JPS6366346B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition, and more particularly to a resin composition with excellent moldability. Polyethylene terephthalate (hereinafter abbreviated as PET) is a typical thermoplastic polyester.
Polybutylene terephthalate (hereinafter abbreviated as PBT)
It is known as an industrial molding material and is widely used in electrical insulation parts, automobile parts, etc. due to its excellent mechanical properties, chemical resistance, electrical properties, heat resistance, etc. Further, these various properties are further improved by adding various additives, such as functional imparting agents such as glass fibers, fillers, and flame retardants, and the range of their application is widened. However, it has been pointed out that when such a functional additive is blended, the fluidity of the resin composition during molding deteriorates. In addition, the demand for thinner molded products, mainly for electrical insulation applications, has become increasingly severe in recent years, and the above-mentioned fluidity during molding has become an essential market-required characteristic. For this reason, various methods have been proposed to improve fluidity. For example, it is known that wax, metal soap, etc. are used as lubricants, but the use of these lubricants certainly does not improve fluidity during molding. However, on the other hand, the addition of these compounds causes a decrease in flame retardancy and molded product strength, resulting in new problems being pointed out. As a result of extensive research to improve the above problems, the present inventors added a specific polycaprolactone derivative to thermoplastic polyester in which at least 50% of all end groups were capped with a capping agent having brominated phenyl groups. It has been found that by doing so, not only the fluidity is significantly improved, but also the strength can be further improved without impairing the flame retardance, and the present invention has been achieved. That is, the present invention comprises (A) per 100 parts by weight of a thermoplastic polyester resin, (B) 0 to 200 parts by weight of a filler, and (C) a number average molecular weight of 20,000 or less and at least 50% of all end groups being bromine. The present invention relates to a resin composition comprising 1 to 30 parts by weight of a polycaprolactone derivative capped with a capping agent having a phenyl group. In the thermoplastic polyester used as component (A) in the present invention, the acid component is terephthalic acid, and the diol component or fatty acid such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, etc. The main target is polyesters consisting of at least one type of group diol. Among these, preferred are polytetramethylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, etc., which have a fast crystallization rate. Further, as the aromatic polyester, a part of the above-mentioned polyester may be substituted with a copolymer component, and examples of such copolymer component include isophthalic acid, phthalic acid; alkyl-substituted phthalate such as methyl terephthalic acid and methyl isophthalic acid. Acids; 2,
Naphthalene dicarboxylic acids such as 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, etc.; 4,4'-
Diphenyldicarboxylic acids such as diphenyldicarboxylic acid and 3,4'-diphenyldicarboxylic acid; aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid such as 4,4'-diphenoxycitanedicarboxylic acid; succinic acid; , adipic acid, sebacic acid, azelaic acid, decane dicarboxylic acid, cyclohexane dicarboxylic acids, etc.; alicyclic diols such as 1,4-cyclohexanedimethanol; dihydroxybenzene such as hydroquinone, resorcinol, etc. 2,2-bis(4-hydroxyphenyl)-
Aromatic diols such as propane, bisphenols such as 2,2-bis(4-hydroxyphenyl)-sulfone, ether diols obtained from bisphenols and glycols such as ethylene glycol; ε-oxycaproic acid; Examples include oxycarboxylic acids such as hydroxybenzoic acid and hydroxyethoxybenzoic acid. Furthermore, a branched component is added to the above-mentioned aromatic polyester.
