JPH1087801A - Composite polyester block copolymer molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite molding having a joint excellent in peeling strength by bonding a molding comprising a thermoplastic resin to a molding comprising a polyester elastomer excellent in flexibility, heat resistance and chemical resistance. SOLUTION: This molding is prepared by bonding a molding (P) of a polyester block copolymer composed of 10-70wt.% hard segments (A) comprising a crystalline polyester made from an acid component comprising an aromatic dicarboxylic acid and a diol component comprising a 2-4C diol and soft segments (B) comprising a polyester having a melting point of 100 deg.C or below or being amorphous and made from an acid component comprising an aromatic dicarboxylic acid and/or an aliphatic dicarboxylic acid and a diol component comprising a 5-15C aliphatic diol and/or a polyoxyalkylene glycol to a molding (Q) of a thermoplastic resin composition comprising 10-100wt.% polycarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded article obtained by joining a polyester block copolymer molded article and a thermoplastic resin molded article, a method for producing the same, and a polyester block copolymer.

[0002]

2. Description of the Related Art Polyester elastomers are widely used as heat-resistant and chemical-resistant thermoplastic elastomers. A method of melting and bonding a polyester elastomer and a crystalline polyester resin has been studied so far, and Japanese Patent Publication No. 8-9187 discloses that a polyester elastomer and a polyalkylene terephthalate having a melting point of 230 ° C. or less are integrally formed. Composite moldings are described.
In order to obtain sufficient adhesive strength by this technique, it is necessary to use a PBT resin having a melting point lower than that of the elastomer.

[0003] Japanese Patent Publication No. 5-75016 discloses a melting point of 80.
It is a hydrogenated product of a block copolymer comprising a vinyl aromatic compound polymer block A and at least one olefin compound polymer block B in a thermoplastic polyester at -180 ° C, wherein the degree of unsaturation of the block B is 20%. A thermoplastic elastomer composition obtained by blending a hydrogenated block copolymer having a molecular weight of at least one or more and / or a modified hydrogenated block copolymer having a molecular unit containing a carboxylic acid group or a derivative thereof bonded to the polymer. Is disclosed as a composition having excellent adhesiveness to a resin having

Japanese Patent Application Laid-Open No. Hei 3-100045 discloses that a heat-sealing property is obtained by blending a hydrogenated SBS block copolymer, an olefin elastomer or the like with a polyester block copolymer having a soft segment comprising polyether or polycaprolactone. Also disclosed are thermoplastic elastomer compositions.

[0005]

However, these conventional techniques do not always provide sufficient adhesive peel strength. Also, Japanese Patent Publication No. 5-75016 or Japanese Patent Laid-Open No. 3-100
In the technique described in No. 045, since a diene compound is added to a polyester elastomer, the heat resistance and chemical resistance of the polyester elastomer may be impaired.

[0006] An object of the present invention is to obtain a composite molded article in which a polyester elastomer and a thermoplastic resin are joined and which has a strong joining strength. More specifically, it is an object of the present invention to obtain a composite molded product having excellent peel strength, in which a polyester block copolymer resin having excellent heat resistance and chemical resistance is bonded to a thermoplastic resin.

Another object of the present invention is to obtain a polyester elastomer which can be integrally molded with a thermoplastic resin containing polycarbonate and which has a high peel strength at the joint interface during integral molding.

[0008]

Means for Solving the Problems The inventors of the present invention produced a molded article having a joint by fusion bonding using a specific polyester block copolymer and a thermoplastic resin composition containing a specific polycarbonate. It has been found that a molded article having excellent bonding strength at the joint can be obtained, and the present invention has been accomplished.

That is, according to the present invention, a polyester having crystallinity comprising an aromatic dicarboxylic acid as an acid component and a diol having 2 to 4 carbon atoms as a diol component is a hard segment (A).
A polyester having an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid as an acid component and an aliphatic diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol as a diol component and having a melting point of 100 ° C. or lower or being amorphous. Is a soft segment (B), and the hard segment (A) is 10 to 70% by weight of the polyester block copolymer (P). When this polyester block copolymer is molded integrally with a thermoplastic resin composition containing 10 to 100% by weight of polycarbonate,
Has strong peel strength at the bonding interface.

The present invention also relates to a polyester block copolymer (P) molded product and a polycarbonate of 10 to 100.
It is a composite molded article which is joined to a thermoplastic resin composition (Q) molded article containing by weight.

