JP3434031B2 - Method for producing polyester resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester resin composition containing a polyester resin and a specific modified block copolymer as main components. The polyester resin composition has excellent impact resistance and is useful as a material for electric / electronic parts, automobile parts and the like.

[0002]

2. Description of the Related Art Polyester resins such as polybutylene terephthalate resins have excellent heat resistance, chemical resistance,
Utilizing various properties such as strength and elongation, it is used in a wide range of fields such as electric / electronic parts and automobile parts. However, polyester resins, especially polybutylene terephthalate resins, have the drawback of low impact strength, and there is a need for improvement. As a method for improving the impact resistance of a polybutylene terephthalate resin, it has been attempted to mix a rubber component with the polybutylene terephthalate resin (for example, Japanese Patent Publication Nos. 46-5224 and 46).
-5225, Japanese Patent Publication No. 46-5227, Japanese Patent Publication No. 46-32866, etc.).

[0003]

When different kinds of polymers are mixed to form a composition, there are generally very few combinations having good compatibility. Even in a composition obtained by mixing the above polybutylene terephthalate resin with a rubber component, in many cases, problems such as non-uniformity due to poor compatibility and interphase peeling occur, and polyester resins such as polybutylene terephthalate resin are produced. The fact is that it is not very effective in improving the impact resistance of resins. An object of the present invention is to provide a method for producing a polyester resin composition having improved impact resistance, particularly a polybutylene terephthalate resin composition having improved impact resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that impact resistance when a specific block copolymer is compounded during a synthetic reaction of a polybutylene terephthalate resin. It has been found that a resin composition having improved properties can be obtained, and that when the resin composition further contains an organic polysiloxane, the impact resistance is further improved, and the present invention has been achieved.

That is, the present invention is firstly, in producing a polyester resin by a transesterification reaction or an esterification reaction and a subsequent polycondensation reaction, vinyl aromatic compound polymer blocks (A-1) and 1,2 −
At least one block (A) selected from the group consisting of hydrogenated polybutadiene blocks (A-2) in the form of hydrogenated polybutadiene having a bonding amount of less than 30%, and hydrogenated polyisoprene blocks (B-1 ) Contact and becomes from at least one block (B) and selected from the group consisting of hydrogenated isoprene / butadiene copolymer block (B-3), modified block copolymer having a hydroxyl group at the end (I), and / Alternatively, a modified block copolymer (I) comprising a vinyl aromatic compound polymer block (C) and a polyisobutylene block (D) and having a hydroxyl group at the terminal (I
The ratio of I) to the total weight of the polyester resin / modified block copolymers (I) and (II) is 98/2 to 4
The method for producing a polyester resin composition is characterized in that the polyester resin composition is added to the reaction system at a ratio of 0/60 until the polycondensation reaction of the polyester resin is completed.

Secondly, according to the present invention, in producing a polyester resin by a transesterification reaction or an esterification reaction and a subsequent polycondensation reaction, vinyl aromatic compound polymer blocks (A-1) and 1,2- At least one block (A) selected from the group consisting of hydrogenated polybutadiene blocks (A-2) in the form of hydrogenated polybutadiene having a bonding amount of less than 30%, and hydrogenated polyisoprene blocks (B-1 ) Contact and becomes from at least one block (B) and selected from the group consisting of hydrogenated isoprene / butadiene copolymer block (B-3), modified block copolymer having a hydroxyl group at the end (I), and / Or vinyl aromatic compound polymer block (C)
And a polyisobutylene block (D), and the ratio of the weight of the polyester resin / the total weight of the modified block copolymers (I) and (II) of the modified block copolymer (II) having a hydroxyl group at the terminal is 98/2 to 40/60 is added to the reaction system until the polycondensation reaction of the polyester resin is completed, and the organic polysiloxane is added at a polyester resin / organic polysiloxane weight ratio of 100. /0.01 to 100/5 in a ratio of before or after completion of the polycondensation reaction, which is a method for producing a polyester resin composition.

In the present invention, the polyester resin means
A thermoplastic polyester resin, which is generally a polycondensation reaction of a dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative),
It is produced by a polycondensation reaction of hydroxycarboxylic acid, a combination of these reactions and the like. Examples of these polyester resins include polyethylene terephthalate (hereinafter referred to as “PET”), polybutylene terephthalate (hereinafter referred to as “PBT”), polyethylene naphthalate, polybutylene naphthalate, poly 1,4-cyclohexane dimethylene terephthalate, p- Examples thereof include hydroxybenzoic acid type polyester and polyarylate.

Among these polyester resins,
Polybutylene terephthalate resin (hereinafter referred to as “PBT resin”) is preferable because the impact resistance is remarkably improved. The PBT-based resin is generally obtained by reacting an acid component mainly composed of terephthalic acid or its ester-forming derivative (lower alkyl ester such as methyl ester or ethyl ester) with a diol component mainly composed of 1,4-butanediol. PBT can be given as a representative example.