For example, an acid capable of forming a trifunctional or tetrafunctional ester, such as tricarballylic acid, trimesic acid, trimellitic acid, etc., or an alcohol capable of forming a trifunctional or tetrafunctional ester, such as glycerin, trimethylolpropane, pentaerythritol, etc. may be copolymerized in an amount of 1.0 mol % or less, preferably 0.5 mol % or less, more preferably 0.3 mol % or less. The above-mentioned aromatic polyester used in the present invention preferably has an intrinsic viscosity of 0.40 or more, more preferably 0.45 or more. Here, the intrinsic viscosity is a value measured at a concentration of 0.2 g/100 ml in orthochlorophenol at 35°C. The above-mentioned aromatic polyester can be produced by a conventional production method, such as a melt polycondensation reaction or a method combining this with a solid phase polymerization reaction. For example, to explain an example of manufacturing polyethylene terephthalate, terephthalic acid or its ester-forming derivative (for example, lower alkyl ester such as dimethyl ester, monomethyl ester, etc.) and ethylene glycol or its ester-forming derivative are heated in the presence of a catalyst. Polyethylene terephthalate can be produced by a method in which the resulting glycol ester of terephthalic acid is polymerized to a predetermined degree of polymerization in the presence of a catalyst. In the present invention, fillers used as component (B) include fibrous materials such as glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, calcium sulfate fibers, steel fibers, ceramic fibers, boron whiskers, etc. , mica, silica, talc, calcium carbonate, glass beads, glass flakes, clay, wollastonite and the like are exemplified by powdered, granular or plate-like inorganic fillers. These fillers are usually blended as reinforcing materials, surface modifiers, or for the purpose of modifying electrical, thermal, and other properties. When used as component B), it not only acts as a reinforcing filler, but also exhibits a high degree of heat resistance and deformation stability in combination with the crystallization promoting effect of the nucleating agent described below. The glass fiber as component (B) used for this purpose is not particularly limited as long as it is generally used for reinforcing resins. For example, a long fiber type (glass roving), short fiber type chopped strand, milled fiber, etc. can be selected and used. Further, the glass fibers may be treated with a sizing agent (eg, polyvinyl acetate, polyester sizing agent, etc.), a coupling agent (eg, silane compound, borane compound, etc.), or other surface treatment agent. Furthermore, it may be coated with a resin such as a thermoplastic resin or a thermosetting resin. usually,
Long fiber type glass fibers are used by being cut into a desired length before or after blending with the resin, and this mode of use is also useful in the present invention. In the present invention, the addition of component (B) is determined by taking into account the effects caused by addition, the loss of the original excellent properties of thermoplastic polyester due to excessive addition, molding problems, especially a decrease in fluidity, etc., and its blending amount It is desirable that the total amount of component (B) does not exceed 200 parts by weight per 100 parts by weight of thermoplastic polyester. Also, when adding component (B), the amount added should be 5
It is preferable that the amount is at least part by weight. If the amount of component (B) added exceeds 200 parts by weight, the melt flowability of the composition will be extremely poor, making it impossible to obtain a molded product with a good appearance. The effect of improving strength, heat resistance, and other properties is undesirable because it reaches saturation. The polycaprolactone derivative used as component (C) in the present invention is based on polycaprolactone with a number average molecular weight of 20,000 or less, and at least 50% of the terminal OH groups and/or terminal COOH groups are replaced with a monovalent nuclear bromine-substituted phenyl compound ( obtained by blocking with a blocking agent). The base polycaprolactone is obtained by ring-opening polymerization of ε-caprolactone, and as a polymerization initiator, for example, n-hexyl alcohol,
Monohydric alcohols such as n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, lauryl alcohol, myristyl alcohol; for example, ethylene glycol, propylene glycol, ethyl ethylene glycol, 2-methyl-1,2-propanediol, pinacol, β-
Glycols such as butylene glycol, diethylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol; trihydric alcohols such as glycerin, 1,2,3-butanetriol, 1,2,3-pentanetriol, etc. class; e.g. erythritol,
Tetrahydric alcohols such as pentaerythritol; e.g. phenol, bisphenol A, 2,4,6
- Aromatic alcohols such as tribromophenol and tetrabromobisphenol A; monovalent carboxylic acids such as benzoic acid, p-methylbenzoic acid, lauric acid, myric acid, 2,3,4 tribromobenzoic acid, and pentabromobenzoic acid Acids; for example, isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, succinic acid, adipic acid, cepacic acid, azelaic acid, decadicarboxylic acid, cyclohexanedicarboxylic acid acid, tetrachlorophthalic acid,
Dihydric carboxylic acids such as tetrabromo terephthalic acid; for example, tricarballylic acid, trimellisic acid,
Trivalent carboxylic acids such as trimellitic acid; Tetravalent carboxylic acids such as pyromellitic acid; For example, ε-
