JP5581099B2 - Composite molded body - Google Patents

Description

The present invention relates to a composite molded article using a thermoplastic elastomer composition for bonding a polyester resin, which has good heat-fusibility to a polyester resin, particularly polybutylene terephthalate, and is excellent in flexibility.

Recently, the sophistication of the performance of the synthetic resin (plastic) manufactured parts and members, strict demand for advanced functions, attempts to complexation with engineering plastics and thermoplastic elastomer with excellent mechanical strength therein There is movement. And in the case of the compounding, it is the most effective to combine both by heat fusion with each other by the injection molding technique which is a molding means common to both.

  Engineering plastics are used for mechanical parts or structural parts that are subject to load. As engineering plastics of this type of thermoplastic resin, polyamide, polyacetal, polycarbonate, modified polyphenylene oxide, polyester resin, polysulfone, wholly aromatic polyester, and the like are widely known.

  On the other hand, a molded body of a thermoplastic elastomer is also molded by an injection molding technique with particularly good productivity and used for many applications. As this type of thermoplastic elastomer, styrene, polyolefin, polyurethane, polyester, polyamide, and the like are known.

  This injection molding method is capable of molding even molded products with complex shapes, and is suitable for mass production. The injection molding method is also applied to the engineering plastics described above, and various machine parts and structural parts are efficient. Well manufactured.

  In general, the heat-fusability between a thermoplastic engineering plastic and a thermoplastic elastomer excellent in rubber elasticity is poor, and the two cannot be firmly bonded. For this reason, when trying to manufacture composite moldings such as composite parts and composite members with high added value by compounding thermoplastic engineering plastics and thermoplastic elastomers, uneven joints are provided at the joints between them. At present, it is unavoidable to employ extremely non-productive joining means such as a mechanical joining method and a joining method by applying an adhesive to the joint between the two.

  Such a composite technology of a thermoplastic engineering plastic and a thermoplastic elastomer is inefficient and has many problems such as the strength of the joint surface and the sealability. That is, the method of mechanically joining by providing a locking part such as a concave-convex fitting has a problem that the structure of the mold becomes complicated or the number of steps increases depending on the structure. In addition, in view of the shape of the final composite molded body, it may not be possible to obtain a strong bonded structure.

  In addition, the bonding method using an adhesive has a problem that the bonding strength is weak due to a process such as application of the adhesive and the deterioration of the adhesive.

By the way, in the prior art, there are no thermoplastic elastomers that are heat-fusible and flexible with respect to polyester resins such as polyethylene terephthalate and polybutylene terephthalate, which are generally difficult to heat-fuse. On the other hand, it is extremely non-productive joining means such as a method of mechanically joining by providing a concave and convex engaging portion at the joint part as described above, a method of joining by applying an adhesive to the joint part of both It was the present situation that we had to adopt.
For example, Patent Document 1 discloses a composite molded article characterized by comprising a thermoplastic polyester resin layer and a styrene elastomer layer, but the adhesive strength between the two is quite insufficient.

JP 2002-127313 A

An object of the present invention is to provide a composite molded body using a thermoplastic elastomer composition having good heat-fusibility to a polyester-based resin and excellent flexibility.

  As a result of intensive studies, the present inventors have surprisingly found that the above-mentioned object can be achieved by adding an acrylic block copolymer in a specific blending amount as a flexible component to a polyester-based thermoplastic elastomer, The present invention has been completed.

  Examples of the molding method using the material of the present invention include a double injection method and an insert molding method. The former molding method in which molding is performed simultaneously or continuously has a higher surface temperature of the adherend, which is advantageous for heat fusion of two materials. However, if the material of the present invention is used, a molded body having sufficient fusion strength can be obtained even by the latter molding method in which one molded body is sufficiently cooled.