The acid component for producing the PBT resin is
Although it may consist of terephthalic acid or an ester-forming derivative thereof, it may contain a small amount (usually 20 mol% or less) of another acid component, if necessary. Examples of such acid components that can be used in combination include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and bis (p-carboxyphenyl).
Aromatic dicarboxylic acids such as methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid and 5-sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid; 1,3 -Cyclohexanedicarboxylic acid,
Examples thereof include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; ester-forming derivatives of these dicarboxylic acids (lower alkyl esters such as methyl ester and ethyl ester). These acid components that can be used in combination may be only one kind or two or more kinds.

The diol component for producing the PBT resin may be composed of only 1,4-butanediol, but if necessary, a small amount (usually 20 mol% or less) of another diol component may be used. May be included. Examples of such diol components that can be used in combination include ethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,5-
Aliphatic diols having 2 to 10 carbon atoms such as pentanediol, cyclohexanedimethanol and cyclohexanediol; and polyalkylene glycols having a molecular weight of 6000 or less such as diethylene glycol, polyethylene glycol, polytrimethylene glycol and polytetramethylene glycol. . These diol components that can be used in combination may be only one kind or two or more kinds.

Further, the PBT resin may contain a small amount of trifunctional or more than trifunctional monomer components such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid, as long as its characteristics are not adversely affected. Good.

The modified block copolymer used in the present invention is a vinyl aromatic compound polymer block (A-
1) and at least one block (A) selected from the group consisting of hydrogenated polybutadiene blocks (A-2) in the form of hydrogenated polybutadiene having a 1,2-bond content of less than 30%; Isoprene block (B-
1) Contact and hydrogenated isoprene / butadiene copolymer block (B-3) becomes from the at least one block selected from the group consisting of (B), modified block copolymer having a hydroxyl group at the end (I), And / or a modified block copolymer (II) comprising a vinyl aromatic compound polymer block (C) and a polyisobutylene block (D) and having a hydroxyl group at the terminal.

Examples of the modified block copolymer (I) include those represented by the following formulas.

(X-Y) _k -OH (Y-X) _l -OH X- (Y-Z) _m -OH Y '-(X-Y) _n -OH

(In each formula, X and Z each represent a block (A), and Y and Y'each represent a block (B).
Where k, l, m and n each represent an integer of 1 or more, and OH represents a hydroxyl group. )

The number of repetitions k, l, m and n of the block (A) and the block (B) in the modified block copolymer (I) is usually preferably in the range of 1 to 5, respectively.

Examples of the modified block copolymer (II) include those represented by the following formulas.

HO-U- (V-W) _p- OH HO-V '-(U-V) _q- OH

(In each formula, U and W respectively represent a block (C), and V and V ′ respectively represent a block (D).
, P and q each represent an integer of 1 or more, and O
H and HO each represent a hydroxyl group. )

The repeating numbers p and q of the block (C) and the block (D) in the modified block copolymer (II) are
Usually, it is preferable that each is in the range of 1 to 5.

As is clear from the above formula, the modified block copolymer contains at least one block (A) and (B) in the molecule, or at least blocks (C) and (D). Although one is contained, it is preferable that two or more blocks (A) or (C) are contained. Among the modified block copolymers (I) and (II), particularly preferred is the formula XYZ-OH (wherein
X, Y, Z and OH are as defined above. ) Is a modified triblock copolymer. When the modified triblock copolymer is used, the resulting polyester resin composition exhibits particularly excellent impact resistance.

Vinyl aromatic compound polymer block (A-
1) and (C) are polymer blocks composed of monomer units mainly composed of vinyl aromatic compound units. Examples of the vinyl aromatic compound providing the vinyl aromatic compound unit in the blocks (A-1) and (C) include styrene; α
-Methylstyrene; o-, m-, or p-methylstyrene; 2,4-dimethylstyrene; vinylnaphthalene;
Examples thereof include vinyl anthracene, and among them, styrene and / or α-methylstyrene is preferable. The blocks (A-1) and (C) may be composed of only one kind of vinyl aromatic compound unit or may be composed of two or more kinds of vinyl aromatic compound units.

The block (A-2) is a hydrogenated polybutadiene block in which polybutadiene having a 1,2-bond content of less than 30% (preferably 25% or less) is hydrogenated. The polybutadiene before hydrogenation is composed of a monomer unit mainly composed of a butadiene unit, and 70 mol% or more (preferably 75 to 100 mol%) of the butadiene unit accounts for 2%.
- butene-1,4-diyl group (-CH ₂ -CH = CH-
CH _2- ; 1,4-bonded butadiene unit) and 3
Less than 0 mol% (preferably 25 to 0 mol%) is a vinylethylene group [—CH (CH═CH ₂ ) —CH ₂ —; 1,2-bond butadiene unit].

