JPH08269306A - Polyester resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition excellent in flame retardancy, low smoke generativeness, flowability, hydrolysis resistance, and mechanical properties by adding a specific compound, melamine cyanurate and a reinforcing filler in a specific ratio. CONSTITUTION: This polyester resin composition comprises 100 pts.wt. of a polyester resin such as polybutylene terephthalate, 0.1-10 pts.wt. of a compound of the formula (R<1> -R<6> are each 1-6C alkyl; (n) is 1-10), 0.1-10 pts.wt. of melamine cyanurate and 0-10 pts.wt. of a reinforcing filler (e.g. glass fibers, wallastonite, alumina) so that the total amount of the compound of the formula and the melamine cyanurate is <=15 pts.wt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester resin composition. For details, flame retardancy, low smoke generation,
The present invention relates to a polyester resin composition having excellent fluidity, hydrolysis resistance and mechanical properties.

[0002]

2. Description of the Related Art Recently, polyester resins have been widely used in a wide range of fields such as automobile parts, electric / electronic parts, household electric appliances parts, office parts, industrial parts, textile products, construction materials, and miscellaneous goods. However, in the above applications, not only mechanical properties but also materials having flame retardancy have been required.

Various types of flame retardants for resins are known, such as inorganic flame retardants and organic flame retardants. For the purpose of flame retarding polyester resins, halogen type organic flame retardants have been often used. Has been. However, a polyester resin flame-retarded with a halogen-based organic flame retardant may corrode molding equipment such as a molding die with hydrogen halide or the like generated by thermal decomposition during molding. In addition to problems, there is a safety problem because a large amount of black smoke and toxic halogen-containing gas are generated during combustion. Moreover, recently, it has been reported that dioxin is contained in the thermal decomposition product of the halogen compound, and from the viewpoint of environmental protection, the use of the halogen compound containing the halogen-based organic flame retardant tends to be restricted. .

For this reason, a movement to use a halogen-free non-halogen flame retardant in place of the halogen-based organic flame retardant is rapidly spreading. Water-containing inorganic compounds such as magnesium hydroxide and aluminum hydroxide are known as non-halogen flame retardants. However, in order to make resins flame-retardant with these non-halogen flame retardants, it is necessary to add a considerably large amount to the resin. However, it is unavoidable that the mechanical properties of the obtained molded product are significantly deteriorated. In addition to these hydrous inorganic compounds, as proposed in Japanese Patent Publication No. 58-5939 and Japanese Patent Publication No. 60-33850,
Although examples of adding a nitrogen compound having a triazine ring have also been proposed, these proposed methods not only have insufficient flame retardancy, but also significantly reduce the toughness of the product,
There are many drawbacks such as adhesion of flame retardant to the mold (plate out) and bleed out to the product surface.

On the other hand, Japanese Patent Publication No. 51-19858, Japanese Patent Publication No. 51-39271, and Japanese Patent Publication No. 6-504563.
There is also a method of adding a phosphoric acid ester-based flame retardant as proposed in the gazettes, etc., but these proposed methods are not only insufficient in flame retardance, but also the crystallinity of the resin composition. However, there is a drawback in that the moldability is significantly deteriorated and the moldability is significantly deteriorated. In order to solve these drawbacks, a method of combining melamine cyanurate and a phosphate ester flame retardant has also been proposed. For example, JP-A-3-2816
In Japanese Patent Publication No. 52, a method of using triphenyl phosphate as a phosphoric acid ester is disclosed, but triphenyl phosphate not only causes severe plate out at the time of molding, but also bleeds out on the surface of the product after molding, It is a cause of poor appearance and contact failure.

