by reacting bisphenol-A with epichlorohydrin, aliphatic glycidyl ethers obtained from the reaction of various glycols and glycerol with epichlorohydrin, novolak type epoxy compounds, aromatic or fatty acids Aromatic carboxylic acid type epoxy compounds, alicyclic compound type epoxy compounds and the like are preferable. As the oxazoline compound, aromatic or aliphatic bisoxazolines, particularly 2,2′-bis (2-oxazoline), 2,2′-m-phenylene Bis (2-oxazoline) is preferred.

In addition, stabilizers, coloring agents, lubricants, ultraviolet absorbers and antistatic agents can be added. Furthermore, other thermoplastic resins in small proportions, such as other polyesters, polyamides, polyphenylene sulfide, polyphenylene ether, polycarbonate, phenoxy, polyethylene and its copolymers, polypropylene and its copolymers, polystyrene and its copolymers , Acrylic and acrylic copolymers, polyamide elastomers, polyester elastomers and the like; thermosetting resins such as phenolic resins, melamine resins, unsaturated polyesters, silicone resins and the like may be blended.

In the resin composition of the present invention, it is preferable that these components are uniformly dispersed, and any method can be used for the compounding method. For example, all or part of the blended components are heated or extruded into a single-screw, twin-screw extruder or the like, and the molten resin extruded into a wire after homogenization by melt-kneading is solidified by cooling. Next, there is a method of cutting into a desired length and granulating, but a method using another blender such as a blender, a kneader, a roll and the like may be used. In addition, a method of sequentially adding the components by using these in combination or repeating a plurality of times can be used.

In order to obtain a resin molded product from the resin composition for molding thus produced, the resin molded product is usually supplied to a molding machine such as an injection molding machine while keeping it sufficiently dried. Furthermore, it is also possible to dry blend the constituent materials of the composition, directly charge them into a molding machine hopper, and melt-knead them in a molding machine.

[0043]

The present invention will be described below in detail with reference to examples. In addition, the measurement of various characteristics in an Example was based on the following method. (1) Intrinsic viscosity: measured at 35 ° C. using an Ostwald viscosity tube using o-chlorophenol as a solvent. (2) Mechanical properties: Tensile test according to ASTM D638, bending test according to ASTM D790, impact test according to ASTM D790
Complies with D256 (Izod, with notch). (3) Solder resistance: A molded product of 12 × 12 × 0.8 mm was immersed in a heated and melted solder bath for 10 seconds, taken out, and tested for the maximum temperature of the solder bath without deformation and surface damage of the molded product.

Examples 1-3, Comparative Examples 1-7 (A) Intrinsic viscosity 0.60 dried at 130 ° C. for 8 hours with hot air
PEN resin (manufactured by Teijin Ltd.), (B) PBN resin (manufactured by Teijin Ltd.) having an intrinsic viscosity of 0.77 dried by hot air at 130 ° C. for 8 hours, and (C-1) benzoic acid ester at both terminals Polyethylene glycol having a molecular weight of 400 (KRM-
4004: Sanyo Kasei Kogyo Co., Ltd.), (C-2) polyethylene glycol having a molecular weight of 1,000 at both ends and methyl ether (Carpol CLE-1000: Asahi Denka Co., Ltd.), (D) glass fiber ( Average fiber diameter 13μm,
3mm chopped strand: NEC Glass Co., Ltd.
And (E) talc (PKNN: Hayashi Kasei Co., Ltd.)
Was uniformly mixed in advance in a tumbler at the ratios shown in Table 1, and then a cylinder temperature of 290 ° C., a screw rotation speed of 150 rpm, and a discharge rate of 50 kg / hr were applied to a vacuum while using a vented twin-screw extruder having a screw diameter of 44 mm for each screw. , And the thread discharged from the die was cooled and cut to obtain molding pellets.

Next, using the pellets, an injection molding machine having an injection capacity of 5 oz. Was used to obtain a cylinder temperature of 280 ° C., a mold temperature of 120 ° C., an injection pressure of 80 MPa, an injection time of 10 seconds, a cooling time of 20 seconds, and a total molding cycle of 45 seconds. A molded article for measuring each property was molded under the following conditions. Further, as the mold releasability at the time of molding under the above conditions, the presence or absence of deformation of the molded article was observed.

As a comparative example, a molded article using a PET resin was also prepared. In that case, a PET resin having an intrinsic viscosity of 0.71 which was dried with hot air at 130 ° C. for 8 hours was used, and the extrusion temperature was 2
Test pieces were prepared under the same conditions as above except that the molding temperature was set to 80 ° C and the molding temperature was set to 270 ° C.

[0047]

[Table 1]

Each characteristic was measured using these molded articles. Table 2 shows the results.

[0049]

[Table 2]

The PEN resin itself has a higher melting point than the PET resin and is expected to be applied to parts that require higher heat resistance, but its moldability is very poor, and glass fibers and talc are blended. A good molded product cannot be obtained even with the composition (Comparative Example 1). Furthermore, no effect is observed even when a polyethylene glycol whose terminal is blocked is blended or a PBN resin is mixed in a small amount (Comparative Examples 2 to 4).

However, the resin components are PEN resin and P
When a suitable amount of a BN resin is mixed and polyethylene glycol having a terminal blocked is blended, injection molding can be performed in a good condition, and its heat resistance is superior to a PET resin composition of the same composition. A molded article utilizing the heat resistance of the resin can be obtained (Examples 1 to 3,
Comparative Example 7).

When the blending amount of the terminal-blocking polyethylene glycol is increased, the heat resistance is limited, so that the generation of smoke and the like at the time of extrusion becomes intense, and molding is not performed in a good state (Comparative Example 6). When the ratio is large, its heat resistance is lower than that of PET resin, so that its value is reduced (Comparative Example 5).

[0053]

According to the present invention, a polyalkylene glycol having a terminal blocked is added to a polyester resin mixture of PEN and PBN.
When glass fiber and a crystal nucleating agent are blended, the moldability of the PEN resin is improved while maintaining the heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71:02)

Claims (1)

[Claims] (1) Polyethylene-2,6-naphthalenedicarboxylate (A) and polytetramethylene (B)
Polyester resin mixture 100 in which 2,6-naphthalenedicarboxylate is mixed with component (A) in a proportion of 50 to 80% by weight based on a total amount of component (A) and component (B) of 100% by weight. Parts by weight, (C) a polyalkylene glycol or a derivative thereof in which at least one terminal is a carboxylic acid ester and / or an alkyl ether
A resin composition comprising 1 to 10 parts by weight, (D) 5 to 60 parts by weight of a fibrous reinforcing material, and (E) 0.01 to 10 parts by weight of a crystal nucleating agent.