The polyester block copolymer (P) used in the present invention comprises a hard segment (A) and a soft segment (B).

[Hard Segment (A)] The hard segment (A) contains an aromatic dicarboxylic acid as an acid component and has 2 to 2 carbon atoms.
Polyester having a crystallinity with a diol of 4 as a diol component, but naphthalenedicarboxylic acids such as terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred as aromatic dicarboxylic acids constituting the hard segment, and terephthalic acid is particularly preferred. . Particularly preferred is tetramethylene terephthalate as the hard segment (A).

[Soft segment (B)] The soft segment (B) comprises an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid as an acid component and a diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol as a diol component. , A polyester having a melting point of 100 ° C. or lower or being amorphous. As the acid component, an aromatic dicarboxylic acid is preferable. Therefore, as the soft segment (B), an aromatic dicarboxylic acid is used as an acid component, and a diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol is used as a diol component. Polyesters having the following melting points or amorphous are preferred. The aromatic dicarboxylic acid is, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, preferably terephthalic acid.
The naphthalenedicarboxylic acid is, for example, 2,6-naphthalenedicarboxylic acid.

The diol having 5 to 15 carbon atoms is preferably an aliphatic diol having 5 to 15 carbon atoms, such as hexamethylene glycol, decamethylene glycol, 3-methylpentanediol, and 2-methyloctamethylenediol.

Among the aliphatic diols having 5 to 15 carbon atoms, there are also aliphatic diols containing an ether group in the carbon chain. Such diols are preferably of the molecular formula HO (CH ₂ CH ₂
O) _i H (i = 2-5), molecular formula HO (CH ₂ CH ₂ CH ₂₎
CH ₂ O) _i H (i = 2 to 3), more preferably HO (CH ₂ CH ₂ O) _i H
(I = 2 to 5), particularly preferably triethylene glycol.

The polyoxyalkylene glycol has an average molecular weight of 500 to 3,000, and is, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol, preferably polytetramethylene glycol.

The soft segment (B) is a polymer comprising units constituting the soft segment and is amorphous or has a melting point of 100 ° C. or lower, preferably 50 ° C. or lower.

[Copolymer Component] An aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid may be copolymerized in the soft segment (B). As the aliphatic dicarboxylic acid, for example, having 4 to 4 carbon atoms
Twelve straight-chain dicarboxylic acids, furthermore, straight-chain dicarboxylic acids having 8 to 12 carbon atoms, particularly succinic acid, adipic acid and sebacic acid. Examples of the alicyclic dicarboxylic acid include cyclohexanedicarboxylic acid.

The soft segment (B) may be copolymerized with an aromatic dicarboxylic acid other than the main component. Non-linear dicarboxylic acids such as phthalic acid and isophthalic acid are preferably used as the aromatic dicarboxylic acid, but terephthalic acid is also preferable when the long-chain diol contains an ether group or when it contains a side chain and is difficult to crystallize. Is an acid.

A diol other than the main component may be copolymerized in the soft segment.
And 4 linear aliphatic diols, for example, diethylene glycol.

The copolymerization ratio of these components is preferably 40 mol%, more preferably 30 mol%, based on the dicarboxylic acid component.
Mol%, particularly preferably 20 mol%.

[Polyester block copolymer (P)]
The polyester block copolymer (P) used in the present invention comprises a hard segment (A) and a soft segment (B), and the ratio is 10 to 70 to 90 by weight.
-30, preferably 25-50 to 75-50. When the number of hard segments is more than this, the flexibility of the molded product of the polyester block copolymer (P) is insufficient, and further,
Melt adhesion to polycarbonate is greatly reduced. If the number of soft segments is more than this, the crystallinity becomes low, and it becomes difficult to produce a composite molded article.

The segment lengths of the hard segment (A) and the soft segment (B) constituting the polyester block copolymer (P) are preferably expressed as a molecular weight of 500 to 7000, more preferably 800 to 5000.
It is.

Although it is difficult to directly measure the segment length, for example, the composition of the polyester constituting each of the soft segment and the hard segment, the melting point of the polyester composed of the components constituting the hard segment, and the weight of the obtained polyester block. From the melting point of the coalescence, it can be estimated using Flory's equation.

The proportion of the copolymer component present in the hard segment (A) and the soft segment (B) is preferably 40 mol%, more preferably 3 mol%, based on the dicarboxylic acid component.
It is 0 mol%, particularly preferably 20 mol%.