Further, in Japanese Patent Laid-Open No. 5-70671,
As the phosphate ester, resorcinol bis (diphenyl phosphate) or resorcinol bis (di-
A method using (p-ethylphenyl phosphate) has been proposed, but these compounds have poor hydrolysis resistance, which is a cause of lowering the durability of the product. In addition, JP-A-6-157880 discloses a method of using bisphenol A bis (diphenyl phosphate) or bisphenol S bis (diphenyl phosphate) as a phosphoric acid ester. Since the ester is a liquid at room temperature, it is inferior in operability and has a drawback that it bleeds out on the surface of the product after molding. Furthermore, in these proposed methods, it is indispensable to add 30 parts by weight or more of a reinforcing filler, and these fillers reduce the toughness and elongation at break of the product, and at the same time reduce the flame retardancy. There was a drawback.

[0007]

The objects of the present invention are as follows. 1. 1. To provide a polyester resin composition flame-retarded with a halogen-free flame retardant. To provide a flame-retardant polyester resin composition in which not only the generation of corrosive gas during molding and processing but also the generation of irritating gas, corrosive gas, and black smoke during combustion is dramatically reduced. 3. To provide a flame-retardant polyester resin composition capable of obtaining a product having excellent mechanical properties and hydrolysis resistance.

[0008]

In order to solve the above problems, the invention according to claim 1 provides a polyester resin 100.
The polyester resin composition is characterized in that the following components are mixed in parts by weight, and the total amount of the components (A) and (B) is 15 parts by weight or less. Component (A): compound represented by general formula [I] ... 0.1 to 10 parts by weight

Embedded image (In the formula [I], R ^{1 to} R ⁸ represent an alkyl group having 6 or less carbon atoms, and n represents an integer of 1 to 10.) Component (B): Melamine cyanurate: 0.1 to 10 parts by weight Component (C): Reinforcing filler ... 0 to 10 parts by weight

The present invention will be described in detail below. In the present invention, the polyester resin means a thermoplastic polyester obtained by polycondensation of one bifunctional carboxylic acid component and at least one glycol component or oxycarboxylic acid.

2 used in the production of thermoplastic polyesters
Specific examples of the functional carboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
2,7-Naphthalenedicarboxylic acid, P, P'-diphenyldicarboxylic acid, P, P'-diphenyletherdicarboxylic acid, adipic acid, sebacic acid, dodecane diacid, suberic acid, azelaic acid, 5-sodium sulfoisophthalic acid or these And the like, and aromatic dicarboxylic acids or their ester-forming derivatives are preferable, and terephthalic acid or terephthalic acid diester is particularly preferable.

Specific examples of the glycol component include HO (CH ₂ ) _n OH, (n is an integer of 2 to 20) represented by the general formula: α, ω-alkylene glycol, neopentyl glycol, 1,4- Cyclohexanediol, 1,4
Examples thereof include cyclohexanedimethanol, bisphenol A, polyoxyethylene glycol, polyoxytetramethylene glycol, and ester-forming derivatives thereof. Among them, ethylene glycol,
Α, ω-alkylene glycols such as 1,4-butanediol are preferable, and 1,4 butanediol is particularly preferable. Specific examples of the oxycarboxylic acid include oxybenzoic acid, 4- (2-hydroxyethoxy) benzoic acid, and ester-forming derivatives thereof.

The thermoplastic polyester is 70 mol of the total acid component or the total diol component forming the polyester.
A copolymer may be used as long as it is a single component in an amount of at least%.
The intrinsic viscosity of the thermoplastic polyester is preferably 0.40 or more. Further, the thermoplastic polyester may be a mixture containing 60% by weight or more of the polyester as described above and 40% by weight or less of another thermoplastic polymer.

The component (A) used for preparing the polyester resin composition according to the present invention (hereinafter sometimes simply referred to as a resin composition) is a phosphoric ester compound represented by the above general formula [I]. Thus, flame retardancy is imparted to the resin composition. formula
In [I], R ^{1 to} R ⁸ represent an alkyl group having 6 or less carbon atoms. Among the alkyl groups, an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is particularly preferable. Also,
In the formula [I], n is an integer of 1 to 10, preferably 3 or less, and 1 is particularly preferable.

