JPS58183744A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin composition having a specific composition and excellent mechanical properties, electrical properties, chemical resistance, surface gloss, etc., by compounding a polytetramethylene terephthalate with a polyester polyether block copolymer. CONSTITUTION:The objective composition is composed of ( I ) 99-5wt% of polytetramethylene terephthalate and (II) 1-95wt% of a polyester polyether block copolymer composed of (A) a dicarboxylic acid mixture consisting of (i) 50- 100mol% of terephthalic acid and (ii) 50-0mol% of isophthalic acid, (B) a diol mixture consisting of (iii) 5-95mol% of the glycol of formula (R1 and R2 are H or 1-4C alkyl provided that R1 and R2 are not H or CH3 at the same time) and (iv) 95-5mol% of tetramethylene glycol and (C) a polyalkylene ether glycol having a number-average molecular weight of 500-3,000, wherein the amount of the component (C) is 5-50wt% (in terms of phthalate) based on the whole copolymers.

Description

[Detailed description of the invention] This book @@ relates to resin compositions.

More specifically, composition KIIIL obtained from polytetramethylene terephthalate and polyester polyether block copolymer, mechanical properties, electrical properties, chemical resistance 1 surface gloss, cold resistance, impact resistance, heat deformation resistance, The present invention relates to a resin composition having excellent properties such as moldability.

Polytetramethylene terephthalate resin (hereinafter abbreviated as PBte resin) is a heat-wearing polyester resin with high crystallinity and good affinity with various fillers and additives. Therefore, is it reinforced by adding glass fiber, My□force, talc, etc.? 117 tree 1i1 exhibits excellent usage characteristics and is therefore widely used in industrial applications such as electrical and electronic parts and automobile parts. That is, PBT
Wood MFi, high mechanical strength, excellent durability.

It has weather resistance, chemical resistance, heat resistance, 1-dimensional stability, and electrical properties. In addition, polyethylene terephthalate tree 1
Compared to No. 1, it has a higher degree of crystallinity, inhibits the crystallization rate, and therefore has a faster cooling and solidification rate, and also has excellent flowability, so it has better moldability. PBT resin is an excellent engineering plastic with a good balance of electrical/mechanical properties and processability.

However, FBT@fat has the following drawbacks. Namely, (1) amorphous and monocrystalline plastics naturally have poor dimensional accuracy and are susceptible to mold temperature distribution. The molding shrinkage rate is highly dependent on the inner thickness, and due to variations in cooling rate, deformation and sink marks are likely to occur. This unfavorable property promotes shrinkage anisotropy due to fiber orientation in reinforced PBT resins reinforced with glass fibers, etc., making the molded product susceptible to deformation and causing so-called warping.

(2) PBτ tree 11, which is not particularly reinforced, is a stone that has drawbacks such as poor flexibility and high notch sensitivity.

In order to improve these drawbacks, some of the terephthalic acid is replaced with aliphatic dicarboxylic acid, or by blending with other resins, the crystallinity is reduced and the shrinkage during wear is reduced. There are methods to minimize deformation, and glass beads have less anisotropy than glass fibers.

Methods using fillers such as talc and FF squid are known, but none that meet the Kyc requirements of users have yet been obtained.

However, as a result of intensive research, the present inventors have found that the impact 5M& is greatly improved by mixing a polyester polyether block copolymer containing a glycol component with an alkyl group in the side chain with PB resin. This led to the present invention.

In other words, zero shot 1! A dicarboxylic mixture consisting of 50 to 100 mol of terephthalic acid and 50 to 95 mol of isophthalic acid, general formula (1) of the queen
A diol mixture consisting of the glycol shown by and 95 to 5 mol of tetramethylene glycol, and a polyester polyether block co-X combination consisting of a polyalkylene ether glycol having a number average molecular weight of 500 to 5000, the polyalkylene ether glycol component is 5 to 50% by weight based on the total copolymer as 7 talates.
A polyester polyether block copolymer (I
) and polytetramethylene terephthalate (2), in the mixing ratio of (■) and (2), The present invention relates to a modified resin composition characterized by the following.

