KR830000973B1 - Polyester composition - Google Patents

Abstract

No content.

Description

Polyester composition

The present invention relates to polyester compositions for use as molding materials, in particular polyester compositions suitable as low temperature molding materials.

More specifically, the present invention relates to a novel polyester composition which exhibits good formability when molded at low molding temperatures of 100 ° C. or less and at the same time provides excellent surface and physical properties.

Polyethylene terephthalate is used in many industrial products such as fibers and films because of its excellent heat resistance, chemical resistance, mechanical properties and electrical properties.

However, when it is used in the plastics field to make injection molded products, many defects are observed due to its special crystallization behavior in the molding phase.

That is, polyethylene terephthalate is originally a crystalline polymer, but because of its high secondary transition temperature, the molded article is formed at a temperature above the secondary transition temperature when it is molded at a low molding temperature of 100 ° C. or below, which is molded into a general mold, especially for use as a general thermoplastic. The shape stability of remarkably worsens. Moreover, it has the disadvantage of requiring a long residence time in the mold and showing bad mold release, and producing the obtained molded articles and / or streaks.

To eliminate these drawbacks, it is necessary to move the crystallization start temperature of polyethylene terephthalate to the lower temperature side and increase the crystallization rate so that crystallization is sufficiently propagated to the molded article surface layer.

In order to increase the rate of crystallization, there is generally a method of adding 0.5 to 1% by weight of crystal nucleating agents, especially inorganic fillers such as talc or titanium oxide.

However, the addition of such an inorganic filler has a very different effect as a nucleation agent depending on its particle size distribution and / or uniform dispersibility, and furthermore, it does not show a satisfactory effect even if the addition amount is increased. In particular, it is difficult to move the crystallization start temperature to a lower temperature side and the crystallization of the surface layer of the molded article formed in the low temperature mold is very insufficient.

In addition, the composition in which the metal salt of mono- or polycarboxylic acid is blended to promote crystallization is disclosed in Japanese Patent Application No. 4097/1972; Known from 14502/1972 et al .; Moreover, the composition compatible with the above-mentioned filler and the metal salt of carboxylic acid is known by Japanese Unexamined-Japanese-Patent No. 32455/1972. However, none of these compositions makes it possible to obtain molded articles having high surface crystallinity, good release properties, and physical properties by molding in low temperature molds below 100 ° C.

Therefore, an object of the present invention is to provide a polyester composition with improved polyethylene terephthalate crystallinity. The other purpose is to show good moldability at low molding temperature below 100 ℃, that is, short molding cycle, good surface property, good moldability such as mold release, and can make molding without streaking and use injection molding machine for normal use. It is to provide a polyester composition having good surface gloss by forming in a low temperature mold.

It is another object of the present invention to provide a polyester composition which can produce molded articles having excellent physical properties even when molded in a low temperature mold. Yet another object of the present invention is to provide a polyester composition which, even when molded in a low-temperature mold, has a low heat shrinkage and thermal deformation at a temperature above the secondary transition temperature, and can produce a molded article having a high deflection temperature and excellent heat resistance. have.

Other objects and effects of the present invention will be apparent from the following detailed description. The inventors have made intensive studies to move the initiation temperature of polyethylene terephthalate to a lower temperature side and to increase the rate of crystallization. As a result, it was found that activating the motility of the glycol portion of polyethylene terephthalate was effective. This discovery led us to the invention.

In short, the present invention is 0.1 to 15% by weight of a compound containing at least one epoxy group and a polyoxyalkylene chain based on polyesters and polyesters comprising polyethylene terephthalate or at least 80 mol% ethylene terephthalate repeating units. The organic crystallization promoter of% is formulated.

The composition of the present invention has a good crystallization rate and high crystallinity and good surface gloss even if it stays in the mold for a short residence time. In addition, there is an advantage that even when molded in a low temperature mold has excellent releasability and surface properties, and the shape stability of the molded article formed in the low temperature mold is excellent at a temperature above the secondary transition temperature. It is not completely known why the particular compound according to the present invention has an excellent crystallization promoting effect, but possible conjectures can be made as follows.

The mobility of the glycol portion of polyethylene terephthalate is activated by the polyoxyalkylene chains of certain compounds, which are compounding agents with low secondary transition temperatures. Furthermore, the epoxy group of the compounding agent and the terminal group of the polyethylene terephthalate react at least partially. This results in the molecular orientation of the polyethylene terephthalate in the mold in injection molding by partial bridge bonding reaction which improves the dispersibility of the above described formulations and many other formulations (described later) and at the same time gives a low bridge density. By these two effects, it is assumed that crystallization is promoted uniformly and effectively.