Examples include oxycarboxylic acids such as oxycarboxylic acid and hydroxyethoxybenzoic acid. Furthermore, using these polymerization initiators, ε-
As a catalyst for accelerating the reaction during ring-opening polymerization of caprolactone, a known ring-opening catalyst such as a tin-based catalyst such as tetraoctyltin or diphenyltin dilaurate or a titanium-based catalyst such as tetrabutyl titanate is used. It is preferable. As the terminal capping agent for the polycaprolactone thus obtained, nuclear bromine-substituted phenylcarboxylic acids and derivatives thereof can be used as the OH terminal capping agent, and more specifically, monobromobenzoic acid, dibromobenzoic acid, tribromobenzoic acid, etc. Examples include tetrabromobenzoic acid, pentabromobenzoic acid, monobromotoluic acid, pentabromobenzoic acid yotyl ester, pentabromobenzoic acid ethyl ester, and pentabromobenzoic acid chloride. Further, as the COOH terminal blocking agent, nuclear bromine-substituted phenols can be used, and more specific examples include tribromophenol, tribromooxytoluene, pentabromophenol, and the like. A known esterification reaction can be used to obtain end-capped polycaprolactone by reacting polycaprolactone with a nuclear brominated phenol, a nuclear bromine-substituted phenylcarboxylic acid, or an ester-forming derivative thereof. This can be easily obtained. The polycaprolactone derivative thus obtained consists mainly of polycaprolactone derivatives represented by the following formula. [R ¹² CO(-O(-CH ₂ )- ₅ CO)- _o O]- _n R ¹¹ [-
CO(-O(-CH ₂ )- ₅ CO)- _o ′OR ¹³ ] _n ′ [However, in the formula, R ¹¹ is a (m+m′)-valent organic group; R ¹² and R ¹³ are monovalent organic groups. is a group, and R ¹² and
50% or more of the total amount of R ¹³ is brominated phenyl;
n and n' are each a number of 2 or more; m and m' are each a number of 0 to 4, and (m+m') is 1
That's all. ] According to the research results of the present inventors, the end-blocked polycaprolactone derivative used in the present invention is effective in improving the fluidity of thermoplastic polyester;
When compounding polycaprolactone-based derivatives with a number average molecular weight greater than 20,000,
While it shows almost no liquidity improvement effect,
It is clear that when a polycaprolactone-based derivative with a small number average molecular weight of 20,000 or less is blended, it not only shows a remarkable effect of improving fluidity, but also shows an effect of improving molded product strength without deteriorating flame retardancy. It became. Therefore, the number average molecular weight of the polycaprolactone derivative used in the present invention is suitably 20,000 or less, preferably 10,000 or less, more preferably 5,000 or less, even more preferably 2,000 or less. The amount of polycaprolactone blended is 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, per 100 parts by weight of the thermoplastic polyester resin. If this amount is less than 0.1 part by weight, it will have no substantial effect on improving the fluidity, which is the objective of the present invention, and if it is more than 30 parts by weight, the thermal stability will be significantly reduced, making it impractical. I don't like it because it has some drawbacks. Any method of compounding can be used to obtain the resin compositions of the present invention. Generally, it is preferable to disperse these ingredients more uniformly, and there is no need to mix or homogenize all or part of them simultaneously or separately using a mixer such as a blender, kneader, roll, extruder, etc., or to homogenize the mixed ingredients. A method can be used in which a part of the components are mixed simultaneously or separately using, for example, a blender, kneader, roll, extruder, etc., and the remaining components are further mixed using these mixers or extruders for homogenization. Furthermore, it is preferable that the polycaprolactone derivative, which is the component (C) of the present invention, be kneaded into a thermoplastic polyester resin. The most common method is to melt and knead a previously dry-blended composition in a heated extruder to homogenize it, extrude it into wires, and then cut it into desired lengths and granulate it. . The resin composition thus prepared is usually kept sufficiently dry before being introduced into a hopper of a molding machine and subjected to molding. Other methods include, for example, a method in which other components are added or mixed during the production of the thermoplastic polyester resin, before the polycondensation, after the polycondensation, or during the polycondensation. In particular, when glass fiber is used as a filler, in order to prevent it from shattering as much as possible during kneading, and to improve workability during composition production,
It may be dry blended without melt-kneading together with other ingredients in an extruder, for example, glass fiber-free thermoplastic polyester resin granules made in an extruder and a predetermined amount of glass chops. The strand or a composition mixed with a thermoplastic resin having a high glass fiber content prepared in advance can be charged into a molding machine hopper and subjected to molding. The resin composition of the present invention may further contain various additives for the purpose of improving other properties. Examples of such additives include decabromo biphenyl ether,