The amount of component (A) compounded is in the range of 0.1 to 10 parts by weight per 100 parts by weight of the polyester resin. If the content of the component (A) is less than 0.1 parts by weight, the flame retardancy becomes insufficient, and if it exceeds 10 parts by weight, the elongation at break and the hydrolysis resistance decrease. The component (B) used for preparing the resin composition according to the present invention is melamine cyanurate. This melamine cyanurate imparts flame retardancy to the resin composition.

Component (B), melamine cyanurate, is an equimolar reaction product of cyanuric acid and melamine. For example, an aqueous solution of cyanuric acid and an aqueous solution of melamine are mixed to obtain 90
It can be obtained by reacting at a temperature of -100 ° C under stirring and filtering the formed precipitate. Melamine cyanurate may have some of its amino groups or hydroxyl groups substituted with other substituents.

The blending amount of the component (B) (melamine cyanurate) is 0.1 to 100 parts by weight of the polyester resin.
It is in the range of 10 parts by weight. If the amount is less than 0.1 part by weight, the flame retardancy becomes insufficient, and if the amount exceeds 10 parts by weight, the toughness and ductility are deteriorated, and bleed out and plate out are caused.

According to the experiments of the present inventors, the blending amounts of the component (A) and the component (B) with respect to the polyester resin are the above when the blending amount of the component (A) and the component (B) is small. However, it was found that the total amount of the component (A) and the component (B) needs to be 15 parts by weight or less with respect to 100 parts by weight of the polyester resin in the case of compounding almost the same. It was If the blending amount of both components exceeds 15 parts by weight,
It is not preferable because the mechanical properties of the product obtained from the resin composition deteriorate. In addition, the preferable range of the blending amount of both components is 2 to 12 parts by weight. The blending ratio of the component (A) and the component (B) in the case of blending both components is not particularly limited, but is usually 1:10 to 10: 1, and particularly 5:10 to 10: 5. preferable.

The component (C) used for the preparation of the resin composition according to the present invention is a fibrous, granular or powdery organic substance or inorganic substance as the reinforcing filler, and strengthens or increases the amount of the product. To do Examples of the fibrous reinforcing filler include glass fiber, alumina fiber, silicon carbide fiber, boron fiber, carbon fiber, aramid fiber and the like. Examples of the granular or powdery reinforcing filler include wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, aluminum oxide. , Metal oxides such as zirconium oxide and titanium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and others, glass beads, glass flakes, boron nitride, silicon carbide and the like. To be

These reinforcing fillers as the component (C) may be used alone or as a mixture of two or more kinds, and may be pretreated with a silane-based or titanium-based coupling agent or the like, if necessary. Good.

The compounding amount of the reinforcing filler of the component (C) with respect to the polyester resin is 10 parts by weight or less based on 100 parts by weight of the polyester. If it exceeds 10 parts by weight, not only the ductility and fluidity of the resin composition are lowered, but also the flame retardancy is remarkably lowered, which is not preferable. A preferred blending amount is 0 to 3 parts by weight, and a particularly preferred range is 0 to 2 parts by weight.

The polyester resin composition according to the present invention is
Even if an auxiliary flame retardant such as an antimony compound or an oxygen-containing compound is not added, the desired excellent flame retardancy is exhibited. The polyester resin composition according to the present invention, in addition to the above three components, other resin additives that do not impair the object of the present invention,
It can be added in an amount that does not impair the object of the present invention.
Other resin additives include heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, preservatives, adhesion promoters, colorants, crystallization promoters, foaming agents, lubricants, bactericides. , Plasticizers, release agents, thickeners, drip-proofing agents, impact modifiers, smoke suppressants, and the like.

To prepare the polyester resin composition according to the present invention, each component may be weighed in a predetermined amount and mixed by a known mixing means. Examples of the mixing means include a dry blending method using a blender and a mixer, and a melt mixing method using an extruder. Usually, a method of melt mixing with a screw extruder, extruding into a strand shape, and pelletizing is preferable.