Therefore, the excellent crystallization promoting effect is a close relationship between the length of the polyoxyalkylene chain and the density of the epoxy group. In any case, it is surprising that certain compounds of the present invention have surprising effects compared to polyalkylene glycols having no epoxy group or ethylene glycol diglycyl ether having an epoxy group but having a short molecular chain. The polyesters used in the present invention comprise polyethylene terephthalates and copolyesters which preferably contain 90 mol% but at least 80 mol% of ethylene terephthalate repeat units. As the copolymer component, known acid components and / or glycol components may be used.

That is, the copolymerization component may be selected from acid components such as isophthalic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, diphenyl ether 4,4'-dicarboxylic acid, adipic acid, sebacic acid, and the like; Glycol components such as propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, 2,2-bis (4-hydroxyphenyl) propane and the like; Oxyacids such as P-oxybenzoic acid, P-hydroxyethoxybenzoic acid and the like.

The polyester is suitably measured at 30 DEG C with a solvent in which phenol and tetrachloroethane are mixed at a weight ratio of 6: 4, preferably at least 0.55 but having an intrinsic viscosity of at least 0.5. Of course, the above-mentioned polyethylene terephthalate and copolyester may be used for compounding.

As the organic crystallization accelerator used in the present invention containing polyoxyalkylene and at least one epoxy group, compounds containing polyalkylene chains and at least one epoxy group in the same molecule are suitable, but they are produced in compounding or molding. It is also possible to use both compounds in combination so as to form a compound containing a polyoxyalkylene chain and at least one epoxy group by reaction. Such compounds containing polyoxyalkylene chains and at least one epoxy group in the same molecule are polyalkylene glycols or derivatives thereof.

Suitable such epoxy compounds include polyalkylene glycol glycidyl ethers represented by the following general formula.

Wherein A: C ₁ to C ₅ aliphatic hydrocarbon group, hydrogen or glycidyl group

R: aliphatic hydrocarbon group of C ₂ ~ C ₅

n is an integer of 2 or more

Specific examples include mono- or diglycidyl of polyethylene glycol; Mono- or diglycidyl ether of polyethylene glycol; Mono- or diglycidyl ether of polytetramethylene glycol; Mono- or diglycidyl ether of polyneopentyl glycol; Mono- or diglycidyl ethers of polyethylene glycol / polypropylene glycol polymers; Mono- or diglycidyl ethers of polyethylene glycol / polytetramethylene glycol copolymers; Monoglycidyl ether of methoxy polyethylene glycol; Monoglycidyl ethers of ethoxypolypropylene glycol; Back

Suitable compounds in addition to those included in the general formula; Mono- or polyglycidyl ethers of polyhydric alcohol / alkylene oxide additives such as mono- or polyglycidyl ethers of glycerin / alkylene oxide adducts; And mono- or polyglycidyl ethers of neopentylglycol / alkylene oxide additives. However, the organic crystallization promoter is not limited to those mentioned above.

It is suitable that the molecular weight of polyalkylene glycol and its derivatives is 5000 or less, More preferably, it is 150-3000, Most preferably, it is 200-1500. When used at a high molecular weight, the compatibility with polyester is lowered and the crystallization promoting effect is lost. As the organic crystallization promoter, a polyglycidyl ether compound containing an average of 1,2 or more epoxy groups in one molecule is particularly suitable.

As the epoxy number (the number of equivalents of epoxide oxygen present in 100 g of the compound), 0.1 to 0.7 is suitable. The compounding quantity of the organic crystallization accelerator is the mold temperature. The amount varies depending on the amount of the inorganic filler and the like, but is usually 0.1 to 15% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the amount of polyester used.

Especially in the case of shaping | molding in a low temperature metal mold | die, 1 weight% or more is preferable. In order to obtain a compound capable of forming an organic crystallization accelerator during the molding process, it may be used in combination with a polyoxyalkylene compound polyepoxy compound having active hydrogen at the terminal such as polyalkalen glycol.

In such a case, a catalyst may be used in combination to promote the reactivity of the two compounds. Therefore, the compounding ratio of the two compounds having an epoxy value of 0.1 to 0.7 can be obtained.

In the present invention, when the inorganic filler is used in combination, the crystallization rate is further accelerated by synergy with the organic crystallization accelerator used.

Inorganic fillers used in the present invention are, for example, talc (main component 3MgO.4SiO ₂ .nH ₂ O), clay (main component Al ₂ O ₃ .2SiO ₂ .2H ₂ O), kaolin (main component Al ₂ O ₃ .2SiO ₂ .2H ₂ O), mica (alminosilicates containing alkali metals, main component 2K ₂ O.3Al ₂ O ₃ .6SiO ₂ .2H ₂ O), asbestos (main component 3MgO.2SiO ₂ .2H ₂ O), calcium silicate ; Silica; It includes gypsum. These may be used alone or in combination. Of these fillers, particularly suitable are silicates. These inorganic fillers have an average particle diameter of 30 micrometers or less, suitably 10 micrometers or less. For calcium silicate and silica, those having an average particle diameter of 500 mμ or less are suitable.