The block (B-1) is a hydrogenated polyisoprene block obtained by hydrogenating polyisoprene composed of a monomer unit mainly containing isoprene units. The isoprene unit is 2-methyl-2-butene-1,4-
Diyl group _{[-CH 2 -C (CH 3)} = CH-CH 2 -; 1,
4-bond isoprene unit], isopropenylethylene group [—CH [C (CH ₃ ) ═CH ₂ ] -CH ₂ —; 3,4-bond isoprene unit] and 1-methyl-1-vinylethylene group [ _{-C (CH 3) (CH =} CH 2) -CH 2 -; 1,
2-bond isoprene unit].

[0025]

The block (B-3) is a hydrogenated isoprene / butadiene copolymer block obtained by hydrogenating an isoprene / butadiene copolymer comprising monomer units mainly composed of isoprene units and butadiene units.
The isoprene unit is 2-methyl-2-butene-1,4-
It is at least one group selected from the group consisting of a diyl group, an isopropenylethylene group and a 1-methyl-1-vinylethylene group, and the butadiene unit is a 2-butene-1,4-diyl group and / or vinyl. It is an ethylene group. The disposition of the butadiene unit and the isoprene unit may be any of random, block, and tapered block.

The block (A-2), it may be the state of the hydrogenation be partially hydrogenated and fully hydrogenated in (B-1) Contact and <br/> (B-3). However, in the modified block copolymer (I), 50 or more carbon-carbon double bonds in the butadiene unit and / or the isoprene unit are included.
% Or more, especially 80% or more is hydrogenated (that is, the degree of unsaturation is 50% or less, and especially 20 mol% or less), heat deterioration resistance and weather resistance are good, and It is preferable in that it is possible to prevent the development of tackiness in the polyester resin composition obtained by using the composition and the molded article obtained from the composition. In the modified block copolymer (I), in the perspective effect of improving impact resistance Ru particularly large dishes, the molar ratio of isoprene units / butadiene unit in a range of 1 / 9-9 / 1, especially 3 /
7-7 / 3 range with going on block (B-3)
Good Masui.

The block (D) is an isobutylene unit [-
It is a polyisobutylene block containing C (CH ₃ ) ₂ —CH ₂ —] as a main monomer unit.

Ratio of total weight of blocks (A) / total weight of blocks (B) in modified block copolymer (I) and total weight of blocks (C) in modified block copolymer (II) / block (D) Although there is no particular limitation on the ratio of the total weight of), it is preferable that the ratio is within the range of 1/9 to 9/1. Weight ratio of block (A) / block (B) in modified block copolymer (I) or block (C) / in modified block copolymer (II)
When the weight ratio of the block (D) is 1/9 or more,
The heat resistance of the polyester resin composition obtained by the production method of the present invention can be maintained at a high level, while
When it is / 1 or less, the effect of improving the impact resistance of the composition becomes particularly large. It is particularly preferable that the weight ratio of block (A) / block (B) or block (C) / block (D) in the modified block copolymer is within the range of 2/8 to 7/3.

Modified block copolymers (I) and (II)
The hydroxyl group of may be located at the terminal of any of the block (A), the block (B), the block (C) and the block (D), but it is a hard block such as the block (A) or (C). It is preferably located at the end of. The content of terminal hydroxyl groups in the modified block copolymer is preferably 0.5 or more per molecule on average, and more preferably in the range of 0.7 to 2. When a block copolymer having no terminal hydroxyl group is used, the particle size of the block copolymer dispersed in the obtained polyester resin composition is large, and as a result, the impact resistance is insufficiently improved. Become.

The number average molecular weight of the block (A) in the modified block copolymer (I) or the block (C) in the modified block copolymer (II) is 4000 to 5000.
It is preferably in the range of 0. The number average molecular weight of the block (B) in the modified block copolymer (I) or the block (D) in the modified block copolymer (II) is 1
It is preferably in the range of 0000 to 100,000. Furthermore, the modified block copolymers (I) and (II) preferably have a number average molecular weight of 15,000 to 150,000. The modified block copolymer used is 1
There may be only one kind or two or more kinds.

In the present invention, the amount of the modified block copolymer added to the synthetic reaction system of the polyester resin is specified by a relative value with respect to the theoretical production amount of the polyester resin when the modified block copolymer is not added. In a weight ratio of the theoretical amount of the polyester resin / the total amount of the modified block copolymers (I) and (II) added.
It is within the range of / 2 to 40/60. When the amount of the modified block copolymer added is too large, the heat resistance inherent in the polyester resin, various properties such as strength and elongation cannot be expressed, and when it is too small, the resistance of the polyester resin composition is The impact improving effect is insufficient. From the viewpoint that both strength and elongation and impact resistance of the obtained polyester resin composition are particularly good, the theoretical production amount of the polyester resin / the total addition amount of the modified block copolymers (I) and (II) is It is preferable to adopt the condition that the weight ratio is within the range of 97/3 to 60/40.