The polyester resin composition according to the present invention is
The target product can be easily manufactured by various molding methods such as injection molding method, extrusion molding method, compression molding method, hollow molding method, and the obtained product is excellent in flame retardancy and mechanical properties. . Further, the product obtained from the resin composition according to the present invention, when used for a long period of time, since sublimation products and decomposition products do not occur, for example, connectors, relays, switches,
It is preferably used for electric / electronic parts such as sensors, actuators, microactuators, microsensors, coil bobbins and the like.

[0024]

INDUSTRIAL APPLICABILITY The present invention has the following special advantageous effects and its industrial utility value is extremely large. 1. The polyester resin composition according to the present invention is excellent in flame retardancy and does not contain a halogen compound, so that the generation of corrosive gas during molding is small, and the irritating gas during combustion, corrosive gas, and black smoke are generated. Is dramatically less. 2. From the polyester resin composition according to the present invention, a product having excellent mechanical properties and hydrolysis resistance can be obtained. 3. The polyester resin composition according to the present invention does not produce a sublimation product or a decomposition product when molding a product or when the product is used for a long period of time, so that the contact characteristics of electric / electronic parts are not deteriorated. Suitable for use.

[0025]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples without departing from the gist thereof. In the examples, "part" means "part by weight". Further, in the following description examples, various properties of the resin composition were evaluated by the following methods.

(1) Elongation at break (%): ASTM D-6
It measured based on 38. (2) Strength retention rate (%): The test piece was exposed to steam at 120 ° C for 2
After 4 hours of exposure, a tensile test was conducted according to ASTM D-638, and the following formula was given: strength retention (%) = {(tensile strength after exposure to steam) / (tensile strength before exposure to steam)} The retention of tensile strength was measured and evaluated based on x100. It can be said that the higher the strength retention rate, the better the hydrolysis resistance. (3) Limiting oxygen index (LOI): ASTM D-2863
It measured according to. (4) Flammability test (UL-94): U of Underwriter's Laboratories Inc.
According to L-94 standard vertical combustion test.

(5) Tc (freezing point of polyester resin composition): Using a DSC (TA-2000) manufactured by DuPont, about 10 mg of a sample was heated to 260 ° C. at 16 ° C./minute under a nitrogen atmosphere, and the state was maintained. After holding for 5 minutes, the temperature was decreased to 30 ° C. at a temperature decrease rate of 16 ° C./minute for measurement. The higher this temperature is, the more it affects the crystallinity and crystallization rate of the composition, and the higher Tc is, the more excellent the crystallinity, moldability, and mold releasability are, and high cycle molding is possible. , Difficult to deform. (6) Presence or absence of plate-out: After molding 30 products in succession, the state of adhesion of the flame retardant to the mold surface was visually observed.

[Examples 1 to 5] Polybutylene terephthalate {manufactured by Mitsubishi Engineering Plastics Co., Ltd.,
A phosphate ester compound represented by the following formula [II] and melamine cyanurate were blended with 100 parts of the product name Novadour, intrinsic viscosity = 0.95} at a ratio shown in Table-1. This blend was kneaded using a 30 mmφ bent type twin-screw extruder at a cylinder temperature of 250 ° C., and extruded into strands to form pellets.

From the pellets, an UL94 combustion test piece and a limiting oxygen index test piece were prepared by using an injection molding machine {J28SA type manufactured by Japan Steel Works Ltd.} with a cylinder temperature of 250 ° C. and a mold temperature of 85 ° C. Molded. The evaluation tests (1) to (6) above were performed on the obtained pellets, test pieces, and the like. The results are shown in Table-1.

[0030]

Embedded image

[Example 6] In the example described in Example 2, polybutylene terephthalate was replaced with polyethylene terephthalate {manufactured by Mitsubishi Chemical Corporation, intrinsic viscosity = 0.65}, and talc {Hayashi as a reinforcing filler was used. Kasei Co., Ltd.
Made, trade name: Micron White} was added and blended. The resulting blend was pelletized by the same procedure as in the same example. UL94 combustion test pieces and limiting oxygen index test pieces were molded from the pellets at a cylinder temperature of 280 ° C. and a mold temperature of 115 ° C. The evaluation tests (1) to (6) above were performed on the obtained pellets, test pieces, and the like. The results are shown in Table-1.