That is, the present invention is as follows.
1. In composite moldings of engineering plastics and thermoplastic elastic bodies,
The engineering plastic is a polyester resin,
The thermoplastic elastic body is
(A) 40-95 parts by mass of a polyester-based thermoplastic elastomer, and (b) a block copolymer 5-60 comprising a block (A) mainly composed of a methacrylic ester and a block (B) mainly composed of an acrylate ester. Parts by mass (however, the total of the components (a) and (b) is 100 parts by mass)
A composite molded article comprising a thermoplastic elastomer composition containing
2. 2. The composite molded article according to 1 above, wherein the (b) block copolymer has a triblock structure.
3. The (b) block copolymer is a block copolymer having an ABA type triblock structure (provided that the A block component is a methacrylic ester and the B block component is an acrylate ester). The composite molded article according to 1 or 2 above.
4). The (b) block copolymer has the following general formula-(A1)-(B)-(A2)-
(Wherein (A1) and (A2) each represent a block component composed of a methacrylic acid alkyl ester, and (B) represents a block component composed of an acrylic acid alkyl ester). 4. The composite molded article as described in 3 above, wherein
5. 5. The composite molded article as described in 4 above, wherein the block copolymer (b) is produced by a living anion polymerization method.
6). 5 to 25 parts by mass of a block copolymer (c) composed of an aromatic vinyl compound modified with a polar group-containing compound and a conjugated diene compound is added to 100 parts by mass of the total of the components (a) and (b). The composite molded article according to any one of 1 to 5, wherein the composite molded article is formed as described above.
7). JIS-D hardness measured according to JISK6253 of said (a) component is 20-60, The composite molded object in any one of said 1-6 characterized by the above-mentioned.
8). 8. The composite molded article according to any one of 1 to 7, wherein the polyester-based resin as the adherend is polyethylene terephthalate and / or polybutylene terephthalate.

By using the thermoplastic elastomer composition of the present invention, a polyester resin and a thermoplastic elastomer such as polyethylene terephthalate and polybutylene terephthalate, it can be strongly melt bonded through efficient heat sealing means. Thereby, a composite molded body having new performance and function is effectively provided.

It is a front view of the test piece for measuring peeling strength. It is sectional drawing of the test piece for measuring peeling strength. It is a figure explaining the measuring method for measuring peeling strength.

Hereinafter, the present invention will be described in more detail.
(A) Polyester thermoplastic elastomer The component (a) used in the present invention is a polyester thermoplastic elastomer composition.
This has a hard segment and a soft segment. This type of polyester-based thermoplastic elastomer includes polyester segments (hard segments) prepared from aromatic dicarboxylic acids and short-chain glycols, and polyethers prepared from aromatic dicarboxylic acids and polyalkylene glycols (long-chain glycols). Polyether ester type copolymers having segments (soft segments) are well known. Also known are polyester ester type copolymers prepared using polycaprolactone as a soft segment.

  A typical polyester-based thermoplastic elastomer is prepared by subjecting dimethyl terephthalate, 1,4-butanediol, and poly (oxytetramethylene) glycol as starting materials to a polycondensation reaction and a transesterification reaction. There is what is shown by the following general formula.

(In the above general formula, m and n represent the number of repeating units and are integers of 1 or more)

  The properties of the polyester-based thermoplastic elastomer vary depending on the ratio of the hard segment to the soft segment, or depending on the type of component of each segment, but the general characteristics are flex resistance, oil resistance, and wear resistance. Excellent heat resistance.

  Examples of commercially available polyester thermoplastic elastomers include Hytrel (trade name, Toray DuPont Co., Ltd.), Perprene (trade name, manufactured by Toyobo Co., Ltd.), and Glais (trade name, Dainippon Ink Chemical Co., Ltd.). .

  In the present invention, from the viewpoint of flexibility, the JIS-D hardness measured according to JIS K6253 of the component (a) is preferably 20 to 60, and more preferably 20 to 40.

(B) Block copolymer The component (b) used in the present invention is a block copolymer comprising a block (A) mainly composed of a methacrylic ester and a block (B) mainly composed of an acrylate ester, Either a linear structure or a radial structure may be used. Moreover, any of block structures, such as AB, ABA, and ABAB, may be sufficient. Preferably, the (b) block copolymer should have a triblock structure in terms of expression of heat-fusibility with a polyester-based resin and flexibility (hereinafter may be referred to as component (b-1)). . Moreover, it is preferable that it is a linear structure.

Component (b-1) The component (b-1) is an ABA type triblock copolymer in which the ABA type A block component is a methacrylic acid ester and the B block component is an acrylic acid ester, preferably the ABA type. It is a block copolymer having a triblock structure.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-tert-butyl, methacrylic acid- n-pentyl, methacrylate-n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, methacrylic acid Phenyl, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid -Hydroxypropyl, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, methacryl Trifluoromethyl methyl acid, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl 2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethacrylic acid Fluoromethyl, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl ethyl methacrylate, meta One or two or more types of combinations such as 2-perfluorodecylethyl laurate and 2-perfluorohexadecyl ethyl methacrylate can be mentioned. Among them, methyl methacrylate exhibits heat-fusibility with a polyester resin, It is preferable in terms of flexibility.

  Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, acrylic acid- n-pentyl, acrylic acid-n-hexyl, cyclohexyl acrylate, acrylic acid-n-heptyl, acrylic acid-n-octyl, acrylic acid-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, acrylic acid Phenyl, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, Ak Glycidyl phosphate, 2-aminoethyl acrylate, γ- (acryloyloxypropyl) trimethoxysilane, γ- (acryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic acid 2-trifluoromethylethyl, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoroacrylate Methylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate One or more combinations of can be cited, among others, heat-welding expression of methyl acrylate and polyester resins, preferred in view of flexibility.

Furthermore, from the viewpoint of the expression and flexibility of heat fusion with a polyester resin, the component (b-1) is preferably represented by the following general formula-(A1)-(B)-(A2)-
(Wherein (A1) and (A2) each represent a block component composed of an alkyl methacrylate, and (B) represents a block component composed mainly of an alkyl acrylate ester). It is what has.

  Examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-tert-butyl, methacrylic acid. -N-pentyl, methacrylate-n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, methacryl Acid phenyl, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, methacrylate 2-hydroxypropyl phosphate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide of methacrylic acid Adduct, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate Perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl methacrylate , 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, or the like, or a combination of two or more thereof. Among them, methyl methacrylate exhibits heat-fusibility with a polyester resin. From the viewpoint of flexibility.

  Examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, and acrylic acid. -N-pentyl, acrylate-n-hexyl, cyclohexyl acrylate, acrylate-n-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, acrylic Phenyl acid, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate Glycidyl acrylate, 2-aminoethyl acrylate, γ- (acryloyloxypropyl) trimethoxysilane, γ- (acryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperacrylate Fluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecyl acrylate One or more combinations such as ethyl can be cited, among others, heat-welding expression butyl -n- acrylate and polyester resins, preferred in view of flexibility.

  Among the above, an ABA type triblock copolymer comprising polymethyl methacrylate and polyacrylic acid-n-butyl is preferable in terms of expression of heat fusion with a polyester resin and flexibility. ABA type triblock copolymer in which the segment is composed of polymethyl methacrylate and the soft segment is composed of poly-n-butyl acrylate is preferable.

  The weight average molecular weight (Mw) of the (b) block copolymer in the present invention is, for example, 10,000 to 1,000,000, preferably 30,000 to 500,000, particularly 50,000 to 150. More preferably, it is 1,000.

  In the present invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer (b) is preferably 1.0 to 1.8, particularly 1 .1 to 1.5 is preferable.

  In addition, examples of the polymerization method of the block copolymer (b) in the present invention include living anion polymerization and living radical polymerization.

Examples of such an acrylic ABA triblock copolymer include LA polymers 2140E and 2250 manufactured by Kuraray, and NABSTAR manufactured by Kaneka. Of these, LA polymer produced by Kuraray, which is synthesized by living anionic polymerization, is preferable in terms of the expression of heat fusion with a polyester resin.
Kuraray's LA polymers 2140E and 2250 have a triblock structure represented by the above general formula-(A1)-(B)-(A2)-, and (A1) and (A2) are polymethyl methacrylate. , (B) is poly-n-butyl acrylate, the weight average molecular weight is 80,000, and the JIS-A hardness is 32 and 65, respectively.

In the present invention, the blending ratio of (a) the polyester-based thermoplastic elastomer and (b) the block copolymer is extremely remarkable. That is, when the total of the components (a) and (b) is 100 parts by mass, the lower limit of the component (a) is 40 parts by mass, and the upper limit of the component (b) is 60 parts by mass. Moreover, the upper limit of the component (a) is 95 parts by mass, and the lower limit of the component (b) is 5 parts by mass.
If the upper limit of the component (a) is exceeded, the flexibility is insufficient, and if it is less than the lower limit of the component (a), the heat-fusibility with the polyester resin becomes insufficient.
The component (a) alone is insufficient in flexibility, whereas the component (b) alone is insufficient in heat fusion with the polyester resin.
In the combined use of the component (a) and the component (b), surprisingly, when the blending amount of the component (b) is increased, the heat-fusibility between the composition of the present invention and the polyester-based resin is as follows: And it improved rather than the heat-fusion property with the polyester-type resin by (b) component simple substance, (a) 65 mass part of component, (b) 35 mass part of component became the maximum.
From the viewpoint of heat fusion with the polyester resin, the upper limit of the component (a) is 75 parts by mass, and the lower limit of the component (b) is 25 parts by mass. Moreover, the minimum of (a) component is 55 mass parts, and the upper limit of (b) component is 45 mass parts.
More preferably, the upper limit of the component (a) is 70 parts by mass, and the lower limit of the component (b) is 30 parts by mass. Moreover, the minimum of (a) component is 60 mass parts, and the upper limit of (b) component is 40 mass parts.