The lower the copolymerization ratio, the higher the melting point of the polyester block copolymer (P), which is preferable. However, copolymerization is also performed to increase flexibility. However, if the copolymerization ratio is too high, it is difficult to crystallize, and the moldability and the like are deteriorated. The copolymerization ratio is such that the melting point of the crystals of the polyester block copolymer is 16
The ratio may be 0 ° C. or higher, preferably 170 ° C. or higher.

The polyester block copolymer (P) is
For example, it can be produced using a method in which a polyester comprising the components constituting the hard segment and the soft segment is produced, and melt-mixed so that the melting point is 2 to 40 ° C. lower than that of the polyester constituting the hard segment. . Since this melting point varies depending on the mixing temperature and time, it is preferable to deactivate the catalyst by adding a catalyst deactivator such as phosphorus oxyacid when the desired melting point is reached.

The polyester block copolymer (P) is
Those having an intrinsic viscosity of 0.6 or more, preferably 0.8 to 1.5, measured in orthochlorophenol at 35 ° C can be applied. If the intrinsic viscosity is lower than this, the strength is low.

The polyester block copolymer (P) is
A polymer other than the polyester block copolymer, for example, a polyester such as polybutylene terephthalate, a stabilizer, a pigment, a dye, a twist-resistant agent, a nucleating agent, a lubricant and other additives may be contained. The amount of these additives and polymers is
It is 0.01 to 50 parts by weight based on 100 parts by weight of the composition of the present invention.

[Thermoplastic Resin Composition (Q) Containing Polycarbonate] In the present invention, a thermoplastic resin composition (Q) containing 10 to 100% by weight of polycarbonate is used.

The polycarbonate is a polycarbonate known per se, preferably an aromatic polycarbonate, more preferably an aromatic polycarbonate obtained by reacting a dihydric phenol with a carbonate precursor. These can be obtained by a known polymerization method, for example, a solution method or a melting method.

The dihydric phenol is, for example, bisphenol A or bis (4-hydroxyphenyl) alkane compound, preferably bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Ethane, 2,2-bis (4-hydroxyphenylpropane), 2,2-bis (4-hydroxy-3
-Methylphenyl) propane, particularly preferably bisphenol A. Dihydric phenols can be used alone or in combination of two or more.

The carbonate precursor is, for example, carbonyl halide, carbonate, or haloformate, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof.

In the production of the aromatic carbonate, a suitable molecular weight modifier, a branching agent, a catalyst and the like can be used.

The polycarbonate used in the present invention is 1
In the thermoplastic resin composition (Q) containing 0 to 100% by weight, the thermoplastic resin is, for example, polyester, ABS, or polyamide, and polyester is preferable. Polycarbonate accounts for 10 to 100% by weight of the total composition, preferably 20 to 100% by weight, particularly preferably 40 to 100% by weight. When the content of polycarbonate is small, the adhesive strength of the joint surface of the composite molded product is low.
In order to obtain a strong adhesive strength, it is necessary to contain at least 10% by weight of polycarbonate.

The thermoplastic resin composition (Q) containing a polycarbonate contains a flame retardant, an inorganic filler, a fibrous reinforcing agent, a nucleating agent, a stabilizer, a pigment, a resin, etc., to such an extent that the object of the present invention is not impaired. A modifier and the like can be contained.

[Composite molded article] The composite molded article of the present invention was brought into contact with a molded article of a thermoplastic resin composition (Q) containing polycarbonate in a molten state of the polyester block copolymer (P). It is preferable to manufacture by cooling and solidifying as it is.

As a method for producing the composite molded article of the present invention, a molded article of a thermoplastic resin composition (Q) containing a preformed polycarbonate is placed in a mold, and the polyester block copolymer is added to the mold. (P) injection molding, injection molding, first one resin is injected into the mold, then the other resin is injected into the same mold from the other cylinder, and two-color molding to obtain a molded product is different. Co-extrusion molding in which a resin is simultaneously extruded from two dies is used. The preferred method is insert molding as described above. Known injection molding machines and extrusion molding machines can be used for molding the composite molded article.

[0039]

The present invention will be described in detail with reference to examples. In the examples, "parts" means "parts by weight", and "wt%" means "% by weight". Hereinafter, polybutylene terephthalate is referred to as PB
T and polycarbonate may be abbreviated as PC. The elastomers used in the examples and the comparative examples and methods for measuring physical properties are as follows.