Comparative Example 1 Pellets were pelletized by the same procedure as in Example 1 except that the phosphate ester and melamine cyanurate were not blended in the example described in Example 1,
A test piece was molded. The evaluation tests (1) to (6) above were performed on the obtained pellets, test pieces, and the like. The results are shown in the table
It is shown in FIG.

[Comparative Example 2] The same as Example 1 except that the amounts of the phosphoric acid ester represented by the formula [I] and melamine cyanurate were changed to the amounts shown in Table 1. Pelletizing and test pieces were performed in the same procedure as in the examples. Regarding the obtained pellets, test pieces, etc., the above (1)
The evaluation test of (6) was performed. The results are shown in Table-1.

Comparative Example 3 A test piece was formed by pelletizing in the same procedure as in Example 2 except that melamine cyanurate was not blended in the example described in Example 2. Regarding the obtained pellets, test pieces, etc., the above (1)
The evaluation test of (6) was performed. The results are shown in Table-1.

[Comparative Example 4] In the example described in Example 2, a phosphoric acid ester represented by the following structural formula [II] was added instead of the phosphoric acid ester represented by the formula [I]. A test piece was formed by pelletizing in the same procedure as in the same example. Regarding the obtained pellets, test pieces, etc., the above (1)
The evaluation test of (6) was performed. The results are shown in Table-1.

[0036]

[Chemical 4]

[Comparative Example 5] In the example described in Example 2, talc was further used as a reinforcing filler (Hayashi Kasei Co., Ltd.).
Manufactured, trade name: Micron White} was added and blended, and pelletized by the same procedure in the same example to form a test piece. The evaluation tests (1) to (6) above were performed on the obtained pellets, test pieces, and the like. The results are shown in Table-1.

[Comparative Example 6] In the example described in Example 3, except that the phosphoric ester represented by the formula [I] was not blended, pelletization was carried out by the same procedure as in the same example to form a test piece. did. The evaluation tests (1) to (6) above were performed on the obtained pellets, test pieces, and the like. The results are shown in Table-1.

[0039]

[Table 1]

The following is clear from Table-1. (1) The polyester resin composition according to the present invention does not contain a halogen compound, but has excellent flame retardancy, and the products have excellent mechanical properties and hydrolysis resistance (Examples 1 to 6). reference). (2) On the other hand, even if the component (A) and the component (B) are within the scope of claim 1, the composition having a compounding amount outside the scope of claim 1 has a significantly deteriorated mechanical property. , Plate-out occurs (see Comparative Example 2). (3) Further, the composition containing only the component (A) but not the component (B) has a low limiting oxygen index (LOI) and T
c also decreases (see Comparative Example 3). The composition in which the component (A) was not blended but only the component (B) was blended had a low elongation at break (%) and poor flame retardancy (see Comparative Example 6). (4) The composition containing the phosphoric acid ester represented by the formula [III] in place of the component (A) has an extremely low strength retention rate (5) (see Comparative Example 4). (5) A composition in which the component (A) and the component (B) are within the scope of claim 1 but the component (C) is outside the scope of claim 1 has remarkably low mechanical properties and flame retardancy. Is also bad (see Comparative Example 5).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 85/02 LSB C08L 85/02 LSB

Claims (2)

[Claims] 1. A polyester resin containing 100 parts by weight of each of the following components, and the total amount of the components (A) and (B) is 15 parts by weight or less. Polyester resin composition. Component (A): compound represented by general formula [I] ... 0.1 to 10 parts by weight (In the formula [I], R ^{1 to} R ⁸ represent an alkyl group having 6 or less carbon atoms, and n represents an integer of 1 to 10.) Component (B): Melamine cyanurate: 0.1 to 10 parts by weight Component (C): Reinforcing filler ... 0 to 10 parts by weight 2. The polyester resin composition according to claim 1, wherein the polyester resin is polybutylene terephthalate.