In this invention, the block copolymer (c) which consists of an aromatic vinyl compound modified with a polar group-containing compound and a conjugated diene compound with respect to a total of 100 parts by mass of the components (a) and (b) is 5 to 25 masses. It is preferable to further blend parts.
By blending such a component (c), the flexibility can be further improved without deteriorating the heat-fusibility to the polyester resin. However, when the component (c) exceeding 25 parts by mass is added, the heat-fusibility is greatly lowered.
The block copolymer (c) composed of an aromatic vinyl compound and a conjugated diene compound may be a hydrogenated product, for example, a styrene-butadiene-styrene copolymer (SBS), a styrene-ethylene butene-styrene copolymer. Polymer (SEBS), Styrene-isoprene-styrene copolymer (SIS), Styrene-isoprene-butadiene-styrene copolymer, Styrene-ethylene-propylene-styrene copolymer (SEPS), Styrene-ethylene-ethylene-propylene -Styrene copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer, SBBS), styrene-isobutylene-styrene copolymer (SIBS), etc. . The polar group-containing compounds include maleic anhydride, (meth) acrylic acid, (meth) acrylic acid esters (glycidyl methacrylate, oxazolyl methacrylate, methyl methacrylate, etc.), allyl ether (allyl glycidyl ether, allyl oxazolyl ether, allyl) Carboxyl ether, etc.). Of these, maleic anhydride is preferred in terms of both flexibility and adhesiveness. Modification methods are known, and the polar group-containing compound may be introduced into the block copolymer according to a known method. The ratio of the modification of the polar group-containing compound is preferably, for example, 0.5 to 5% by mass with respect to the block copolymer.
As the component (c), a commercially available product can be used. For example, Tuftec M1913 (product of Asahi Kasei Chemicals Corporation), which is a styrene-ethylene-butene-styrene copolymer (SEBS) modified with maleic anhydride, JIS-A hardness 84, maleic acid grafting rate 2 mass%), Kraton FG1901X (Clayton polymer product, JIS-A hardness 71, maleic acid grafting rate 2 mass%).
The amount of component (c) is preferably 5 to 25 parts by mass, and 10 to 20 parts by mass with respect to a total of 100 parts by mass of component (a) and component (b) in terms of heat fusion with the polyester resin. More preferably. Within this range, flexibility can be improved while maintaining heat-fusibility to the polyester resin. If it exceeds 25 parts by mass, the heat-sealing property to the polyester resin is remarkably deteriorated.

Other ingredients (d)
In addition to the above components, the composition of the present invention may further contain various anti-blocking agents, sealability improvers, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, and lubricants as necessary. It is also possible to contain a crystal nucleating agent, a colorant and the like. Here, examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like, phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. 0-3.0 mass parts is preferable with respect to a total of 100 mass parts of said (a) and (b) component, and, as for antioxidant, 0.1-1.0 mass part is especially preferable.

Production of the above-mentioned thermoplastic elastomer composition The thermoplastic elastomer composition of the present invention comprises the components (a) and (b) or, if necessary, the component (c) and the like. In addition, it can be manufactured by melt-kneading.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 180 to 220 ° C.

Moreover, this invention provides the laminated body formed by laminating | stacking the polyester-type resin adhesive thermoplastic elastomer composition of the said this invention, and a polyester-type resin.
Examples of the polyester-based resin as the adherend include polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like. Are preferred, and polybutylene terephthalate is particularly preferred.
Examples of the method for laminating the polyester-based resin-bonded thermoplastic elastomer composition of the present invention and the polyester-based resin include an extrusion molding method and an injection molding method. Among these, the injection molding method is preferable from the viewpoint of productivity. The injection molding conditions are not particularly limited, and examples include a method in which the adherend is in a molten state, such as a double injection molding method, and an insert injection molding method in which an already cooled and solidified adherend is inserted into a mold. The composition of the present invention has excellent heat-fusibility even in insert injection molding that is more severe to heat-sealing.