In the production method of the present invention, any method similar to that used in the usual synthesis of polyester resins can be adopted except that the modified block copolymer is added. As a typical example, when the dicarboxylic acid component is a dicarboxylic acid such as terephthalic acid, an esterification reaction with a glycol such as 1,4-butanediol is carried out,
In the case of a dicarboxylic acid ester such as dimethyl terephthalate, a method in which a transesterification reaction with a glycol is performed, and the product obtained by the esterification reaction or the transesterification reaction is then subjected to a polycondensation reaction at high temperature under reduced pressure. Is mentioned.

According to the present invention, the modified block copolymer is added until the polycondensation reaction for producing the polyester resin is completed. The timing of addition of the modified block copolymer is not particularly limited as long as it is the time until the polycondensation reaction of the polyester resin is completed, and examples thereof include before the esterification reaction, during the esterification reaction, and the transesterification reaction. Before, during the transesterification reaction, before the polycondensation reaction, during the polycondensation reaction, or any other time. That is, in the production method of the present invention, it is important that the modified block copolymer is kneaded in the reaction system at least during the polymerization for obtaining the polyester resin. As a result, a resin composition excellent in impact resistance in which fine particles of the modified block copolymer are uniformly dispersed in the polyester-based matrix resin as described below can be obtained. However, from the point that the impact resistance improving effect becomes particularly remarkable, the modified block copolymer may be added before the esterification reaction, during the esterification reaction, before the transesterification reaction, during the transesterification reaction, before the polycondensation reaction, or The stage of the initial stage of the polycondensation reaction (the period in which the intrinsic viscosity of the polyester resin is 0.5 dl / g or less when measured at a temperature of 30 ° C. in an equal weight mixed solvent of phenol and tetrachloroethane) is preferable.

According to the production method of the present invention, (1) in a matrix resin mainly composed of polyester resin,
(2) Mainly selected from the group consisting of a vinyl aromatic compound polymer block (A-1) and a hydrogenated polybutadiene block (A-2) in the form of hydrogenated polybutadiene having a 1,2-bond content of less than 30%. At least one block (A) and a hydrogenated polyisoprene block (B)
-1) Contact and hydrogenated isoprene / butadiene copolymer block (at least one block selected from the B-3) consists of the group (B) and becomes from, modified block copolymer having a hydroxyl group at the end (I) , And / or a vinyl aromatic compound polymer block (C) and a polyisobutylene block (D), and a particle having an average particle diameter of 1.0 μm or less, which is composed of a modified block copolymer (II) having a hydroxyl group at the terminal. It is possible to obtain a polyester resin composition that is present in a dispersed state. The average particle size of the particles mainly composed of the modified block copolymer is preferably in the range of 0.01 to 0.7 μm from the viewpoint of improving the impact resistance of the polyester resin. The polyester-based resin composition is presumed to be produced as a result of a part of the added modified block copolymer reacting in the synthetic reaction system of the polyester-based resin, the modified block copolymer and the polyester-based resin. (Eg, modified block copolymer block / diblock copolymer of polyester resin block, modified block copolymer block / polyester resin block / triblock copolymer of modified block copolymer block) have.

The modified block copolymer (I) as described above
The polyester-based resin composition obtained by adding and / or (II) to the reaction system by the time the polycondensation reaction of the polyester-based resin is completed is more excellent when it contains an organic polysiloxane. The impact resistance is demonstrated. Such an organic polysiloxane has

-Si (R ¹ ) (R ² ) -O-

(In the formula, R ¹ and R ² each represent an alkyl group, an aryl group or an aralkyl group.)

The unit consisting of the repeating unit represented by
It is preferable from the viewpoint of the effect of improving impact resistance. Examples of the alkyl group include a methyl group and an ethyl group, examples of the aryl group include a phenyl group, and examples of the aralkyl group include a benzyl group. In addition, the repeating unit of the organic polysiloxane may be composed of only one kind, or may be composed of two or more kinds. When it is composed of two or more kinds of repeating units, the repeating units may be arranged in any of a random shape, a block shape, and a tapered block shape. As the organic polysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane,
Diphenyl polysiloxane, methylbenzyl polysiloxane and the like are preferable, and among these, dimethyl polysiloxane is particularly preferable. The viscosity of organic polysiloxane is
At 25 ° C., the range of 10 to 1,000,000 centistokes is preferable, and the range of 50 to 10,000 centistokes is more preferable. As the organic polysiloxane, only one kind may be used, or two or more kinds may be used in combination. In addition, commercially available organic polysiloxanes include those in which inorganic particles such as silica particles are blended as a dispersant, but additives are blended as long as they do not substantially affect the effects of the present invention. Organopolysiloxanes may be used.