1 2 (However, in the formula, R1 and R are hydrogen or an alkyl group having 1 to 4 noble atoms, except when R1 and R2 are both hydrogen or methyl.) Although it is not clear whether a polyester resin composition having impact properties can be obtained, the following may be considered.

Molecular chain F1 of thermoplastic polyester polyether elastomer is substantially composed of linear polyester units and linear polyether units, the linear polyester units form hard segments, and the linear polyether units form soft segments. There is.

Conventionally, the hard segments of thermoplastic polyester polyether elastomers are condensation polymers of dicarboxylic acids, mainly tele-7I acid, and alkylene glycols that do not have any side chains, such as ethylene glycol and tetramethylene glycol, but the soft segments are Polyalkylene ether glycols such as polytetramethylene ether glycol have been used.

However, by using 1,5-propanediol having an alkyl group in the side chain as the glycol component constituting the F′i hard segment of the polyester polyether block copolymer (1) used by the present inventors, flexibility was achieved. It is an elastomer with excellent characteristics.

The highly flexible polyester polyether block copolymer (1)ii according to No. 11 has K PBT segments in its structure, so it is an elastomer with high affinity for PBTΦ) and is excellent in improving the impact resistance of PBT. This is considered to be effective.

Polytetramethylene terephthalate@ used in the present invention is a polyester synthesized using terephthalic acid and tetramethylene glycol as starting materials, and inphthalic acid as another component.

Orun-7thalic acid, naphthalene dicarboxylic acid, adipine dicarboxylic acid, sebacic acid, dodecane dicarboxylic acid.

1. Aromatics such as 4-cyclohexanedicarboxylic acid.

Fat knights, alicyclic dicarboxylic acids, and diol components include ethylene glycol, propylene glycol, pentamethylene glycol, hexamethylene glycol, and decamethylene glycol.

Neopentyl glycol, 2-mefk-1,! I
-Propanediol, cyclobencunediol.

Aliphatic, alicyclic, aromatic diols such as cyclohexane diol, cyclohexane dimetatool, cyclohexane jetanol, 1,4-benzenedimetatool, 1,4-benzenedethanol, etc. are used in appropriate amounts depending on the purpose. I'm sorry for the inconvenience. Other oxy acids such as oxybenzoic acid and hydroxyethoxybenzoic acid may also be used.

For the synthesis of polytetramethylene terephthalate, a conventional polyester manufacturing method can be applied to its t'1 stage. That is, either a direct method in which a dicarboxylic acid compound and a diol compound are directly subjected to a polycondensation reaction 1, or a transesterification method in which a lower alkyl ester compound of a dicarboxylic acid compound and a diol compound are reacted and a polycondensation reaction is carried out by transesterification. can also be produced.

As an example, to show a method for producing a polymer obtained from terephthalic acid and tetramethylene glycol, 1 mole of dimethyl terephthalate and an excess number of moles, that is, a total of 1.1 to 2.0 times the mole of tetramethylene glycol, are Using an esterification catalyst, under a nitrogen stream, at normal pressure, about 1J
The transesterification reaction is carried out at a temperature of 0 to 240°C.

Let the methanol accumulate! After adding additives such as catalyst 1 color inhibitor according to the conditions, polycondensation is carried out at about 200 to 280° C. under reduced pressure of 5 μHg or less. A wide range of catalysts can be used as the catalyst, including titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraiso-propoxytitanium, tetrabutoxytitanium, di-n-butyl-tin-dilaurate, di-n-butyl-tin-oxide, dibutyl-tin-
Ruiyoshi tin compounds such as diacetate,! Examples include a combination of an acetate of magnesium, calcium, zinc, etc. and antimony oxide or the above-mentioned metal titanide.

These catalysts have a concentration of 0.002~
It is preferable to use it within the range of O$ weight bag.

9. Fi phosphorous acid, phosphoric acid, tri-methyl 7-osphite, tridecyl phosphite, tri-7-enyl 7-osphite, trimethyl phosphate, as a color inhibitor.
Phosphorus-containing compounds such as tridecyl phosphate and triphenyl phosphate are effective; It is preferable to use it within a range of about 100 yen.

The molecular chain of the polyester-polyether block copolymer used according to the invention consists essentially of polyester units and polyether units, with the polyester units forming hard segments and the polyether units forming soft segments. There is.