Halogen-containing compounds such as octabromobiphenyl ether, hexabromobiphenyl ether, halogenated polycarbonate oligomers (for example, polycarbonate oligomers produced using brominated bisphenol A as a raw material), halogenated epoxy compounds, halogenated polystyrene, etc.: Red phosphorus , phosphorus compounds, phosphorus-nitrogen compounds such as phosphonic acid amide, flame retardant aids (eg, antimony trioxide, zinc borate, etc.), and the like. Furthermore, a known compound commonly used as a crystal nucleating agent can be added to promote crystallization of thermoplastic polyester resin. Examples of these nucleating agents include talc, titanium dioxide,
Examples include benzoates, metal stearates, sodium and lithium salts of mono- or polycarboxylic acids, and ionic copolymers of α-olefins and α,β-unsaturated carboxylates. Furthermore, for the purpose of improving heat resistance, antioxidants such as hindered phenol compounds and sulfur compounds, or heat stabilizers, such as phosphorus compounds such as trimethyl phosphate, triphenyl phosphate, triphenyl phosphite, etc., may be added. You can also do it. In addition, for the purpose of improving melt viscosity stability and hydrolysis resistance,
Various epoxy compounds may be added. Examples of epoxy compounds include bisphenol A type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin, aliphatic glycidyl ethers obtained by reacting various glycols or glycerol with epichlorohydrin, and novolac type epoxy compounds obtained from novolac resins and epichlorohydrin. compounds, alicyclic compound type epoxy compounds obtained from alicyclic compounds, etc. are preferable, and particularly preferable epoxy compounds include bisphenol A
type epoxy compounds and diglycidyl ethers of low molecular weight polyethylene glycols. Examples of other additives include ultraviolet absorbers, antioxidants, colorants, lubricants, antistatic agents, and foaming agents. In addition, in small proportions other thermoplastic resins such as sterol resins, acrylic resins, polyethylene,
Polypropylene, fluororesin, polyamide resin,
Polycarbonate resin, polysulfone, etc.: Thermosetting resin, such as phenolic resin, melamine resin,
Unsaturated polyester resin, silicone resin, etc.: Furthermore, soft thermoplastic resins such as ethylene-vinyl acetate copolymer, polyester elastomer, etc. may be added. The resin composition of the present invention can be easily molded by a conventional method using a general thermoplastic resin molding machine. Moreover, it exhibits extremely good molding fluidity, and the toughness and strength of molded products with thinner walls or complex shapes are significantly superior to conventional products. Hereinafter, the present invention will be explained in detail with reference to Examples. In addition, the intrinsic viscosity of the thermoplastic polyester described in the examples is a value measured at 35° C. in an orthochlorophenol solution. Furthermore, parts mean parts by weight. Various properties in the examples were measured by the following methods. (1) Static strength: Tensile test... Based on ASTM D-638. Impact strength: Conforms to ASTM D-256. (Thickness 1/8, with isotto notch) (2) Melt fluidity: Compliant with JIS-K7210. (Test load: M=100Kgf, die diameter: Dd=1
mm, die length: Dt = 10 mm) Reference example <Synthesis of terminally modified polycaprolactone (A)> 100 parts of ε-caprolactone, 4.31 parts of ethylene glycol and tin octylate as a polymerization initiator
Add 0.09 parts and heat to 180℃, and at this temperature 6
Polycaprolactone was obtained by stirring and polymerizing for hours. Polycaprolactone thus obtained
100 parts of the mixture was mixed with 100 parts of toluene and 20 parts of pyridine, and 70 parts of pentabromobenzoic acid chloride was added little by little while stirring the mixture thoroughly. Further, heating was continued for 30 minutes while vigorously stirring under toluene reflux. After the reaction was completed, the solvent was distilled out of the system, and the reaction product was washed with water to obtain modified polycaprolactone (A). <Synthesis of terminal-modified polycaprolactone (B)> Add 40 parts of tetrabromobisphenol A and 0.1 part of tin octylate as polymerization initiators to 100 parts of ε-caprolactone, heat to 180°C, and polymerize by stirring at this temperature for 6 hours. Polycaprolactone was obtained. 100 parts of the polycaprolactone thus obtained was mixed with 100 parts of toluene and 20 parts of pyridine, and 20 g of tribromo-para-toluic acid chloride was added little by little while stirring the mixture thoroughly. Further, heating was continued for 30 minutes while vigorously stirring under toluene reflux. After the reaction was completed, the solvent was distilled out of the system, and the reaction product was washed with water to obtain modified polycaprolactone (B). Example 1 and Comparative Examples 1 to 2 A fluidity improver and a flame retardant were added to polybutylene terephthalate (PBT) dried at 120°C for 5 hours in the amounts shown in Table 1, and mixed uniformly. Barrel temperature 250 with 65mmφ extruder
The mixture was melt-mixed at ℃, and the thread discharged from the die was cooled and cut to obtain pellets for molding. Next, using this pellet, the melt fluidity (flow value (Q)) at 260℃ was measured, and the cylinder temperature was 240℃, the mold temperature was 60℃, and the injection pressure was
A test piece for strength measurement was molded at 1000 Kg/cm ² and static strength was measured. The results are shown in Table-1.