The timing of adding the organic polysiloxane is not particularly limited, and even during the synthetic reaction of the polyester resin,
Further, it may be after completion of the synthetic reaction of the polyester resin in the presence of the modified block copolymer. The addition amount of the organic polysiloxane, when viewed as a relative value to the theoretical production amount of the polyester resin when the modified block copolymer and the organic polysiloxane are not added, is the theoretical production amount of the polyester resin / organic polysiloxane. It is preferable that the weight ratio of the added amount is within the range of 100 / 0.01 to 100/5. When the weight ratio of the polyester resin / organopolysiloxane is 100 / 0.01 or less,
When the impact resistance is greatly improved and is 100/5 or more, the physical properties such as heat resistance and strength and elongation derived from the polyester resin are effectively exhibited. When the organic polysiloxane is added to the polyester resin composition after the synthesis reaction of the polyester resin, the organic polysiloxane can be melt-kneaded with the polyester resin composition according to a conventional method. For the melt-kneading, a kneading machine such as a single-screw extruder, a twin-screw extruder, a kneader or a Banbury mixer can be used. The conditions of melt-kneading can be appropriately selected depending on the polyester resin composition to be used, the device, etc.,
Usually, it is sufficient to carry out at 180 to 300 ° C. for 3 to 15 minutes.

In the production method of the present invention, an antioxidant, a thermal decomposition inhibitor, an ultraviolet absorber, a crystallization nucleating agent, a crystallization accelerator, a colorant may be further added during or after the synthesis reaction of the polyester resin. , Flame retardants, reinforcing agents, fillers, release agents, plasticizers, antistatic agents, hydrolysis inhibitors, adhesion aids,
Adhesives, other polymers (polyolefins such as polyethylene and polypropylene; polystyrene, etc.) and the like can be optionally added. The polyester resin composition obtained by the production method of the present invention can be molded by any molding method such as injection molding, extrusion molding, press molding, blow molding, calender molding, cast molding and the like.

[0042]

In the polyester resin composition obtained by the production method of the present invention, the fine particles of the modified block copolymer are uniformly dispersed in the polyester resin, and the original elongation of the polyester resin is excellent. The impact resistance, which was lacking in polyester resins, is greatly improved without significantly impairing various properties. Although the reason for these is not clear, as described above, since the modified block copolymer is added during the synthesis of the polyester resin, a copolymer of the modified block copolymer and the polyester resin is produced. It is presumed that this is because the compatibility between the polyester resin and the modified block copolymer was improved due to the fact that the copolymer coexists in the resin composition.

[0043]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. The modified block copolymer used is indicated by the following abbreviations.

EPS-OH: Diblock body of hydrogenated polyisoprene block (number average molecular weight: 20,000) / polystyrene block (number average molecular weight: 10,000) having a hydroxyl group at the terminal of the polystyrene block (hydroxyl group content:
0.8 / molecule; styrene unit content on the basis of block copolymer before hydrogenation: 33% by weight; 1,4-bond content in polyisoprene block before hydrogenation: 92%, 3,4-bond content : 8%; Unsaturation based on hydrogenated polyisoprene block: 5%; number average molecular weight: 30,000)

SEP-OH: Hydrogenated polyisoprene block A diblock body of a polystyrene block (number average molecular weight: 10000) / hydrogenated polyisoprene block (number average molecular weight: 20000) having a hydroxyl group at the terminal (hydroxyl group content: 0. 7 / molecule; styrene unit content based on the block copolymer before hydrogenation: 33% by weight; 1,4-bond content in the polyisoprene block before hydrogenation: 92%, 3,
4-bond amount: 8%; degree of unsaturation based on hydrogenated polyisoprene block: 5%; number average molecular weight: 30,000)

SEPS-OH: A polystyrene block (number average molecular weight: 6000) / hydrogenated polyisoprene block (number average molecular weight: 28,000) / polystyrene block (number average molecular weight: 6000) having a hydroxyl group at one polystyrene block terminal. Triblock (hydroxyl group content: 0.8 / molecule; styrene unit content based on the block copolymer before hydrogenation: 30% by weight; 1,4-bond content in the polyisoprene block before hydrogenation: 92% , 3,
4-bond amount: 8%; degree of unsaturation based on hydrogenated polyisoprene block: 5%; number average molecular weight: 40,000)

[0047]

