JPS5938255A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent characteristics in that the compsn. exhibits excellent crystallizability at conventional mold temperature and very small warp of glass-reinforced plastics, and has excellent mechanical properties, particularly flexural properties. CONSTITUTION:A crystallizability improver consisting of 0.1-5pts.wt. nucleating agent (e.g. monoclinic inorg. powder having a weight-average particle size of 50mu or below) and 0.5-10pts.wt. crystallization accelerator (e.g. an olefin having a solubility parameter of 7.5-12) is incorporated in 100pts.wt. polyethylene terephthalate or copolyester wherein at least 80% of the repeating unit is composed of ethylene terephthalate units. 10-15pts.wt. glass fiber (e.g. fiber having a weight-average fiber length distribution such that the 50% cumulative point in the logarithmic normal distribution is 0.2-0.4mm.) and 15-45pts.wt. inorg. powder (e.g. powder having a weight-average particle size of 2-100mu) are incorporated in 100pts.wt. above compsn. to obtain the titled compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention exhibits excellent moldability, especially crystallinity at a mold temperature of 100°C or less. The present invention also relates to a glass-reinforced polyester resin that exhibits extremely low warp distortion, which inevitably appears in glass-reinforced plastics, and exhibits excellent mechanical properties, especially bending properties.

Particularly in injection molding of polyester resin, a major problem has traditionally been that the glass transition point of the resin is approximately 80°C.
The resin crystallization does not proceed sufficiently at temperatures below 100°C, which is the normal molding temperature range, so mold temperatures of 120°C or higher and close to 150°C are required for large molded products. Further, even if the mold temperature is raised in this way, a sufficient degree of crystallinity is often not achieved unless a considerably long cooling time of over 60 seconds is taken.

In the heavy-duty general molding industry, it is a serious problem that the mold temperature exceeds 100°C. In other words, in order to achieve a gold temperature of 100° C. or more, it is not possible to control the mold temperature by circulating hot water, which requires heat retention using a special heating medium, dowsome oil, etc., and requires capital investment and modification. Also, if the cooling time is long, the total time to take out one molded product,
This increases the so-called cycle time and reduces production efficiency.

In order to deal with this problem, attempts are often made to increase the crystallization rate below 100C by adding a crystal nucleating agent to polyester resin (for example, Patent Publication No. 1973).
-26225. (Sho 54-38623).

Measures focused only on improving the crystallization speed alone cannot
In extreme cases, this may have a negative effect, especially on polyester resins reinforced with glass fibers. In other words, when glass fiber is added with the aim of strengthening the resin, operations are carried out to prevent the glass fibers from being cut in the chip-forming crosstalk machine and to increase the strength of the molded product as much as possible9.Usually, the glass fibers in the chips are The fraction of those with a length of 0.4 (turn) or more increases. When such a chip is molded, the long glass fibers are inevitably aligned in the flow direction within the mold, and the anisotropy of molding shrinkage in the direction perpendicular to the flow direction (the latter being larger) increases, causing warp distortion in the molded product. Severe distortion occurs in the molded product.

The wave field of the melt inside the mold is essentially an elongated wave field with no rotational component, except near the gate and very close to the inner surface of the mold, and the glass fibers hardly move relative to each other, and the flow direction If the glass fiber length distribution is particularly biased toward the part of 0.4 mm or more, not only will the mechanical strength become extremely weak in the direction perpendicular to the flow, but it will also cause large warps, which are troublesome for forming. A problem occurs.

In particular, when a crystal nucleating agent is added, which is the conventional technique described above, the degree of crystallinity of the resin increases, so the effect of molding shrinkage is rather aggravated, and the warp strain becomes significantly larger than when no nucleating agent is used.

In order to reduce the influence of glass fiber orientation, some effect can be expected by lowering the content of the glass itself, but lowering the glass content is not preferable from the viewpoint of resin reinforcement.

The inventors of the present invention have arrived at the present invention as a result of their earnest efforts to solve the problems of improving crystallinity and suppressing warp deformation, which are inherent in glass-reinforced polyester resins, in a well-balanced manner.