[Elastomer 1] 175 parts of dimethyl isophthalate, 23 parts of dimethyl sebacate and 140 parts of hexamethylene glycol were subjected to a transesterification reaction with a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure to give an intrinsic viscosity of 1.06. Thus, an amorphous polyester having no endothermic peak due to melting of the crystals as measured by the DSC method was obtained.

A polybutylene terephthalate chip having an intrinsic viscosity of 0.98, obtained by separately polycondensation with the polyester, was dried, and 107 parts were added. After reacting at 240 ° C. for 45 minutes, phenylphosphonic acid was added at 0. The reaction was stopped by adding one part.

The melting point of the obtained polyester block copolymer was 190 ° C. and the intrinsic viscosity was 0.93. This is called elastomer 1.

[Elastomer 2] 125 parts of dimethyl isophthalate, 54 parts of dimethyl sebacate and 140 parts of hexamethylene glycol were subjected to a transesterification reaction with a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure to give an intrinsic viscosity of 1.
No. 06 was obtained.

Using this polyester and 107 parts of polybutylene terephthalate, a polyester block copolymer was obtained in the same manner as in Elastomer 1. This is called elastomer 2.

[Elastomer 3] After transesterification of 194 parts of dimethyl terephthalate and 160 parts of triethylene glycol with a dibutyltin diacetate catalyst, polycondensation was carried out under reduced pressure to obtain a starch-like polyester having an intrinsic viscosity of 0.76. Was.

After adding 107 parts of polybutylene terephthalate to the polyester and reacting at 250 ° C. for 75 minutes, the reaction was stopped by adding 0.1 parts of phenylphosphonic acid.

The melting point of the obtained polyester block copolymer was 176 ° C., and the intrinsic viscosity was 0.83. This is called elastomer 3.

[Elastomer 4] Transesterification of 180 parts of dimethyl terephthalate, 20 parts of dimethyl sebacate, 140 parts of tetraethylene glycol and 30 parts of diethylene glycol with a dibutyltin diacetate catalyst was conducted, followed by polycondensation under reduced pressure to obtain an intrinsic viscosity. 1.06 polyester was obtained.

Using this polyester and 107 parts of polybutylene terephthalate, a polyester block copolymer was obtained in the same manner as in Elastomer 1. This is called elastomer 4.

[Elastomer 5] 245 parts of dimethyl terephthalate, 399 parts of polytetramethylene glycol (average molecular weight: 2,000), and 159 parts of tetramethylene glycol are polymerized by a conventional method using tetrabutoxytitanate as a catalyst to give an intrinsic viscosity of 1.42. Hard segment amount 38
A wt% polyester block copolymer was obtained. This is called elastomer 5.

[Elastomer 6] 613 parts of dimethyl terephthalate, 185 parts of polytetramethylene glycol (average molecular weight: 1000), 398 parts of tetramethylene glycol
Is polymerized by a conventional method using tetrabutoxytitanate as a catalyst to obtain an intrinsic viscosity of 1.61 and a hard segment amount of 7
9 wt% of a polyester block copolymer was obtained. This is called elastomer 6.

[Amount of Hard Segment] The amount of hard segment was calculated from the amount of polytetramethylene glycol charged based on the weight of polymer after polymerization.

[Peel strength] 180 ° based on JIS K6854
The peel adhesion strength (peel strength) was measured. Test speed is 20
0 mm / min.

[Peeling Test Piece] In conducting a peeling test, a mating material (PBT, PC, PBT / PC) was previously prepared.
Was subjected to injection molding to prepare a flat test piece having a thickness of 1.5 mm and a size of 15 cm × 10 cm. Then, the flat plate was placed in a mold capable of forming a flat plate having a thickness of 3 mm, and thereafter, the elastomer described in Examples and Comparative Examples was injection-molded to obtain a composite molded product in which the mating material and the elastomer were melt-bonded. Then, a peel test specimen having a width of 2 cm was cut out from the composite molded product. The mold temperature at the time of melt bonding by injection molding is 60 ° C. in all cases.

[Examples 1 to 5] Using the pellets of each of the elastomers 1 to 5, the mating material was changed to PC by the above method.
(Trade name: Panlite L-122, manufactured by Teijin Chemicals Limited)
A peel test piece obtained by insert molding described in 5) was obtained, and the peel strength was measured by the above method.