SEEPS-OH: A block of a hydrogenated product of a polystyrene block (number average molecular weight: 6000) / 1,3-butadiene and isoprene copolymer having a hydroxyl group at one terminal of the polystyrene block (number average molecular weight: 28000) / polystyrene block (number average molecular weight: 6000) triblock (hydroxyl group content: 0.8)
Number / molecule; styrene unit content based on block copolymer before hydrogenation: 30% by weight; molar ratio of isoprene unit / 1,3-butadiene unit is 1/1; and 1,3-butadiene before hydrogenation Amount of 1,4-bond in 1,3-butadiene unit in copolymer block with isoprene: 95%, 1,2
-Bonding amount: 5%, 1,4-bonding amount in isoprene unit: 95%, 3,4-bonding amount: 5%; based on block of hydrogenated product of copolymer of 1,3-butadiene and isoprene Unsaturation: 5%; number average molecular weight: 40000)

The resins and resin compositions of the following Examples and Comparative Examples were evaluated by the following measuring methods.

(1) Impact resistance evaluation: JIS K 71
According to 10, the notched Izod impact strength was measured at 23 ° C.

(2) Measurement of elongation: JIS K 7113
The elongation was measured according to.

(3) Measurement of average size of modified block copolymer particles: A part of the test piece was broken, and the modified block copolymer dispersed in the form of particles was extracted with toluene, followed by scanning electron microscope. The fracture surface was observed using. The average particle size was determined by image processing of this fracture surface.

(Example 1) Dimethyl terephthalate 74.
8 parts by weight, 41.7 parts by weight of 1,4-butanediol, and 0.03 part by weight of tetraisopropyl titanate were charged into a reaction tank (theoretical production amount of PBT: 85 parts by weight), and 170 to 230 ° C. under normal pressure. The transesterification reaction is carried out by gradually heating to 23.8% of methanol.
The transesterification reaction was stopped when part by weight was distilled. Then, 15 parts by weight of EPS-OH was added, and then the system was depressurized and transferred to the polycondensation reaction system. That is, it took about 30 minutes to raise the reaction temperature from 230 ° C. to 250 ° C. and reduce the pressure from normal pressure to 0.2 mmHg. Under this reaction temperature and pressure, the polycondensation reaction was carried out for about 60 minutes. Next, the polycondensation reaction was stopped by supplying nitrogen gas to the reaction tank and returning the system to normal pressure, to obtain a PBT resin composition. The evaluation results are shown in Table 1.

(Example 2) Dimethyl terephthalate 74.
8 parts by weight, 41.7 parts by weight of 1,4-butanediol, and 0.03 part by weight of tetraisopropyl titanate were charged into the reaction vessel (theoretical production amount of PBT: 85 parts by weight), and then 15 parts by weight of EPS-OH. Parts were added. Then, the temperature is gradually raised from 170 ° C. to 230 ° C. under normal pressure to perform a transesterification reaction by heating, and methanol is reduced to 23.8.
The transesterification reaction was stopped when part by weight was distilled. Next, the system was depressurized and transferred to the polycondensation reaction system. That is, it takes about 60 minutes to change the reaction temperature from 230 ° C to 250 ° C.
The temperature was raised to 0 ° C., and the pressure was reduced from normal pressure to 0.2 mmHg. Under this reaction temperature and pressure, about 60
The polycondensation reaction was carried out in minutes. Next, the polycondensation reaction was stopped by supplying nitrogen gas to the reaction tank and returning the system to normal pressure, to obtain a PBT resin composition. The evaluation results are shown in Table 1.

(Example 3) The addition amount of EPS-OH was adjusted to P
The theoretical weight ratio of BT theoretically produced / EPS-OH added is 7
Transesterification reaction and polycondensation reaction were carried out in the same manner as in Example 1 except that the amount was changed to 0/30, and PBT was added.
A resin composition was obtained. The evaluation results are shown in Table 1.

Example 4 The transesterification reaction was carried out in the same manner as in Example 1, and then 15 parts by weight of SEP-OH was added. Next, a polycondensation reaction was performed in the same manner as in Example 1 to obtain a PBT resin composition. The evaluation results are shown in Table 1.

(Examples 5 to 7) Instead of EPS-OH, SEPS-OH was used, and the theoretical production amount of PBT / SEPS-O.
The weight ratio of the added amount of H is 95/5 (Example 5), 90/1
A transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 except that the amount was 0 (Example 6) or 85/15 (Example 7) to obtain PBT-based resin compositions, respectively. . The evaluation results are shown in Table 1.

[0058]

[0059]

[Table 1]

(Examples 10 to 12) SEEPS-OH was used instead of EPS-OH, and the theoretical production amount of PBT / SEE
The weight ratio of the added amount of PS-OH was 95/5 (Example 1
0), 90/10 (Example 11) or 85/15 (Example 12), except that the transesterification reaction and the polycondensation reaction were performed in the same manner as in Example 1 to obtain PBT-based resins, respectively. A composition was obtained. The evaluation results are shown in Table 2.