The polyester that is the object of the present invention is polyethylene terephthalate obtained by condensing terephthalic acid or its ester-forming derivative with an ester-forming derivative such as ethylene glycol or ethylene oxide in a molten state, or has a content of 80% or more of ethylene terephthalate repeating units. A copolymerized polyester (containing, for example, polyalkylene glycol units).

The crystallinity improver according to the present invention is composed of a combination of a nucleating agent that supplies energy for generating crystal nuclei and an accelerator that supplies energy for moving polymer molecules to the nuclei, and the nucleating agent is a paste polymer. The accelerator is contained in an amount of 0.1 to 5% by weight, and the accelerator is contained in an amount of 0.5 to 10% by weight.

If the amount of the nucleating agent is less than 0.1% by weight, it will not be effective in adding sufficient surface energy for nucleation, and if it is added in excess of 5% by weight, the surface area of the nucleating agent will increase rapidly. Therefore, it interferes with the movement of the polymer and inhibits crystal formation. Further, the dispersion of the nucleating agent itself into the polymer tends to become non-uniform, which is not preferable.

Examples of inorganic nucleating agents include polyethylene terephthalate crystal system and triclinic crystal type.
) is preferable, and in particular, as described in the scope of the present invention, monoclinic type (monoclinic type) is preferable.
It is effective to use inorganic crystal powder belonging to the group ``Crystal''.

Examples include talc, mica, kaolin, etc. with a particle size of 50 μm or less. Furthermore, the number of carbon atoms (:'10- C2Q fatty acid metal salts 9 such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid zinc, calcium, lead, magnesium, barium, cadmium, aluminum .

Sodium, potassium, and lithium salts are effective as organic nucleating agents, and special stearic acid, sodium, potassium, aluminum, and lithium salts show great effects. In addition, products containing pendant carboxyl groups in the main chain and partially neutralized types9, such as copolymer salts of ethylene or styrene and methacrylic acid, and ionomers also show remarkable nucleating effects, especially those of ethylene and methacrylic acid. Sodium, potassium, and zinc salts of copolymers of acids are effective.

These organic nucleating agents have good affinity with resins, impart internal lubrication to the resin, and also act as plasticizers to improve operability, so when combined with inorganic nucleating agents, they significantly improve the moldability of the resin.

Further, the accelerator to be combined with the above-mentioned nucleating agent can be more easily calculated by Small's method.

Solubility parameter (δ) constant is preferably in the range of 7.5 or more and less than 12.

If it is outside this range, the affinity with polyethylene terephthalate will drop significantly, making uniform blending with the resin difficult.

For example, polyethylene is a polymer-based product.

Examples include polystyrene, polymethacrylate, polyvinyl chloride, and polypropylene, and particularly preferred are polypropylene, polyethylene, and modified products thereof, such as propylene and ethylene copolymers.

The amount of the accelerator to be added may be less than 0.5 parts to 10 parts per 100 parts by weight of the resin, as stated in the claims. If it is less than 0.5 parts, there is no effect of promoting crystallization;
If it exceeds 0 parts, the solubility in polyester approaches the limit and uniform dispersion becomes impossible. Furthermore, if the accelerator is added in excess of 10 parts, the plasticizing effect on the polymer becomes too large, resulting in a decrease in the hardness of the molded product, and the resin leaks from the mold during molding, causing flaking, which is undesirable. More preferably, the amount of the accelerator added is 1 part or more and 5 parts or less.

As described in the claims, ketones having a solubility parameter of 7.5 or more and less than 12 can also be selected as the accelerator.9 For example, acetone (δ=9.6).

Dioxane (δ = 9.9) can be mentioned, but from the viewpoint of operational considerations such as volatilization during operation, substances that are solid at around room temperature 9 For example, benzophenone (melting point 48.5°C, δ = 10.7)
is easy to handle.

The concentration of such ketones is 0.1 relative to the base polymer.
It is desirable that the weight ratio is greater than or equal to 5%.

Now, it is important to adjust the concentration of the glass fibers contained in the composition of the present invention to 1Q or more and 15% or less based on the total composition weight, and if it is less than 10%, the influence of the flow orientation of the glass is small. Although the warp deformation of the molded product is reduced, the strength of the molded product is significantly reduced, and the viscosity of the composition in the melt state is also reduced, resulting in so-called flashing and extrusion of the resin from the mold.