Polyesterha, a polyester polyether block copolymer used in Main I14. - segment is 50
A dicarboxylic acid mixture consisting of ~100 moles of terephthalic acid and 50 to 0 moles of isophthalic acid;
It is composed of a mixed diol component consisting of propanediol having t-molar alkyl group side chain and tetramethylene glycol having 95 to 57 molar groups.

Depending on the purpose of the resin composition of isophthalic acid constituting the mixed dicarboxylic acid component used in the polyester polyether block copolymer, the isophthalic acid is preferably mixed with terephthalic acid up to 50 mol at sO mol at. .

That is, by mixing isophthalic acid, the copolymer is essentially amorphous or difficult to crystallize.
The flexibility is improved by relatively increasing the content of hard segments of propylene intatalate and polytetramethylene intartrate having an alkyl group in the chain. If used as such, the heat resistance will deteriorate so much that it will no longer be suitable for practical use.

An example of 1,3-propanediol having an alkyl group represented by the above formula (1) in the side chain, which constitutes the mixed diol component of the -7F polyester polyether block copolymer, is 2-ethyl-2-butyl-1. -1-propanediol, 2,2-diethyl-1,5-propanediol, 2
-Methyl-! - globy-1,5-propanediol,
Examples include 2-ethyl-11s-propanediol, 2-methyl-1,1-propanediol, and 2-methyl-1,5-propanediol is particularly preferred.

1. Having these alkyl groups in the side chain. ! $−7'Bo7
A polyester polymer obtained by condensation polymerization with terephthalic acid, which has an alkyl group at the lovandiol position, has an irregular structure, thereby making the polymer soft and amorphous.

On the other hand, tetramethylene glycol undergoes condensation polymerization with, for example, terephthalic acid to yield a tough, crystalline polyester exhibiting a high melting point, ie, polybutylene terephthalate.

The polyester polyether block copolymer (I) fl used in the present invention has improved flexibility and mechanical strength by combining the properties of each of these two diols.

The mole of 1,3-propanediol/tetramethylene glycol having an alkyl group to be warmed, S~
! 5 moles/95 to 5 moles, preferably 10 to 70
If the amount of 1,5-propanediol having an alkyl group in its side chain is less than 5 moles, the above-mentioned effects imparted by the diol will not be exhibited.

If the amount is more than 95 moles, the thermal and mechanical strength will drop significantly, which is not preferable.

In addition to the above-mentioned mixed dicarboxylic acid component and mixed diol component, polyester polyether plotter copolymer (for the purpose of increasing the melt viscosity of the polymer and increasing the polymerization rate, polycardic acid having five or more functional groups) It is also possible to copolymerize a small amount of polyol, etc. depending on the purpose.

Examples of the wrinkled polycarbonate include trimellitic acid, trimesic acid, so-called bimellitic acid, and their acid anhydrides and esters, and examples of the polyol include trimethylolpropane and glycerin.

Examples include pentaerythritol.

The polyester polyether block copolymer (I) used in the present invention F'i and other components of the copolymer include polyvalent aliphatic carboxylic acids such as adipic acid, azelaic acid and heptapacic acid, isophthalic acid, 2. Polyvalent aromatic carboxylic acids such as 6-naphthalene dicarboxylic acid, ethylene glycol.

Propylene glycol, 1,6-hexanediol, 1
, 4-cyclohexidenediol and the like can be used in an appropriate amount depending on the purpose.

The component forming the soft segment of the polyester polyether block copolymer used in the present invention is polyalkylene ether glycol having a number average molecular weight of 5oo-iooo. The proportion of the polyalkylene glycol is 5 to 50 parts by weight based on the total copolymer, and 10 to 41 parts by weight.
It is preferable that the material is 40% softer than 5% by weight, otherwise the flexibility is insufficient, and if it is more than 50% by weight, it becomes extremely soft and undesirable.

What is the polyalkylene ether glycol?

Polyethylene glycol, poly(1,2- and 1,I
s-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hequinamethylene oxide) glycol, copolymers thereof, etc.
Alternatively, these may be used in combination. The number average molecular weight of polyalkylene ether glycol is 500~! 5000
1 particularly preferably Fiaoo to 2ooo, soo
If it is smaller, the heat resistance of the final poly T- will be lowered.