As a result, in Examples 1 to 4, the peel strength was 45 kg / cm or more, and the base material of the elastomer layer was broken, resulting in peeling. Table 1 shows the results.

[Examples 6 to 10] Using the pellets of each of the elastomers 1 to 5, the counterpart was made P
A peel test piece was obtained by insert molding using C / PBT (a blend of 50% by weight of PC and 50% by weight of PBT), and the peel strength was measured by the above method. Table 1 shows the results.

PC / PBT (50/50) is 50% by weight of PC
And 50% by weight of PBT (C7000N manufactured by Teijin Limited) were pelletized using a twin-screw extruder (TEX44 manufactured by Nippon Steel Corporation).

[0059]

[Table 1]

[Comparative Examples 1 to 5] Using the pellets of each of the elastomers 1 to 5, the counterpart was made PC
/ PBT (a blend of 5% by weight of PC and 95% by weight of PBT) was used to obtain a peel test piece by insert molding, and the peel strength was measured by the above method. Table 1 shows the results.
PC / PBT (5/95) is 5% by weight of PC and 95% by weight of PBT
% Was pelletized using a twin-screw extruder (TEX44, manufactured by Nippon Steel Corporation). The peel strength was extremely reduced. Table 2 shows the results.

[Comparative Example 6] A peel test specimen was prepared in the same manner as in Example 1 and the peel strength was measured by using Santoprene 201-87 manufactured by Monsanto Chemical Co., Ltd., which is an olefin elastomer, as the elastomer and using the mating material as PC.
As a result, no adhesive effect was observed, and the sample peeled off during the measurement. Table 2 shows the results.

Comparative Example 7 A peeling test piece was prepared in the same manner as in Example 1 except that elastomer 6 was used as the elastomer and the mating material was PC, and the peel strength was measured. Table 2 shows the results.

[0063]

[Table 2]

[0064]

EFFECTS OF THE INVENTION Moldings made of thermoplastic resin and flexibility,
This is a composite molded article obtained by joining molded articles made of a polyester elastomer having excellent heat resistance and chemical resistance, and a composite molded article having excellent peel strength at a joint can be obtained.

Claims (6)

[Claims] 1. An aromatic dicarboxylic acid comprising an acid component having 2 carbon atoms
Polyester having crystallinity by using diols of Nos. To 4 as a diol component as a hard segment (A), and an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid as an acid component;
An aliphatic diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol is used as a diol component.
A polyester having a melting point of not higher than 0 ° C or less or an amorphous polyester is used as a soft segment (B), and a hard segment (A) is 10 to 70% by weight. %
A composite molded article formed by joining a thermoplastic resin composition (Q) molded article contained therein. 2. The soft segment (B) constituting the polyester block copolymer (P) has an aromatic dicarboxylic acid as an acid component and an aliphatic diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol as a diol component. The composite molded article according to claim 1, which is a polyester having a melting point of 100 ° C or less or an amorphous polyester. 3. The soft segment (B) constituting the polyester block copolymer (P) contains at least one kind selected from terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid as an acid component, and HO (CH ₂ CH)
_3. The composite molded product according to claim 1, wherein the polyester is a polyester having a diol represented by ₂ O) _i H (i = 2 to 5) as a diol component and having a melting point of 100 ° C. or less or being amorphous. 4. An aromatic dicarboxylic acid comprising an acid component having 2 carbon atoms.
Polyester having crystallinity by using diols of Nos. To 4 as a diol component as a hard segment (A), and an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid as an acid component;
An aliphatic diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol is used as a diol component.
A polyester block copolymer comprising a soft segment (B) comprising a polyester having a melting point of not higher than 0 ° C. or amorphous as a soft segment (B) and 10 to 70% by weight of a hard segment (A). 5. An aromatic dicarboxylic acid as an acid component, having 2 carbon atoms.
Polyester having a crystallinity comprising a diol having a diol of from 4 to 4 as a hard segment (A), an aromatic dicarboxylic acid as an acid component, an aliphatic diol having 5 to 15 carbon atoms and / or a polyoxyalkylene glycol as a diol component. A polyester block copolymer in which a polyester having a melting point of 100 ° C. or less or an amorphous polyester is used as a soft segment (B), and the hard segment (A) is 10 to 70% by weight. 6. The method according to claim 1, wherein the polyester block copolymer (P) is brought into contact with a molded article of the thermoplastic resin composition (Q) containing polycarbonate in a molten state and solidified. A method for producing a composite molded product according to any one of the above.