Furthermore, when taking the molded product out of the mold, the molded product is not stiff enough to cause operational problems such as difficulty in ejecting the knock bottle. If it exceeds 15%, the influence of the orientation of the glass fibers becomes large, and the difference in molding shrinkage rate between the flow direction and the direction perpendicular to it becomes large, making warpage more likely to occur.

In addition, the melt viscosity of the composition 9 increases rapidly, resulting in poor resin flow within the mold, and in the case of a mold with a complex shape.
! The resin cannot be filled into the H section, which causes a serious problem.

Also, as stated in the claim of the present invention, the weight average distribution of glass fiber length is north of the average value of 0.2 wm, 0.4? It is important that the range below FF+ is a "lognormal distribution" with a tail at length t-# and fiber $111, and if the fiber length distribution deviates even slightly from this distribution, operators will also consider that the molding resin There are also many problems.

In other words, if the glass tightening and elongation distribution exceeds an average of 0.4 rpm and the long edge
f. Long glass tends to float up like fluff, which impairs the flow of chip solids in the molding machine hopper and prevents smooth supply to the screw. In this respect, 0.
There are claims that the presence of fibers with a length of 4 or more is advantageous, but this is not necessarily valid (/I♀Koshō 44-457)
. In addition, the glass fiber length distribution has an average of 0.2 questions and no droplets,
If the short fibers are biased toward the long side, the effect of the glass as a reinforcing agent will be significantly impaired.

In order to achieve the glass weight-average fiber length distribution referred to in the present invention, it is important to control the shearing force applied to the glass fibers. This is more possible than K.

For example, the maximum shear force (tmax) applied to the resin melt in a single-screw and double-screw mixed wire extruder
is approximately given by the following 2o) (1) - Axial Ruder (tmax is generated on the barrel surface) μ: Melt viscosity D = Ruder barrel inner diameter N Niscrew rotation speed H Niscrew groove depth 2) Biaxial Ruder (tmax is screw (occurs on the channel surface) tma
It is desirable that the value of x be in the range of 10'-10'dynes/c-J in order to control the length distribution of the glass fibers. If tmax is less than 10 dynes/rJ, the glass fibers will be less likely to bend, and the glass fiber length distribution will tend to be biased toward long fibers of 0.4 or more. Also tm
9. If ax exceeds 109 dynes/ffl, the glass fibers will break excessively.9. The distribution of glass fiber length tends to be uneven in order of 0.2 or less.

The diameter of the glass fiber referred to in the present invention is not particularly limited, but the preferred range is from 10 microns to 13 microns due to the above-mentioned shearing force and the way the glass is broken (lance). The fibers may be subjected to various surface treatments to increase the interfacial adhesion strength.For example, nine examples of trialkoxysilane-based treatment agents include vinyltriethoxysilane, β-(3,4-epoxycyclohexyl)- Ethyltrimethoxysilane, γ-
Examples include glycidoxypropyltrimethoxysilane and r-aminopropyltriethoxysilane.

What makes the effect of the present invention even more complete is this.

Inorganic powder with a particle size of 2 microns or more and 100 microns or less is added to the glass fiber with the above-mentioned length distribution, with a particle size of 2 microns or more and 45 inches or less for the entire composition, 2 times or more and 3 times or less in heavy killing. That's true. By combining this inorganic powder with the above-mentioned crystallinity improver and glass fiber, the present inventors have found that the crystallinity is extremely good, the assimilation within the mold is extremely short, and it is possible to remove the powder from the mold. They discovered that it is possible to produce glass-reinforced polyester molded products with extremely good dimensional stability and less warpage afterward.

If the particle size of the inorganic powder exceeds 100 microns, the degree of filling in the resin will be poor (not densely packed), causing problems such as making the molded product brittle. Furthermore, if the particle size is less than 22 microns, the surface adsorption force between the particles will increase and the dispersibility of the particles will decrease, and the surface area of the particles will increase rapidly, which will impede the flow of the resin and inhibit crystallization. do. Therefore, the 2 particle size is 2
The range is preferably from 5 microns to 100 microns, and more preferably from 5 microns to 50 microns. Further, as mentioned above, from the viewpoint of particle dispersibility and influence on the physical properties of the resin, the desirable addition amount of the powder is in the range of 20% by weight or more and 451% by weight or less based on the total composition.