In particular, as a composition for molding a thin molded article, it is preferable to use a particulate inorganic filler having a particle size of 500 mμ or less in combination with an inorganic filler having a particle size of 30 μm to 500 μm in terms of moldability and dimensional stability in the presence of heat.

A relatively small amount is sufficient to promote crystallization, but if dimensional stability and heat resistance are considered, the amount is 5-10% by weight. The compounding amount of the organic crystallization accelerator may be slowed down by blending the inorganic filler.

When the amount of the inorganic filler exceeds 40% by weight, not only the fluidity and breaking elongation of the molded article and the adhesive strength of the product are reduced, but also the surface properties of the molded article are weakened. Furthermore, by blending the polyester-based elastic resin having a secondary transition temperature of 10 ℃ or less in the composition of the present invention, it is possible to enhance the dispersibility of the organic crystallization promoter and to promote crystallization. As the polyester-based elastic resin used herein has a glass transition temperature of 10 ° C. or less, the soft part may be polytetramethylene glycol, polyethylene glycol, polyethylene glycol / polypropylene glycol block copolymer, polyhydric alcohol / alkylene oxide additives, or the like. Polyalkylene glycol residues such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene para-oxybenzoate, polyethylene terephthalate / adipate, polyethylene terephthalate / sebacate, polyethylene Aromatic polyester / polyether tan which is aromatic polyester residues such as naphthalate, polybutylene terephthalate / adipate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / ethylene terephthalate, etc. There is a holy resin.

The above-mentioned elastic resin has a glass transition temperature of normally 10 ° C. or lower, suitably -15 ° C. to -60 ° C .; Its molecular weight is more than 10,000 and suitably more than 30,000; Its polyalkylene glycol has a molecular weight of 650 or more, suitably 800-6,000; And its polyalkylene glycol moiety constitutes 20% by weight or more, and suitably 20 to 80% by weight aromatic polyaryl ester / polyalkylene glycol block copolymer.

Other polyester-based elastic resins that can be used here include polymeric polyester elastomers having a molecular weight of 10,000 or more wherein the soft portion thereof is aromatic tailings such as polyalkylene adipates, polyalkylene sebacates and the like and the aromatic polyester tailings mentioned above. And aromatic dicarboxylic acids such as terephthalic acid and naphthalene carboxylic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and alcohol components, and straight chain glycols such as ethylene glycol and butylene glycol, and branches such as neopentyl glycol. The polymeric polyester elastic resin of the molecular weight 10,000 or more obtained by copolymerization and condensation of the glycol which has an excitation is mentioned. However, those suitable in terms of uniform and easy combination, crystallization promoting effect, and surface properties (external phenomenon, etc.) are aromatic polyester / polyether block-polymer elastomers, in particular aromatic polyester / polytetramethylene glycol block-polymer elastomers. In other polybutylene terephthalate / polytetramethylene glycol block polymeric elastomeric resins.

The compounding quantity of such an elastic resin is 0.2-20 weight% based on polyethylene terephthalate or other main polyester. Other auxiliary dispersants for organic crystallization accelerators are capable of blending such elastomeric resins in bulk, but a blending amount of at least 20% by weight raises the drop in heat deflection temperature.

Especially suitable compounding quantity is 1 to 10 weight%.

In the present invention, a fibrous reinforcing material may be added to further increase the dimensional stability in the heat of the heat deformation temperature. Fibrous reinforcements that can be used include carbon fibers, graphite fibers; Metal carbide fibers, such as silicon carbide fibers, silicon nitride fibers, boron carbide fibers, and metal nitride fibers; Glass fibers; Heat-resistant organic fibers and the like. Among these fibers, glass fibers are particularly suitable.

This glass fiber may be a glass fiber used for reinforcing plastics. In particular, the diameter of 3 ~ 30μ is good, depending on the production method, various types of fibers, such as twisted or short cut can be used. Among such glass fibers, for example, silane-treated or chromium-treated ones are suitable for improving adhesion in plastics.

The blending amount of such fibers is from 0 to 50% by weight, suitably from 5 to 40% by weight, based on the total resin amount. The combination of fibrous reinforcements further improves the surface properties and significantly increases the heat deflection temperature. As a result of this improvement, the stability of the molded article formed in the low temperature mold in the presence of heat in a high temperature environment of more than 100 ℃ can be improved. Such molded articles can be used as industrial plastics with heat resistance.

In the case of the composition of the present invention, the total blending amount of the inorganic filler and the fibrous reinforcement is 10 to 60% by weight, in particular 15 to 50% by weight, based on the total composition, and is formed by forming at a high heat deformation temperature and a low temperature mold below 100 ° C. Even molded parts have very good dimensional stability.