  EXAMPLES Next, although an Example and a comparative example further demonstrate this invention, this invention is not limited to the following examples, unless it deviates from the summary.

1. Raw materials used The raw materials used in Examples and Comparative Examples are as follows.
(1) Polyester thermoplastic elastomer component (a)
(A-1) TPEE-1: Hytrel 2401 (product of Toray DuPont Co., Ltd., JIS-D hardness = 37, polyester segment (hard segment) prepared from aromatic dicarboxylic acid and short-chain glycol, and aromatic dicarboxylic acid And polyether ester type copolymer having polyether segment (soft segment) prepared from polyalkylene glycol (long chain glycol)
(A-2) TPEE-2: Hytrel 2551 (product of Toray DuPont Co., Ltd., JIS-D hardness = 60, polyester segment (hard segment) prepared from aromatic dicarboxylic acid and short-chain glycol, and aromatic dicarboxylic acid And polyether ester type copolymer having polyether segment (soft segment) prepared from polyalkylene glycol (long chain glycol)

(2) Block copolymer component (b)
(B-1) LA polymer 2140E (Kuraray product, compound name: acrylic block copolymer, polymerization method: living anion polymerization, JIS-A hardness 32)
(B-2) LA polymer 2250 (Kuraray Co., Ltd., compound name: acrylic block copolymer, polymerization method: living anion polymerization, JIS-A hardness 65)
(B-3) NABSTAR N700AS (Kaneka Corporation, compound name: acrylic block copolymer, polymerization method: living radical polymerization, JIS-A hardness 22)
(B-4) Ethylene / acrylic terpolymer rubber having carboxyl group: VAMAC G (DuPont product, compound name: ethylene-alkyl acrylate random copolymer rubber, JIS-A hardness 15)

(3) Other components (c)
(C-1) Styrene-ethylene butene-styrene copolymer modified with maleic anhydride (SEBS): Tuftec M1913 (Kuraray Co., Ltd., JIS-A hardness 84, maleic anhydride modified amount = 2 mass%)

(Examples 1-9 and Comparative Examples 1-4)
1. Preparation of Composition After blending a predetermined amount (parts by mass) of each component in the amount shown in Table 1, the composition is composed of the compositions of Examples and Comparative Examples in a twin-screw extrusion kneader (manufacturing temperature 180 ° C.) having a screw diameter of 20 mm. A pellet was prepared. The following various evaluations were performed using the obtained various compositions.

2. Evaluation Method (1) Hardness: Based on JIS K 6253, the hardness of each composition prepared above was measured. A 6.3 mm thick press sheet was used as the test piece.

(2) Tensile strength: Based on JIS K 6251, the tensile strength of the various compositions prepared above was measured. As a test piece, a 1 mm thick press sheet was punched into a No. 3 type with a dumbbell and used. The tensile speed was 500 mm / min.

(4) Elongation at break: The elongation at break of the various compositions prepared above was measured according to JIS K 6251. As a test piece, a 1 mm thick press sheet was punched into a No. 3 type with a dumbbell and used. The tensile speed was 500 mm / min.

(5) Heat-fusible strength Using the test piece 1 shown in FIGS.
1 to 3, a polyester resin plate 3 having a length of 150 mm, a width of 25 mm, and a thickness of 4 mm was prepared by injection molding under the following injection conditions. The resin used for the resin plate preparation is as follows.
(A) Polyethylene terephthalate resin: TR-8550 (manufactured by Teijin Limited)
(B) Polybutylene terephthalate resin: Toraycon 1401 X06 (manufactured by Toray Industries, Inc.)
(The injection conditions of the resin plate conformed to the recommended injection conditions of the resin manufacturer used.)
Injection molding machine: FS-120 manufactured by Nissei Plastic Industry Co., Ltd.
Molding temperature: (A) 270-290 ° C, (B) 230-250 ° C
Mold temperature: (A) 60 ° C, (B) 80 ° C
Injection speed: 30 to 40 mm / second for both (A) and (B) Injection pressure: 180 to 200 MPa for both (A) and (B)
Holding pressure: (A), (B) both 40-60 MPa
Injection time: 10 seconds for both (A) and (B) Cooling time: 30 seconds for both (A) and (B)

  After the polyester resin plate obtained above was allowed to cool to room temperature for 48 hours or longer, the paper 4 was attached to a part of the resin plate 3 with a double-sided tape and inserted into a mold, and then the thermoplastic elastomer composition was The test piece which inject | poured on the following conditions and heat-bonded the polyester resin board 3 and the thermoplastic elastomer composition board 2 in the location of A was created.