The type of inorganic powder referred to in the present invention is not particularly limited as long as it falls within the particle size range and addition amount range described above.

It is preferable to use a material that has a high affinity with polyester; for example, it may be treated with a titanate or silane coupling agent. An example is glass peas powder.

Glass milled fiber, talc, calcium carbonate.

Mica powder, kaolin clay, magnesium carbonate.

Calcium silicate, (silica), carbon black.

Examples include alumina oxide, titanium oxide, zinc white, and the like.

The mellow effect of adding these inorganic powders greatly improves the bending properties of the molded product, and in particular, shows a remarkable increase in the bending elastic modulus.

That is, as described in the examples, when inorganic powder is used in combination with glass fiber, warp distortion not only disappears.

The flexural modulus of the molded product is between 200% and 300%.

According to the inventors' opinion, by densely filling the gaps between the glass fibers with inorganic powder, the movement of the ester resin due to shrinkage during cooling and crystallization can be greatly suppressed, and in particular, the resin flow This is to suppress dimensional changes in the direction 9, which is perpendicular to the direction 9, which normally causes large shrinkage. The ratio of the coefficient of thermal expansion of glass fibers and polyester resin is said to be about 1:10, and the presence of inorganic powder in the resin gap between glass fibers has a tremendous effect. In addition, inorganic powder also has the effect of suppressing the flow of resin, as shown by the effect of increasing the bending elastic modulus, increasing the thermal deformation temperature under a constant load and suppressing sick leap deformation.

Next, the effects of the present invention will be explained in detail using examples.

Note that measurements in the following examples were performed as follows.

(1) Bending strength and bending elastic modulus According to ASTM D 790, width 1/2" (13 ears) x
A test piece with a thickness of 1/4" (6,4 mm) x 5" (127 scales) was made, and a concentrated load was applied to the center as a double-sided frame with a span length of 102 mm (measurement).

(2) Heat distortion temperature according to ASTM D 648, width 1/2" (13 towns) x
A test piece with a thickness of II (13 m) x 5” (127 m) was prepared and measured by applying a fiber charge of 186 Kg/rJL.

(3) Crystallization rate differential thermal lid analyzer (Perkin Elmer Inc.,
I) Isothermal crystallization for half an hour (tllo) at 100°C using SC-2 type)2. ) is measured 1~. The measurement is 280
Melt at °C F+11. Samples were rapidly frozen from 0°C to 320°C.
The temperature was rapidly raised at 100° C. and held at 100° C. The time integral value of the exothermic peak was measured, and the time when the value reached 1/2 of the final value was defined as half an hour of crystallization. Similarly to half-hour crystallization measurements, a sample that had been thawed and frozen was heated at a constant rate of 20°C.

The peak temperature of the exothermic peak (due to crystallization and molecular arrangement of the amorphous part) that appears from 100℃ to 120℃ (
Tp) was measured. It is considered that the lower Tp is on the lower temperature side, the greater the mobility of polymer molecules and the easier it is to crystallize.

(,, +1 Dissolve the glass fiber length distribution sample chip in a solvent for viscosity measurement (1Nol/tetrachloroethane = 6/4 mixture).

The precipitated glass fibers were placed on a slide and sandwiched between cover glasses to serve as a sample.

This sample was applied to a projection magnifier, and the length of the glass fibers on the screen was measured by an automatic phototube type fiber length measuring device (manufactured by Sun Engineering Co., Ltd., digitizer) connected to the interface and the length distribution. was automatically measured. The number of fibers measured was 300 to 500.

(5) Measurement of amount of warp A disk like the one shown in Figure 1 was formed with a thickness of 3 cm and a diameter of 100 mm.
mm), after heat treatment at 130C for about 2 hours 1 Sum of warpage amount (a + b) when points a and b (flow direction) in Figure 1 are held alternately, and points c and d are held alternately Measure the sum of the amount of warpage (c + d) at the time.