When the total blending amount is 60% by weight or more, the fluidity in the molding and the surface characteristics of the molded article are deteriorated, and at the same time, the breaking elongation is weakened and the adhesive strength of the molded article is reduced.

When the composition of the present invention is used in combination with a release agent, a synergistic effect is generated together with an organic crystallization accelerator, and the formability is improved to obtain very good surface properties even by molding at low temperature.

Suitable as release agents used herein are esters of C ₁₅ to C ₅₀ fatty acids with alcohols; Salts of the aforementioned fatty acids and metals of Groups IA, IIA of the Periodic Table of the Elements and mixtures thereof. For example, the metal salt of stearic acid, such as sodium stearate, magnesium stearate, calcium stearate, etc., and the metal salt of montanic acid, such as sodium montanate, calcium montanate, etc. are mentioned. These can be used individually or in mixture of 2 or more. The compounding quantity of a mold release agent is 0 to 3 weight% normally based on polyester.

Overall, metal salts of fatty acids also have activity and effects as reaction promoters for epoxy compounds. Therefore, the polyoxyalkylene compound containing active hydrogen is used in combination with the polyepoxy compound to make the organic crystallization accelerator, and particularly preferably a fatty acid metal salt is blended.

The present invention is completely different from the traditional and general polyethylene terephthalate moldings which must be molded as quickly as possible using high molding temperatures such as 140 ° C. That is, the present invention is to obtain a molding material having excellent moldability and surface properties even when molded at a low temperature, such as other industrial plastics such as nylon, polycarbonate, polyacetal. This object is achieved by blending an appropriate amount of the organic crystallization promoter of the present invention, and it is impossible to produce polyethylene terephthalate-based molding materials having excellent moldability and surface properties in low temperature molding using conventionally known crystallization promoters.

In addition, by blending the inorganic filler and the fibrous reinforcing material, the moldability is improved, and it is possible to obtain a molded article having excellent heat resistance, that is, less heat deformation and heat shrinkage at high temperatures even when molded in a low temperature mold. Moreover, moldability can be improved further by using a mold release agent. Of course, the composition may be molded at a high molding temperature of 140 ° C. as in conventional methods.

In this case, the molding effect is increased because the crystallization rate is increased and the molding cycle is shortened.

The composition of the present invention may be blended with polyester stabilizers such as antioxidants and ultraviolet absorbers depending on the use and purpose, or may be blended with a plasticizer, lubricant, flame retardant antistatic agent, colorant, mold inhibitor, foaming agent and the like. .

Flame retardants include, for example, compounds containing halogens or phosphoric acids, such as organic halogen compounds and organophosphates, and metal compounds of group Vb of the periodic table such as antimony trioxide are used as auxiliary to the flame retardants. Especially the tint of molded parts. Suitable flame retardants in terms of physical properties and flame retardancy are carbonates of halogenated bisphenols or their oligomers as promulgated in US Pat. No. 3,833,685 and such oligomers are halogenated triazine halogenated bisphenols, monohydric phenols or mono Obtained by reaction with hydric alcohol (terminal stator).

The carbonates of halogenated bisphenols and their oligomers are represented by the following formula (I).

X ¹ and X ² are each a bromine or chlorine atom; p and q are integers from 1 to 4, respectively; n is an integer from 2 to 4; r, t are each 0 or an integer from 1 to 20; Y means an alkylene group, an alkylidene group, -O-,-CO-, -S-,-SO _2- , or-(where two benzene rings are directly connected).

Suitable are oligomers having an average degree of polymerization of 2-30. In the formula (I), any organic group such as, for example, a phenyl group, a substituted phenyl group, or an alkyl group may be an end group. The oligomer obtained by the reaction of halogenated triazine and halogenated bisphenol is represented by the following (II).

Where X ¹ , X ² , p, q, n, r, t, Y mean the same as in formula (I); R ₁ means a halogen atom, a lower alkali group, a halogenated lower alkyl group, a phenyl group, a halogenated phenyl group, or the like.

Suitable are oligomers having an average degree of polymerization of 2-30. The terminal group in formula (II) may be any of the groups as in formula (I). The organic crystallization promoter of the present invention can improve flame retardant dispersibility into polyester and can regenerate flame retardancy. The compounding quantity of a flame retardant is 2-50 weight% based on resin total amount, Preferably it is 5-30 weight%.

The blending amount of the flame retardant adjuvant is usually 50% by weight or less based on the flame retardant, preferably 10 to 40% by weight and 10% by weight or less based on the total amount of the resin.