(Example 13) 73.5 parts by weight of terephthalic acid and 27.5 parts by weight of ethylene glycol were charged into a reaction tank (theoretical amount of PET produced: 85 parts by weight), and 250
The esterification reaction was carried out for 2 hours at 2.5 ° C. and 2.5 kg / cm ² . Then add to this antimony trioxide 0.0
3 parts by weight, 0.01 parts by weight of phosphorous acid and SEPS-O
15 parts by weight of H was added, and then the system was depressurized and transferred to the polycondensation reaction system. In other words, it takes about 45 minutes,
The reaction temperature was raised from 250 ° C. to 280 ° C., and the pressure was reduced from normal pressure to 0.2 mmHg. Under this reaction temperature and pressure, the polycondensation reaction was carried out for about 90 minutes. Next, the polycondensation reaction was stopped by supplying nitrogen gas to the reaction tank and returning the system to normal pressure, to obtain a PET resin composition. The evaluation results are shown in Table 2.

[0062]

(Example 15) SEEPS-OH was used instead of SEPS-OH, and the theoretical production amount of PET / SEEPS
An esterification reaction and a polycondensation reaction were performed in the same manner as in Example 13 except that the weight ratio of the added amount of —OH was 85/15, to obtain a PET resin composition. The evaluation results are shown in Table 2.

Comparative Example 1 A PBT was produced in the same manner as in Example 1 except that no modified block copolymer was added. The evaluation results are shown in Table 2.

Comparative Example 2 PET was prepared in the same manner as in Example 13 except that no modified block copolymer was added.
Was manufactured. The evaluation results are shown in Table 2.

[0066]

[Table 2]

(Example 16) Dimethyl terephthalate 7
4.8 parts by weight, 1,4-butanediol 41.7 parts by weight, and tetraisopropyl titanate 0.03 parts by weight were charged into a reaction vessel (theoretical production amount of PBT: 85 parts by weight), and from 170 ° C. under normal pressure. The transesterification reaction was carried out by heating while gradually raising the temperature to 230 ° C., and the transesterification reaction was stopped when 23.8 parts by weight of methanol was distilled. Thereafter, 15 parts by weight of EPS-OH and 0.25 part by weight of dimethylpolysiloxane (viscosity at 25 ° C .: 100 centistokes; SH-200 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, and then the system was added. The pressure was reduced and transferred to the polycondensation reaction system. That is, it takes about 30 minutes and the reaction temperature is changed from 230 ° C. to 250
The temperature was raised to 0 ° C., and the pressure was reduced from normal pressure to 0.2 mmHg. Under this reaction temperature and pressure, about 60
The polycondensation reaction was carried out in minutes. Next, the polycondensation reaction was stopped by supplying nitrogen gas to the reaction tank and returning the system to normal pressure, to obtain a PBT resin composition. The evaluation results are shown in Table 3.

Example 17 The amount of EPS-OH added was
A transesterification reaction and a polycondensation reaction were performed in the same manner as in Example 16 except that the weight ratio of the theoretical production amount of PBT / the addition amount of EPS-OH was changed to 70/30.
A BT resin composition was obtained. The evaluation results are shown in Table 3.

(Examples 18 to 20) SEPS-OH was used instead of EPS-OH, and the theoretical production amount of PBT / SEPS
The weight ratio of the added amount of —OH was 95/5 (Example 18), 9
0/10 (Example 19) or 85/15 (Example 2)
The transesterification reaction and the polycondensation reaction were performed in the same manner as in Example 16 except that the PBT-based resin composition was added in an amount of 0). The evaluation results are shown in Table 3.

[0070]

(Examples 23 to 25) SEEPS-OH was used instead of EPS-OH, and the theoretical production amount of PBT / SEE
The weight ratio of the added amount of PS-OH was 95/5 (Example 2
3), 90/10 (Example 24) or 85/15 (Example 25), except that the transesterification reaction and the polycondensation reaction were performed in the same manner as in Example 16 to obtain the PBT-based resin. A composition was obtained. The evaluation results are shown in Table 3.

Example 26 100 parts by weight of a PBT resin composition obtained by carrying out a transesterification reaction and a polycondensation reaction in the same manner as in Example 7 and dimethylpolysiloxane (viscosity at 25 ° C .: 100 cm) Stokes; SH manufactured by Toray Dow Corning Silicone Co., Ltd.
-200) of 0.25 parts by weight in a twin-screw extruder
By melt-kneading at 0 ° C., a PBT resin composition containing dimethylpolysiloxane was obtained. The evaluation results are shown in Table 3.