This was used as a comparison standard for sleds.

Example 1 100 parts by weight of copolymerized polyethylene terephthalate containing 10 wt% of polyethylene glycol (molecular fl 4000) having an intrinsic viscosity [η:] = 0.60 measured with a phenol/tetrachloroethane (6/4) mixed solution as a copolymerization component In contrast, one part of talc (
Made by Nippon Talc, Micro Ace-11 particle size average 50μ)
, 3 parts of modified polyolefin (Toa Fuel Sekiyu, Himic anhydride added) as a crystallization accelerator.

Impact-resistant heavy duty IPP, Grade 102-L) is added, and 10% glass fiber (manufactured by Asahi Glass, 3-cut length chopped strand, thread diameter 10 microns) is added to the all-resin electric switch. A429
) and 20q6 mica powder (Shiraishi Kogyo, titanate treatment 3
25 Metsuyu WhiteWater Ground M
ica) and the heat stabilizer Irganox 1010 at a rate of 0.2
After adding 0.1 part of calcium stearate as a life-sustaining agent, premixing was carried out in a V-type blender, and then directly put into a 45 mm screw diameter twin-screw chip forming machine (PCM made by Ikegai Iron Works).
45 type, Vent type) was used as a molding tip.

Molding conditions are 2 screws rotating in the same direction at 200 revolutions per rotation.
r p m w Cylinder temperature is 280U. The glass fiber length distribution in the thus manufactured chip was approximately a straight line when plotted on log-normal distribution probability paper, and the 50% cumulative point was 0.32.

The chips were then dried under vacuum at 120D for 24 hours;
A test disk was molded using a 100 m II + screw diameter injection molding machine (J100S type, manufactured by Nippon Steel Corporation).

The disk thus obtained was placed on a horizontal surface plate for 1N, and the amount of warpage of the disk was read using a caliper using the method described above.

The injection molding conditions are 240-27 with the cylinder on the hopper side.
The temperature is 0-280-280C, and the mold temperature is 100C.

The injection pressure was 3130 Kg/cnl, and the injection time x cooling time was 10 seconds XIO seconds.

Example 2 Based on 100 parts by weight of the same copolymerized polyethylene terephthalate as in Example 1, 1 part of talc (Nippon Talc, Micro Ace -1) and 3 parts of ethylene-methacrylic acid were added as a crystal nucleating agent. Copolymer sodium neutralized product (D
u: Font, Surlyn heat stabilizer Irganox 1010 (Ciba, Gaiki) 0.1 part, mold release agent polyethylene wax (Hoechst wax PE-190)
) Added 0.1 part, further 10% based on the total composition weight
For the same glass fiber and total composition Ml as in Example 1, 25
% mica powder (Seto Kogyo white mica, average particle size 10μ)
The mixture was premixed in a V-type blender and then chipped using the same twin-screw kneader as in Example 1.

The molding conditions are cylinder temperature 280℃, screw rotation,
The rotation speed is 250 rpm in the two-axis rotation direction. The glass fiber length distribution in the chip thus obtained was a clean straight line on the log-normal distribution probability paper, and the 50-chi cumulative point was (1.29 mm). After drying the chip at 120 C under vacuum for 24 hours, Example 1 A test disk was molded in the same manner as in step 1.

Example 3 Intrinsic viscosity [η] determined by the same method as Example 1 = 0
．． 68 polyethylene terephthalate as a base, 100 parts by weight of the same as a nucleating agent, talc (Nippon Talc, Micro Ace K-1), 5 parts O, neutralized sodium ethylene-methacrylic acid copolymer (DuPont, Surlyn 1555) and 1 part of the modified polypropylene used in Example 1 as an accelerator, and 0.5 part of benzophenone (Reagent Grade 1, manufactured by Seiretsu Ryakuyaku Co., Ltd.), and further glass fiber (manufactured by Asahi Glass Co., Ltd.).

3-cho long chopped strand, Grade &
419, yarn diameter 13 μ), 15 times the total composition weight.

It was made into chips using an axial kneader (Irganox 1
010 Calcium stearate content 1 C Same as Example 1).