In order to improve impact resistance, the present invention may be blended with an elastic material such as polyamide or rubber. Examples of the elastic material such as rubber include those having a glass transition temperature of 0 ° C. or lower and suitably −20 ° C. or lower, and they are not compatible with polyester and can be dispersed in a fine by-product phase in the polyester. Suitable rubbery elastomers are copolymers composed of 30-95% by weight ethylene composition and 70-5% by weight ethylenically unsaturated units or partially saponified such copolymers.

The copolymer may be further copolymerized or conjugated with a unit having functional groups such as acrylic acid, methacrylic acid, glycidyl methacrylate, hydroxyalkyl acrylate, and the like. The organic crystallization promoter of the present invention not only improves the dispersion of the polymer having improved impact resistance into polyester, but also increases intermediate adhesion between the polymer having improved impact resistance and polyester so as to increase the adhesion strength.

Moreover, the blending of the above polymers improves the strength of the joint of the molded article.

The compounding quantity is usually 30% by weight or less, suitably 1 to 20% by weight, based on the total resin.

The polyester composition production process of the present invention is not particularly limited and may be made by any method.

In such a fixation; Entering the extruder in which the polyester and other compositions are premixed and the mixture melt mixed therein; Other compositions, except polyester and fibrous reinforcement, are first mixed and the mixture is placed in an extruder.

The melt is, for example, coated around the glass roving to cool to cool and then cut into appropriate lengths (so-called wire coating method); A fibrous reinforcement or inorganic filler is blended into the polyester during or after the polymerization step and then all other compositions; A process in which a polyester, an inorganic filler, a fibrous reinforcement material, an organic crystallization promoter are mixed and the brothers are blended in the molding process; After polyester polymerization, the organic crystallization promoter is compounded to give a part of it like the end groups of the polyester, and then all other additives are blended; Any several compositions are kneaded together to form small grains and other compositions are melted and mixed with the small grains; There is such a process as the polyester is divided into several parts and these parts are separately mixed with various other compounding agents to form kernels of different compositions, and then the small particles are melt mixed.

However, the mixing step and the compounding time are not limited to the above.

In the present invention, the polyester composition can be easily obtained and the molded article of the composition obtained at a molding temperature of 100 ° C. or lower, in particular at a molding temperature of 85 ° to 90 ° C., gives surface layer crystallinity (described later) of 0.5 or more. .

However, particularly suitable compositions are those which give a surface crystallinity of at least 0.7.

Surface layer crystallinity (A) is a factor which can express the crystallization property of a molded article.

When polyethylene terephthalate is molded at a molding temperature of 100 ° C. or less, the surface layer of the molded article becomes almost transparent and the value of (A) is 0.15 or less.

On the other hand, when it is heat treated at 150 ° C. for one hour, crystallization is almost completely made and the value (A) is increased to 1.05. Thus, since the low-crystallized molded article is changed to a high-crystallized molded article by heat treatment, but the product is molded by heat, the present invention provides a polyester composition which makes a molded article having high surface crystallinity without heat treatment after low temperature molding.

In the case of flat parts obtained from the composition of the present invention, crystallization is sufficiently performed even under general molding conditions, and the molded article has excellent dimensional stability and mechanical properties in the presence of heat.

Therefore, the composition of the present invention can be widely used for molding various molded parts, sheet-like articles, tubular articles, laminates, containers, etc., but is well suited for molding electric parts, automobile parts, etc. in consideration of excellent electric resistance.

The present invention will be described below by way of example, which means by weight unless otherwise indicated. In the example, molding of test pieces and various evaluations of molded articles are carried out according to the following method.

(1) forming of test pieces

An amount of polyethylene terephthalate (extreme viscosity 0.60; melting point 264 ° C.) and a compounding agent are added and mixed in a tumbling blender. Then, unless otherwise indicated, the mixture is placed in a hopper of a 40 mm diameter vented extruder and melt mixed to produce a compound chip of the composition at a cylinder temperature of 250 ° to 275 ° to 280 ° C. (temperatures are in turn from the hopper side). do.

Compound chips are dried under reduced pressure at 120 ° C. for 4 hours and the dried chips are molded into test pieces by an injection molding machine. The molding machine is used Nippon Seikosho Ankerberg N-95. Molding conditions are:

Cylinder temperature: 280 ° -280 ° -275 ℃

Molding temperature: 85 ° or 90 °

Injection holding time: 15 seconds

Cooling time: 15 seconds

Injection pressure: 300 ~ 600kg / ㎠

(2) heat deformation temperature

인치 히중 18.6kg/㎠로 측정된다.The heat deflection temperature is determined by the thickness of the test piece in accordance with ASTM D-648.

Inch weight is measured at 18.6 kg / cm 2.

(3) Deformation amount (δ120) at 120 ° C

인지와 하중18.6kg/㎠의 시험 조각을 120℃로 가열해서 이 온도에서 변형량을 mm로 측정한다.Thickness of the test piece according to the heat deflection temperature measurement method

A test piece with a cognitive and load of 18.6 kg / cm 2 is heated to 120 ° C. and the strain is measured in mm at this temperature.