[0073]

[Table 3]

[0074]

According to the present invention, as is apparent from the above examples, it is easy to prepare a polyester resin composition having improved impact resistance while retaining the original excellent performance of the polyester resin such as elongation. Can be obtained. Moreover, the polyester resin composition of the present invention is lightweight. Therefore, the resin composition can be used in a wide variety of applications as a molding material for electric / electronic parts, automobile parts, machine parts and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 53/00-53/02 C08L 67/00-67/04

Claims (8)

(57) [Claims] 1. When producing a polyester resin by a transesterification reaction or an esterification reaction and a subsequent polycondensation reaction, the vinyl aromatic compound polymer block (A-1) and the 1,2-bond content are less than 30%. At least 1 selected from the group consisting of hydrogenated polybutadiene blocks (A-2) in the form of hydrogenated polybutadiene
The seed of the block (A), from at least one block selected from the group consisting of hydrogenated polyisoprene block (B-1) Contact and hydrogenated isoprene / butadiene copolymer block (B-3) (B) A modified block copolymer having a hydroxyl group at the terminal (I) and / or a modified block copolymer having a vinyl aromatic compound polymer block (C) and a polyisobutylene block (D) and having a hydroxyl group at the terminal The polycondensation reaction of the polyester resin is completed at a ratio of (II) weight ratio of polyester resin / total weight of modified block copolymers (I) and (II) of 98/2 to 40/60. A method for producing a polyester resin composition, characterized in that the polyester resin composition is added to the reaction system during the period up to. 2. A vinyl aromatic compound polymer block (A-1) and a 1,2-bond content of less than 30% in producing a polyester resin by a transesterification reaction or an esterification reaction and a subsequent polycondensation reaction. At least 1 selected from the group consisting of hydrogenated polybutadiene blocks (A-2) in the form of hydrogenated polybutadiene
The seed of the block (A), from at least one block selected from the group consisting of hydrogenated polyisoprene block (B-1) Contact and hydrogenated isoprene / butadiene copolymer block (B-3) (B) A modified block copolymer having a hydroxyl group at the terminal (I) and / or a modified block copolymer having a vinyl aromatic compound polymer block (C) and a polyisobutylene block (D) and having a hydroxyl group at the terminal The polycondensation reaction of the polyester resin is completed at a ratio of (II) weight ratio of polyester resin / total weight of modified block copolymers (I) and (II) of 98/2 to 40/60. Add to the reaction system until the temperature reaches 100%, and the weight ratio of the polyester resin / organic polysiloxane is 100 / 0.01.
A method for producing a polyester resin composition, characterized in that the polycondensation reaction is added before or after the completion of the polycondensation reaction in a ratio of about 100/5. 3. The method according to claim 1, wherein the polyester resin is a polybutylene terephthalate resin. 4. The modified block copolymer (I) has the formula X-
A modified triblock copolymer represented by Y-Z-OH (wherein X and Z each represent a block (A), Y represents a block (B), and OH represents a hydroxyl group). The method according to 1, 2, or 3. 5. A matrix resin composed mainly of a polyester resin, wherein (2) a vinyl aromatic compound polymer block (A-1) and polybutadiene having a 1,2-bond content of less than 30% are hydrogen. At least one block (A) selected from the group consisting of hydrogenated polybutadiene block (A-2) in the added form, hydrogenated polyisoprene block (B-1) and hydrogenated isoprene / butadiene copolymer block A modified block copolymer (I) having at least one type of block (B) selected from the group consisting of (B-3) and having a hydroxyl group at the terminal, and / or a vinyl aromatic compound polymer block (C). And a polyisobutylene block (D), and a modified block copolymer (I
A polyester resin composition comprising particles of I) having an average particle diameter of 1.0 μm or less dispersed therein. 6. A matrix resin comprising (1) a polyester resin as a main component, (2) a vinyl aromatic compound polymer block (A-1) and a polybutadiene having a 1,2-bond content of less than 30% as hydrogen. and added forms of hydrogenated polybutadiene block at least one block selected from (a-2) composed of a group (a), a hydrogenated polyisoprene block (B-1) Contact and hydrogenated isoprene / butadiene copolymer A modified block copolymer (I) having at least one type of block (B) selected from the group consisting of blocks (B-3), having a hydroxyl group at the terminal, and / or a vinyl aromatic compound polymer block (C). ) And a polyisobutylene block (D), and a modified block copolymer (I) having a hydroxyl group at the terminal
A polyester resin composition characterized in that particles of I) having an average particle diameter of 1.0 μm or less are present in a dispersed state and further contains an organic polysiloxane. 7. A polyester resin composition according to claim 5 or 6 polyester resin is a polybutylene terephthalate resin. 8. The modified block copolymer (I) has the formula X-
A modified triblock copolymer represented by Y-Z-OH (wherein X and Z each represent a block (A), Y represents a block (B), and OH represents a hydroxyl group). The polyester resin composition according to 5 , 6, or 7 .