The glass fiber length distribution in the obtained chip is a lognormal probability paper, and is a straight line as in the previous example, and the 50% cumulative point is 0.3.
Two torsos were shown.

Prepare this chip as before (after air drying).

Test discs were molded as before.

Example 4 Intrinsic viscosity [η) = 0.6 measured in the same manner as the previous example
2, 10 wt% polyethylene glycol (molecular weight approximately 30
A mixed chip was prepared by blending the copolymerized polyethylene terephthalate prepared by copolymerizing 00) with the polyethylene terephthalate described in Example 3 at a ratio of 50,150. For 100 parts by weight of this chip.

Neutralized sodium ethylene-methacrylic acid copolymer (manufactured by Du Pont, Surge Y 1560) as a crystal nucleating agent
and 3 parts of the modified polypropylene described in Example 1 as an accelerator were added, and 10 parts of glass fiber (A419 manufactured by Asahi Glass as described above) was added to the total composition.

In addition, talcum powder (manufactured by Nippon Talc, -1 to Micro Ace)
) was added (stabilizer, mold release agent type and content were the same as in Example 2), and chips were formed in the same manner as before.

The glass fiber distribution in the chip was a straight line on a log-normal probability plot, and the cumulative score of 50 chips was 0.27 vys. A test disk was prepared in the same manner as in the previous example.

Example 5 For 100 parts by weight of the mixed chips of copolymerized polyethylene terephthalate and polyethylene terephthalate described in Example 4, 1 part of talc (same as in the previous example) and 3 parts of talc as a nucleating agent were added.
Part of neutralized sodium ethylene-methacrylic acid copolymer (
Du Pont Co., Surlyn 1555) with the addition of 3 parts of the modified polypropylene described in Example 1 as an accelerator;
Based on the total composition, 10% by weight of glass fiber with the above specifications (Asahi Glass A429) and 20% by weight of glass beads (Asahi Glass,
Glassron particle size 20μ) is mixed with Irganox 10.
10 and Hoechstwax PE-190 (containing 0.1 parts each in 100 parts by weight of total base polyester), Example 1
It was also made into a chip. In the tip! The J Shirasu fiber length distribution has a lognormal distribution, and the 50% cumulative point is 0.32.
It was tmm. The test disk was created as in the previous example.

Comparative Example 1 Using the same polyethylene terephthalate ([?) = 0.68) as used in Example 3 as a base, 3 parts of talc was added as a nucleating agent to 100 parts by weight, and no other (A
4A 9. Stabilizer Egano Cus 10100.
After adding 2 parts, # type agent calcium stearate 0.1 part,
Chips were made using a 40 m screw diameter single-screw router (manufactured by Nippon Steel Corporation). Cylinder temperature is 25 from hopper side
At 0-260-280-280℃, screw rotation 20
It was rpm.

The glass fiber length distribution in the chip deviates greatly from a straight line on the lognormal probability plot toward the long fiber side, and the cumulative point of 50 chips is 0.
It was 45 mR.

Comparative Example 2 Base polyethylene terephthalate resin (equal blend of polyethylene terephthalate and copolymerized polyethylene terephthalate) nucleating agent (Surlyn 15) described in Example 4
60), accelerator (modified polypropylene described in Example 1), glass fiber (Asahi Glass A419)-stabilizer (Irganox 1010), mold release agent (Hoechst wax PE
-190) in exactly the same proportions and kneaded into chips using the 40-shaft kneader described in Comparative Example 1 (the molding conditions were also the same as in Comparative Example 1).

The glass fiber length distribution in the chip does not follow a lognormal distribution;
The 50% cumulative point was 0.42 mm.

- The chips of Comparative Examples 1 and 2 were used as test disks under the same conditions as the Examples, but the appearance of the samples was not good due to large warp distortion.

Comparative Examples 1 and 2 do not contain the inorganic powder specified in the present invention, which should be used in combination with the glass fibers that perfectly normalize the effects of the present invention, and it is considered that the molding distortion was large.

Next, Table 1 shows the composition of each side, and Table 2 shows the measurement data.