(4) heat shrink

A disc 100 mm in diameter and 3 mm thick was molded. Length at an angle of 45 ° C. with respect to the sidegate. The heat shrinkage rate is determined by the following equation, taking the length after heat treatment at 150 ° C or 160 ° C for 1 hour in l:

Heat shrinkage = t-4

(5) Mold Releasability and Surface Characteristics

This formation is determined by whether the molding disc or molding spout having a diameter of 100 mm and a thickness of 3 mm is easily or hardly released. Surface characteristics are determined by the surface gloss and the stripe of the original. ◎ Extremely good, ○ Good, △ Fairly good, X bad, XX extremely bad

(6) Surface crystallinity from IR spectrum

Cut one test piece (40 x 18 mm) from the disc.

An IR absorption spectrum is taken by a total reflection IR spectrum analyzer (type 285, manufactured by Hitachi).

From the crystal absorption band obtained at 1335 cm ^-1 (I) and the correction band obtained at 1405 cm ^-1 (Io), the surface crystallinity of the molded article is obtained according to the following equation:

(7) tensile strength and elongation

ASTM D-638

(8) flexible strength

ASTM D-790

(9) falling weight impact strength

Downweight impact strength is determined by the measured energy value when an injection molded part of 3 mm thickness is split 6.3 mm from the outside to the center.

(10) flame retardant

(인치)의 성형조각이 UL-94(언더라이터라보. 인코오포레이션 보고서 U-94에 기술된) 시험법에 따라 난연도가 측정된다.

Molding pieces (in inches) are flame retardant according to the test method UL-94 (described in Underwriters, Inc. Report U-94).

(11) water absorption rate

A molded disc 100 mm in diameter and 3 mm thick was immersed in water at 23 ° C. for 3 days. Moisture absorption is obtained from the following equation:

Example 1

Polyethylene terephthalate, glass strand chopped to 3 mm in length (Glassron Fand Strand 486A: Asai Fiber Glass Co., Ltd.), talc (degum powder PK, Hayashi Kasei Co., Ltd.) with an average particle diameter of 10 μm, calcium silicate (silmos T, Shiraishi calcium Co.) and an organic crystallization promoter are combined at the magnification shown in Table 1 and the mixture is molded at a molding temperature of 85 ° C. to form disc shaped test pieces.

The molded article thus obtained is tested for release properties, surface properties, thermal strain temperature, thermal strain, and thermal shrinkage.

The results are shown in Table 1.

TABLE 1

** Dinacol EX-821 (Nagase, Polyethylene Glycol (EO4mol) diglycidyl ether)

EG.DGE = ethylene glycol diglycidyl ether

* PET = polyethylene terephthalate

Table 1 (continued)

As shown in Table 1, the composition of the present invention including polyethylene glycol diglycidyl ether exhibits excellent crystallization promoting effect even in a low temperature mold and can greatly improve the heat shrinkage at high temperature of the low temperature molded article.

Incorporating glass fibers into this composition can improve surface properties and dimensional stability in the presence of heat and significantly increase the heat distortion temperature.

When the inorganic layer agent is blended in place of the glass fiber, the releasability and surface properties are remarkably improved by the synergistic effect with the polyethylene glycol diglycidyl ether.

In addition, when both the glass fiber and the inorganic filler are blended, the releasability, surface properties, heat deformation temperature in the presence of heat, and dimensional stability are further improved to be a very useful composition for industrial plastics having heat resistance.

Example 2

Polyethylene terephthalate, talc (decompactor PK, Hayashi Kasei Co., Ltd.) having an average particle diameter of 10 μm, calcium silicate having an average particle diameter of 50 mμ (SiLMOS T, Shiraishi Calcium Co., Ltd.), glass strands cut into 3 mm lengths (Glassone strand strand 486A) , Asahi Fiberglass Co., Ltd.) and an organic crystallization accelerator are blended in the ratios shown in Table 2 and the mixture is molded into test pieces as in Example 1.

The mold release properties, surface properties, heat deformation temperature, heat deformation amount (δ120) at 120 ° C., and the heat yield after treatment at 150 ° C. for 1 hour were measured to obtain the results shown in Table 2.

TABLE 2

* PEG = polyethylene glycol DGE = diglycidyl ether

PPG = polypropylene glycol EG = ethylene glycol

TABLE 2

The compositions of the present invention containing polyalkylene glycol diglycidyl ethers, as shown in Table 2, exhibit excellent isomerism, surface properties and low heat distortion in the presence of heat.