[Table] As is clear from Table 1 above, the intrinsic viscosity is
The flow value (Q) of the flame retardant composition based on PBT of 1.05 is small, indicating poor fluidity during molding (Comparative Example 1), but when terminal-modified polycaprolactone (A) is added to it In this embodiment (Example 1), as the flow value increases, the tensile elongation at break and the impact strength also increase, indicating that the toughness and strength are improved. In addition, when adding the same amount of low molecular weight polyethylene wax (Comparative Example 2), the flow value increases, but in terms of strength, it not only results in a decrease in toughness, but also in the flammability test according to UL-94. Also, the melt dripping was severe and the flame did not disappear during the dripping, resulting in a ranking of V-2. Examples 2 to 4 and Comparative Example 3 Glass chopped strands with a length of 3 mm, modified polycaprolactone, and other fillers were added to chips of polyethylene terephthalate (PET) with an intrinsic viscosity of 0.71 that had been dried at 130°C for 5 hours, as shown in Table 2. They were added in the amounts shown in the figure below and mixed uniformly using a V-type blender. The resulting mixture was heated to a barrel temperature using a 65mmφ extruder.
The mixture was melted and mixed at 270°C, and the thread discharged from the die was cooled and cut to obtain pellets for molding. Next, the pellets were dried with hot air at 130°C for 5 hours, and then a test piece mold for measuring physical properties was attached to a 5-ounce injection molding machine, and the pellets were cooled at a cylinder temperature of 270°C, a mold temperature of 85°C, an injection pressure of 800 kg/cm ² . The test piece was molded under molding conditions of 20 seconds and a total cycle of 35 seconds. The tensile elongation, impact strength, and flame retardance according to UL94 of the thus obtained molded article were measured. These results are shown in Table-2.

[Table] Comparative Example 4 In place of the modified polycaprolactone (A) of Example 1, 5 parts by weight of modified polycaprolactone (C), which does not contain a nuclear substituted halogen and is end-capped with benzoic acid, was used as an end-blocking agent. A polybutylene terephthalate resin composition containing modified polycaprolactone (C) and a flame retardant was obtained under the same conditions as in Example 1. The fluidity (flow value Q) of this resin composition at 260℃ is 0.095, and the tensile elongation at break of a molded product test piece molded at 240℃ is 20%, the impact strength is 3.2Kg・cm/cm, and UL94. The flame retardancy according to the standard was VO. Comparing Example 1 and Comparative Example 4, it was found that polycaprolactone end-capped with a capping agent containing a halogen-substituted aryl group exhibited excellent fluidity during melt molding. In addition, comparative example 4
The modified polycaprolactone (C) used in the above was a commercially available polycaprolactone whose terminal group is a hydroxyl group (manufactured by Daicel Corporation; trade name Plaxel #205,
Number average molecular weight 550) 100 parts by weight of methyl benzoate
Adding 100 parts by weight and 0.14 parts of manganese acetate, 190 parts by weight
The reaction mixture was heated to ~210°C and stirred for 10 hours while removing methanol distilled out from the reaction system. Furthermore, it was obtained by removing an excess amount of methyl benzoate under reduced pressure and had a hydroxyl value (measured according to JIS K1557) of 2.1.

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of thermoplastic polyester resin, (B) 0 to 200 parts by weight of filler, and (C) 0.1 to 0.1 to end-blocked polycaprolactone with a number average molecular weight of 20,000 or less. 30 parts by weight, in which caprolactone accounts for at least 50 of the total end groups.
% of a polycaprolactone derivative capped with a capping agent having a brominated phenyl group. 2 Polycaprolactone (C) has the following formula [R ¹² CO(-O(-CH ₂ )- ₅ CO)- _o O]- _n R ¹¹ [-
CO(−O(−CH ₂ )− ₅ CO)− _o ′OR ¹³ ]− _n ′ [However, in the formula, R ¹¹ is an (m+m′)-valent organic group; R ¹² and R ¹³ are monovalent is an organic group, and R ¹² and
50% or more of the total amount of R ¹³ is a brominated aryl group; n and n' are each a number of 2 or more; m,
m' is a number from 0 to 4, and (m+m')
is 1 or more. ] The resin composition according to claim 1, which is polycaprolactone represented by the following. 3. The resin composition according to claim 1, wherein the thermoplastic polyester (A) is polyethylene terephthalate. 4. The resin composition according to claim 1, wherein the thermoplastic polyester (A) is polybutylene terephthalate. 5. The resin composition according to claim 1, wherein the thermoplastic polyester (A) is a mixture of 95 to 5 wt% polyethylene terephthalate and 5 to 95 wt% polybutylene terephthalate.