(IJPEG 300010wt% Copolyme
r C'j] = 0.62 (2JP EG 4000
10wt% Copolymer ['7) =
0.60(3) P E T [:η] = 0.
68 (4) Talc (Japanese talc, '1 -1 to Micro Ace) (5) Chi Lin 1555. Surlyn 1560
(Ionomer manufactured by Du Pont) (6) Modified PP (Tonen Petrochemical, added with Himic anhydride.

I (A102-L) (7) PE (Mitsui Petrochemicals Gai, low pressure method low density PE, Ultzex 20200J) (8) Hensiphenon (Ishizu Pharmaceutical 11) C9) W,
G, Mica (Shiraishi Kogyo) (11 Seto Mica (Seto Ceramics) C1l) Calcium carbonate (Shiraishi Kogyo, Boiten SB
-2) (1 scent glass fiber A429 (manufactured by Asahi Glass, thread diameter 1 () 3 items) A419 (# 13 #) (I9) Glass powder (manufactured by Asahi Glass, glassron powder) II12III Regular day I example Pb: Bending Strength (Ky/cJ) Eb: Flexural modulus (#) I (DT; Heat Deflection Tem
p (℃) (Heat distortion temperature) tl/2: Isothermal (100
C) Crystallization rate (-) Tp: Exothermic peak temperature during temperature rise (a+b): Amount of warp in flow direction (-) (e+d):
The crystal nucleating agent, accelerator, glass fiber and inorganic powder specified in the present invention were evaluated based on the results of Table 2. It is believed that the combination of these four properties produces a glass-reinforced polyester resin with extremely good crystallinity, excellent low-temperature formability, no warp strain, and excellent thermal stability and bending properties.

[Brief explanation of drawings]

FIG. 1 shows a test disk for measuring the amount of warpage. a-
)1) is the resin flow direction, and c->d is the direction perpendicular to it. The gate position corresponds to point a. FIG. 2 shows an example of a log-normal distribution plot of glass fiber length. Line A is Example 1. Pure 13 is the fiber length distribution of Comparative Example 1. Patent π "Applicant: Unitika Co., Ltd. Figure 1 procedural amendment (spontaneous) February 17, 1980 Director General of the Patent Office 1, Indication of the case Patent Application No. 149516/1982 2, Name of the invention Polyester resin composition 3 , Relationship with the case of the person making the amendment Patent applicant address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture
"Indicates a significant increase" on page 15, line 14 of the specification.
[showing a significant increase]. ” he corrected.

Claims (1)

[Scope of Claims] 1. (a) 0.1 part to 5 parts of a crystallization nucleating agent (b) based on 100 parts by weight of polyethylene terephthalate or a copolyester consisting of 80% or more of ethylene terephthalate repeated coagulation. Contains a crystallinity improver consisting of a combination of 0.5 parts or more and 10 parts or less of a crystallization promoter, and 15 parts of glass fiber and 15 parts of Hio or more and 15 parts or less based on 100 parts by weight of the total composition. A polyester resin composition containing 45 parts or less of an inorganic powder. 2. The crystallization nucleating agent is an inorganic powder with an average particle size of 50 microns or less that aggregates in a monoclinic system, or a fatty acid metal salt having 10 or more and less than 20 carbon atoms, or ethylene or styrene containing pendant carboxyl groups. The polyester resin composition according to claim 1, which is a partially neutralized product of a copolymer of methacrylic acid or a combination thereof. 3. The crystallization promoter has a solubility parameter of 7.5 or more1
In the range of less than 2. Claims 1 and 2 are olefins or ketones or mixtures thereof.
The polyester resin composition described in . 4. Claims 1 and 4, wherein the distribution of the weight average fiber length of the glass fibers follows a lognormal distribution, and the 50% cumulative point of the distribution is in the range of 0.2 mm or more and less than 0.4 m. The polyester resin composition according to item 2. 5. Claims 1 and M in which the weight average particle size of the inorganic powder is 2 microns or more and 100 microns or less
The polyester resin composition according to item 2. 6. The weight average of the inorganic particle size is 2 microns or more and 100 microns or less, and 15 cm or more and 45% of all composition types iK.
Claim 1, characterized in that it contains less than
The polyester composition according to Items 2 and 5.