On the other hand, the comparative composition containing polyethylene glycol, ethylene glycol glycidyl ether or wax showed that the release property and the improvement of the surface properties were insufficient or on the contrary deteriorated, and those with bad release properties exhibited a large amount of deformation in the presence of heat. The comparative composition containing polyethylene glycol increased the water absorption of the molded article, but the composition of the present invention containing a special organic crystallization accelerator was hardly changed in terms of water absorption.

Example 3

In the same manner as in Example 1, the test piece was 69% polyethylene terephthalate, 20% talc (degumming powder PK) with an average particle diameter of 10 μm, 2% calcium silicate (silmos T) with an average particle diameter of 50 μm, and 6% stump It was molded from a composition consisting of glass strands (Glasron chop strand 485) and polyethylene glycol (molecular weight 600) diglycidyl ether (Dinacol EX-841, Nagase & Company).

The test pieces were molded by dry mixing the release agents shown in Table 3 at the time of molding. The so-obtained grades were measured so that the releasability, deformation at surface characteristics of 120 ° C. (δ120), and the like were obtained in Table 3.

TABLE 3

* 1) calcium montan salt (Hoest JAPAN)

* 2 parts by weight per 100 parts by weight of resin

As shown in Table 3, the release agent improved the release property and surface properties.

Example 4

Polyethylene terephthalate, talc (talcum powder PK) with an average particle size of 10 μm, calcium silicate (silmos T) with an average particle size of 50 mμ, chopped glass chopsticks (Glaston chopped strand 486A) of length 3 mm, and various organic crystallization accelerators The test pieces were formulated at the ratios shown in Table 4 and the test pieces were molded at 85 ° C. or 90 ° C. in the same manner as used in Example 1.

The surface crystallinity of the molded article thus obtained was measured from the crystal absorption band of the IR spectrum to obtain the results shown in Table 4.

TABLE 4

* EX-821: Dinacol EX-821, polyethylene glycol (EO4 mol) diglycidyl ether, Nagase Corporation

EX-931: dinacol EX-931 polypropylene glycol (PO11 mol) diglycidyl ether, Nagase Corporation

ED-503: adecaglycile ED-503 ethylene glycol diglycidyl ether, Asahi Denka Kogyo Co., Ltd.

EX-810: Dinacol EX-810, Polyethylenedidlycidyl Ether, Nagase Corporation

NER-100: glycerin diglycidyl ether, nagasesa.

As shown in Table 4, the composition containing the polyalkylene glycol diglycidyl ether produced a molded article having large surface crystallinity and excellent gloss. There is also a significant difference between polyalkylene glycol diglycidyl ether and ethylene glycol diglycidyl ether, which indicates that the polyalkylene glycol diglycidyl ether used in the present invention is an excellent crystallization promoter. have.

Example 5

The polyethylene terephthalate, talc, calcium silicate, and glass fiber used in Example 4 were combined with the organic crystallization promoter shown in Table 5 in the proportions shown in Table 5 and the mixture was molded in the same manner as in Example 1 at 85 ° C. Molded into test pieces. The physical properties of the molded article thus obtained were measured to obtain the results in Table 5.

TABLE 5

Furtherance

1) Polyethylene glycol 2) * See Table 4

3) Polyethylene glycol (molecular weight 600) diglycidyl ether

Table 5 (continued)

As shown in Table 5, the composition containing polyethylene glycol diglycidyl ether has a large surface crystallinity and makes a molded article excellent in gloss.

In addition, the composition makes a molded article having a low water absorption and excellent heat resistance. On the other hand, the comparative example composition containing polyethylene glycol not only has low moldability and physical properties but also high water absorption, indicating that it is not suitable as an electric component molding material. Comparative examples containing ethylene glycol diglycidyl ether have poor moldability.

Example 6

The polyethylene terephthalate, talc and glass fibers used in Example 4, the organic crystallization accelerator and the polyester elastomer resin shown in Table 6 were blended in the proportions shown in Table 6, and the mixture was formed at the molding temperature in the same manner as in Example 1. Molded at < RTI ID = 0.0 >

The elastic resin is a block polymer of polybutylene terephthalate / polytetramethylene glycol (polytetramethylene glycol molecular weight 2000, butylene terephthalate: polyether = 4: 1 mol, Tg = about -58 ° C, molecular weight about 45,000) .

The physical properties of the molded article thus obtained were measured to obtain the results in Table 6.

TABLE 6

1) Nagase Corporation, polyethylene glycol (molecular weight 600) diglycidyl ether

2) Asahi Denka Kogyo Co., ethylene glycol diglycidyl ether

As shown in Table 6, a molded article having very good moldability and excellent heat resistance was obtained as a relatively small amount of the accelerator by low temperature molding by synergistic effect caused by using a polyester elastic resin and a specific organic crystallization accelerator in combination.

Blending an excessive amount of elastic resin has the disadvantage of lowering the heat deformation temperature.