) The larger the size, the worse the compatibility with the hard segment.

The polyester polyether block copolymer (I) used in the present invention consists of the dicarboxylic acid component, diol component, and polyalkylene ether glycol component as described above, and can be produced by a generally known copolymerized polyester production method, that is, dicarboxylic acid component, diol component, and polyalkylene ether glycol component. It can be produced by a method in which an acid and a glycol are directly reacted, or by a method using a transesterification reaction between a lower alkyl ester of a dicarboxylic acid and a glycol. To give an example of the latter method, dimethyltere7thalate) t it, <a mixture of dimethyltere7merate and dimethyliso7talate 1
4 ru and over 11i 4 ni number, that is, the total is 1.1 to 2
．． A mixture consisting of 0 times the mole of 2-methyl-1,3-putapanediol and tetramethylene glycol was heated under a nitrogen stream at normal pressure using a common esterification catalyst for about 15
Transesterification is carried out at a temperature of 0 to 240°C, methanol is accumulated, and then polyalkylene ether glycol is converted to polyalkylene ether glycol tm, t, s under reduced pressure of less than 200 to 200 s Hg.
Polycondensation is carried out at 80°C. Polyalkylene ether glycol.

It may be added before the transesterification reaction.

Suitable catalysts used in such reactions include, for example, tetramethoxytitanium, tetramethoxytitanium, and tetran-propoxytitanium.

Titanium compounds such as tetraiso-propoxy titanium, tetrabutoxy titanium, etc., tin compounds such as di-n-butyl-tin-dilaurate, di-n-butyl-tin-oxide, dibutyl-tin-diacetate, etc., magnesium, calcium, Examples include a combination of an acetate such as zinc, antimony oxide, or the above titanium compound. Among them, the preferred catalyst is an organic titanium compound. These catalysts have o, oo1 to
It is preferable to use it in a range of 6% by weight.

In the composition according to the invention, these two types of polymers are mixed in a proportion such that the polyester polyether block copolymer (R) is 1 to 95% by weight and the polytetramethylene terephthalate (2) is 99 to 5% by weight. .

When the amount of the polyester polyether block copolymer used in the present invention is 1 weight or less, the impact resistance of the composition is improved! Not noticed. If the weight of the polyester polyether block copolymer is more than 95% by weight, the heat deformation temperature will drop significantly and the properties of the present invention cannot be achieved. It can be carried out at any temperature above the melting point of , preferably between 100 and 500°C.

Specific methods for blending include a chemical method of dissolving and mixing in a solvent, and a mechanical method of kneading with a similar Fi roll, pan, p < IJ remixer, extruder, molding machine, etc. The methods and apparatus described can be used.

In carrying out the present invention, other additives may be added depending on the various physical properties and desired IT effects of the composition of the present invention.

Specifically, carmen platters, titanium oxide, other harmful alumina, silicon oxide, and glass spherules.

Inorganic and organic fillers and reinforcing materials such as glass fibers and carbon fibers, lubricants such as organic acid afds,
Other crystals, nucleating agents, antioxidants.

These include ultraviolet absorbers, antistatic agents, and AM fuels.

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited thereby. In the examples, parts mean parts by weight, and the measured values are as follows. This was obtained using the field determination method.

1) Intrinsic stiffness of polytetramethylene terephthalate is a value measured at 25C in orthochlorophenol. Polyester polyether block copolymer? Measurements were made at 25 DEG C. at a concentration of Q, 5fAt in a mixed solvent of -160 parts by weight of phenol and 40 parts by weight of 1,14,2-tetrachloroethane.

The measurement was carried out using a Tensilon UTM-500 universal testing machine manufactured by Toyo Baldwin Co., Ltd., which is similar to 21100 Cyst Mojitsusum 87M D-658K.

5) Vicat softening temperature Yasuda Seiki Seisakusho Mu148-) IDRAutomati
c Using HeeLtDistortion Te5t@r, apply a load of 1kl to a steel needle with a diameter of 1m at 50℃/
The temperature was increased by Hr, and the temperature at which the needle directly penetrated 1u+ was determined as #j.