Injection molding machine: FS-120 manufactured by Nissei Plastic Industrial Co., Ltd.
Molding temperature: 220-270 ° C
Mold temperature: 30-60 ° C
Injection speed: 75 to 85 mm / sec Injection pressure: 200 MPa
Holding pressure: 0 MPa
Injection time: 5 seconds Cooling time: 30 seconds

  Next, about the obtained test piece, 180 degree peel strength was measured by bend | folding the thermoplastic elastomer composition board 2 as shown in FIG. 3, and pulling the both ends of 2 and 3 in the direction of the arrow, respectively.

(6) Injection moldability: 130 mm × 130 mm × 2 mm sheets of the various compositions prepared above are injection molded under the following injection molding conditions, the appearance is visually observed, and whether or not flow marks and sink marks are generated. Evaluation was made according to the following criteria.
○: Good, ×: Bad

Injection molding conditions:
Molding temperature 250 ° C
Mold temperature 30 ℃
Injection speed 70-80 mm / sec Injection pressure 100-160 MPa
Holding pressure 0-30 MPa
Injection time 5 seconds Cooling time 30 seconds

  The results are shown in Table 1.

As shown in Table 1, Examples 1 to 9 have good heat-fusibility with respect to the polyester resin and are excellent in flexibility.
Comparative Examples 1 and 2 are examples in which (a) a polyester-based thermoplastic elastomer and (b) a block copolymer are used alone, respectively, (a) alone is hard, and (b) alone is heat to the polyester-based resin. The fusion strength is not sufficient.
Comparative Example 3 has a blended composition of 30 parts by mass of (a) polyester-based thermoplastic elastomer (70 parts by mass of (b) block copolymer), but in this region, the heat-sealing strength to the polyester resin is small.
Comparative Example 4 is an example in which (a) a polyester-based thermoplastic elastomer is blended, but (b) a block copolymer is not blended, and an acrylic rubber which is a random copolymer is blended instead. Yes, it was inferior in heat-fusibility and injection moldability to polyester resins.

DESCRIPTION OF SYMBOLS 1 Test piece 2 Thermoplastic elastomer composition board 3 Polyester resin board 4 Paper A Thermal fusion part

Claims (8)

In composite moldings of engineering plastics and thermoplastic elastic bodies,
The engineering plastic is a polyester resin,
The thermoplastic elastic body is
(A) 40-95 parts by mass of a polyester-based thermoplastic elastomer, and (b) a block copolymer 5-60 comprising a block (A) mainly composed of a methacrylic ester and a block (B) mainly composed of an acrylate ester. Parts by mass (however, the total of the components (a) and (b) is 100 parts by mass)
A composite molded article comprising a thermoplastic elastomer composition containing The composite molded body according to claim 1, wherein the (b) block copolymer has a triblock structure. The (b) block copolymer is a block copolymer having an ABA type triblock structure (provided that the A block component is a methacrylic ester and the B block component is an acrylate ester). The composite molded article according to claim 1 or 2. The (b) block copolymer has the following general formula-(A1)-(B)-(A2)-
(Wherein (A1) and (A2) each represent a block component composed of a methacrylic acid alkyl ester, and (B) represents a block component composed of an acrylic acid alkyl ester). The composite molded article according to claim 3, wherein the composite molded article is provided . The composite molded body according to claim 4, wherein the block copolymer (b) is produced by a living anion polymerization method. 5 to 25 parts by mass of a block copolymer (c) composed of an aromatic vinyl compound modified with a polar group-containing compound and a conjugated diene compound is added to 100 parts by mass of the total of the components (a) and (b). The composite molded article according to any one of claims 1 to 5, wherein The JIS-D hardness measured according to JISK6253 of said (a) component is 20-60, The composite molded object in any one of Claims 1-6 characterized by the above-mentioned. The composite molded body according to any one of claims 1 to 7, wherein the polyester-based resin as an adherend is polyethylene terephthalate and / or polybutylene terephthalate.

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