When a small amount of release agent is formulated, excellent moldability can be obtained with a small amount of organic crystallization promoter.

Example 7

The polyethylene terephthalate, talc and glass fibers used in Example 4 and the olefinic elastomer resins shown in Table 7 were blended down at the ratios shown in Table 7.

The mixture is then put into a hopper of a two-hole 40 mm diameter extruder and melted and mixed to obtain a compound chip at a cylinder temperature of 250 ° C to 275 ° C. Using this compound chip, a test operation was molded at a molding temperature of 90 ° C. in the same manner as in Example 1.

The moldability and physical properties of the molded article were measured and shown in Table 7.

TABLE 7

1) Compounding amount (part) per 100 parts by weight of total composition excluding catalyst

2) Ethylene composition = 70%, Tg = about -60 °, melt index = 9.0 (230 ℃)

3) Nagasase, polyethylene glycol (molecular weight 600) diglycidyl ether

4) Ethylene composition = 67%, Tg = 20 ℃ or less, melt index = 2.0 (230 ℃)

5) Ethylene composition = 55%, Tg = about -20 ℃, melt index = 60 (230 ℃)

6) Compounds in which glycidyl methacrylate is formed of polymer 5) described above in the presence of dicumyl peroxide

7) Nagasesa, ethylene glycol diglycidyl ether.

As shown in Table 7, moldability worsens when an olefin type polymer is mix | blended. However, the organic crystallization promoter is effective even with such a composition and shows excellent formability.

In combination with the present organic crystallization accelerator, the intermediate adhesion between the two polymers was improved so that the dispersibility and adhesion strength of the olefin polymer to the polyester were improved.

Example 8

(두께)×

(폭)×5(길이)인치가 되게 시험 조각을 만든다.The polyethylene terephthalate, talc and glass fibers used in Example 4, and the organic crystallization accelerator, flame retardant and antimony trioxide (Nippon Seiko Co., Ltd.) shown in Table 8 were blended in the proportions shown in Table 8, and the mixture was formed into a disc having a thickness of 3 mm. After molding at 85 ℃

(Thickness) X

Make a test piece so that it is (width) × 5 (length) inches.

The physical properties of the molded article thus obtained were quantified and the results are shown in Table 8. Flame retardants were synthesized in the following manner.

Synthesis of tetrabromo bisphenol A carbonate ester oligomer (flame retardant A).

To the solution of tetrabromobisphenol A-544 parts by weight and p-tert-butylphenol to 3000 parts by weight of 10% sodium hydroxide and 2000 parts by weight of methylene chloride to form a solution. The phosgene gas is blown through the solution at PH12 while maintaining the temperature 25 ± 5 ℃.

After blowing up the phosgene gas, 8% triethyl amine is added as a catalyst and the reaction mixture is allowed to react at 20 ° to 30 ° C for two hours.

After the reaction, the methylene chloride layer was separated. After rinsing thoroughly with water, it is poured into 10 times the weight of methanol to precipitate the reaction product.

The precipitate is then filtered and dried to obtain white powder. The aromatic polycarbonate thus obtained has, on average, about 14 repeats and 53.6% bromine content at a softening point of 260 ° C. Synthesis of Cyanuric Ester Oligomer (Flame Retardant B) 27.65 g (0.15 mole) cyanuric chloride, 66.6 g (0.1 mole) tetrabromobisphenol, 82.7 g (0.25 mole) tribromophenol and triethyl benzyl ammonium chloride '400 g of methylene chloride are added to form a solution in a four-liter flask equipped with a stirrer, thermometer and reflux condenser.

Cool to 20 ° C or lower while stirring temperature.

While maintaining this temperature, slowly add a solution of 21.0 g (0.525 mol) of sodium hydroxide in 50 g of water. After the addition, the reaction solution was maintained at 25 ° C. for 4 hours and refluxed for 3 hours. Subsequently, methylene chloride is distilled off and the remaining solid is taken out of the flask.

It is then filtered, washed with water, dilute acid, water and finally with methanol to dry to obtain 140 g of cyanuric ester in the form of white powder (bromine content 60%, molecular weight about 33,000).

As shown in Table 8, the blending of the organic crystallization promoter improves the dispersibility of the flame retardant into the polyester and makes a molded article having excellent surface properties.

Incidentally, there is no difficulty in breaking down the small kernels, in which the small kernels are destroyed. In addition, it is possible to reproduce the flame retardant effect, and thus can exhibit excellent flame retardancy with a small amount of flame retardant.

TABLE 8

Claims (1)

A polyester having polyethylene terephthalate or at least 80 mole% of ethylene terephthalate repeating units and 0.1 to 15% by weight of polyoxyalkylene chains based on the polyester and an organic crystallization promoter having at least one epoxy group Polyester composition, characterized in that.