4) - Ge elasticity modulus It was measured in accordance with M8TM D-790.

5) Tensile fracture stretch Tensilon t) TM-1[-6 manufactured by Toyo Baldwin Co., Ltd.
)Izotsu impact test Measured using Toyo Seiki Seisakusho's Izotsu impact tester.Mu8TM D-256Kl! I went there.

Synthesis Example-1 400 parts of dimethyltere (7 tally) and 590 parts of tetramethylene glycol were mixed with 0.1 parts of titanium tetrabutoxide catalyst.
2. The mixture was charged into a reaction vessel equipped with a double helical ribbon stirring blade and heated at 140°C under normal pressure and a nitrogen stream for 5 hours. Then, 0.36 parts of titanium tetrabutoxide catalyst was added again and the mixture was heated for 1.5 hours. The temperature was raised to 250°C, and a theoretical amount of 9,491 methanol was distilled out. Next, 0.02 part of tridecyl 7-osphere was added to the Xiao mixture, and the pressure in the system was reduced to 0.2 ml/g over 111 parts. Polymerization was carried out for S time.

The obtained polytetramethylene terephthalate had an intrinsic viscosity of 0.69 and a melting point of 221 tl.

Synthesis Example-2 145.5 parts of dimethyltere (7 thale), trimeri)
j104111 tetramethylene glycol 99.9 parts,
45.9 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 102o was charged together with 0.17 parts of titanium tetrabutoxide catalyst into a reaction vessel a equipped with a double helical ribbon lid stirring blade, and the mixture was heated at 180°C under a nitrogen stream at normal pressure. de1
The mixture was then heated at 250° C. for 2.6 hours to allow the theoretical amount of methanol to be distilled out. After the temperature of the reaction mixture reached 250°C, the pressure in the system was reduced to 0 over about 40 minutes.
．． The pressure was reduced to s HH, and polymerization was carried out for 5.5 hours under these conditions. The physical properties of the obtained elastomer are shown in 1) and 9.

Synthesis Example-S~6 Polymerization was carried out under exactly the same heavy metal conditions as in Synthesis fIl-2 using the amounts of each raw material shown in Table 1. Physical property values of each obtained polymer are shown in i#1.

Table-1 Preparation 7 Amount Examples-1 to 4 and Comparative Examples-1 to! Polytetramethylene terephthalate obtained in Synthesis Example-1 and synthetic gar! - 9 polyester polyether block copolymer obtained in step 4 were mixed in the proportions shown in Table 2, at which time 0 tridecyl phosphite was added to the total mixed polymer.
．． 2 mts were added. These mixtures were blend extruded at 240° C. using an extruder (Osaka Seiki 40-carbon extruder). The obtained blend composition was dried at 80° C. for 8 hours and then molded at 250° C. using a molding machine (Nissei injection molding machine τ8-100 model) to obtain a test piece. Table 2VC shows the results of measuring the mechanical strength of each test piece obtained.
Shown all together.

In addition, the mechanical strength of the polyester polyether block copolymer obtained from the PBT resin obtained in Synthesis Example 1 and the glycol component without side chains obtained in Synthesis Example 2 is shown in Reference Examples 1 and 2. It was shown to.

Claims (1)

[Claims] A dicarboxylic acid mixture consisting of 50 to 100 mol of terephthalic acid and 50 to 0 mol of isophthalic acid, 5~! Glycol represented by the following general formula (1) of S molar ratio and! 5
A block polyether polyester copolymer consisting of a diol mixture consisting of ~5 mol of tetramethylene glycol and a polyalkylene ether glycol having a number average molecular weight of 500 to 5000, wherein the scissors polyalkylene ether glycol component is entirely copolymerized as a phthalate. A composition consisting essentially of a polyester polyether block copolymer (I) and polytetramethylene terephthalate (n) having a weight of 5 to 50% by weight based on the combined weight, the mixing ratio (!) being 1 to 95%. Arrogant, (ID is 99
Resin composition 02 characterized by having a weight of ~5% (wherein R1 and R7 are hydrogen or an alkyl group having 1 to 4 carbon atoms) s *, , x are both water volume or methyl Except in case <o)