JP3989502B2 - Molding resin composition - Google Patents

Description

  The present invention relates to a molding resin composition.

Moisture enters an electric wire, such as a harness, used in an automobile or the like from a ground portion or the like. Usually, in order to prevent the moisture from entering the automobile, the conductor 53 that is joined to the joining portion 52 via the caulking portion 51 is cut off in the middle of the harness 50 shown in FIG. It was necessary to provide. For this reason, there is a problem that the design and the like are restricted by the wiring turning, which is disadvantageous in terms of cost.
For the connector, a method such as injection-curing a one-part silicone resin composition or the like to make it waterproof and water-stopping, specifically, the molded part 61 is made of ethylene / propylene as in the connector 60 shown in FIG. It is known that a one-pack type silicone resin composition or the like is injected into a portion where a joint 62 and a conductor 63 are joined using a rubber member such as a copolymer (EPDM). Since the curing time of the resin composition or the like is long, there is a problem that it is necessary to leave it for about 1 to 2 hours in the factory.

Various polyester resins having characteristics such as flexibility, heat resistance, chemical resistance, oil resistance, stretchability and moldability are known. However, conventionally known polyester resins having some of the above characteristics have a problem that the balance between moldability and flexibility is poor and cannot be used as a hot melt material for molding. For example, if the resin is low viscosity and easy to mold, the flexibility after molding is very low, and conversely, molding is difficult with a resin having flexibility.
Other examples include urethane hot melts, polyamide hot melts, EVA hot melts, and silicone fillers, but they cannot be used as molding hot melt materials.

  In response to the above problems, the present inventors have proposed a molding resin composition that contains an aromatic polyester and can be used as a molding hot melt resin composition (see Patent Documents 1 and 2).

  By the way, soft polyvinyl chloride (PVC) has been conventionally used as a coating material for wires of harnesses and connectors. However, conversion to polyolefin-based materials is being promoted for dehalogenation.

JP 2003-213099 A JP 2004-210893 A

  The molding resin compositions described in Patent Documents 1 and 2 are excellent in flexibility, heat resistance, oil resistance and stretchability, and further have low viscosity and excellent moldability, but have insufficient adhesion to polyolefin. There wasn't. On the other hand, hot melts containing polyolefin as a main component could improve adhesion to polyolefins but could not secure adhesion to metals and PVC. Usually, since a metal is used for the caulking portion of the harness, the polyolefin-based hot melt cannot be used as these sealing materials. In addition, polyolefin hot melt has a problem that whitening occurs due to contact with gasoline for a long time, and cracks or the like may occur in some cases.

  Then, in order to solve the said problem, an object of this invention is to provide the resin composition for shaping | molding excellent in the adhesiveness with respect to polyolefin, a metal, and PVC, and gasoline resistance.

  As a result of intensive studies, the inventor contains an aromatic polyester, a tackifier, a polyol compound, and a polyolefin. When the content of the polyolefin is within a specific range, the adhesiveness to polyolefin, metal, and PVC. In addition, the present inventors have found that the gasoline resistance is excellent and completed the present invention.

That is, the present invention provides the following (1) to (14).
(1) An aromatic polyester (a), a tackifier (b), a polyol compound (c) having two or more hydroxy groups in one molecule, and a polyolefin (d),
The molding resin composition whose content of the said polyolefin (d) is 5-40 mass parts with respect to a total of 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d).
(2) The molding resin composition according to (1), wherein the polyolefin (d) has a polar group.
(3) The molding resin composition according to (2), wherein the polar group is at least one selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group.
(4) The resin composition for molding according to (1), wherein the polyolefin (d) has an epoxy group, a carboxy group, and / or an acid anhydride group.
(5) The molding resin composition according to (3) or (4), wherein the carboxy group is a carboxy group derived from maleic acid, and the acid anhydride group is a maleic anhydride group.
(6) The said (1)-(5) content of the said tack fire (b) is 1-50 mass parts with respect to a total of 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d). The molding resin composition according to any one of the above.
(7) Said (1)-whose content of said polyol compound (c) is 0.5-50 mass parts with respect to a total of 100 mass parts of said aromatic polyester (a) and said polyolefin (d). (6) The molding resin composition according to any one of the above.
(8) The molding resin composition according to any one of (1) to (7), wherein the viscosity at 190 ° C. is 10 to 500 Pa · s.
(9) The aromatic polyester (a) is selected from the group consisting of an acid component containing terephthalic acid and / or isophthalic acid, ethylene glycol, polytetramethylene ether glycol, neopentyl glycol and 1,4-butanediol. The resin composition for molding according to any one of the above (1) to (8), which is a polyester obtained by reacting with a hydroxy group component containing at least one kind.
(10) Polyester A obtained by reacting an acid component containing terephthalic acid and isophthalic acid and a hydroxy group component containing ethylene glycol and neopentyl glycol as the aromatic polyester (a),
(1) to (1) above containing an acid component containing terephthalic acid and isophthalic acid, and a polyester B obtained by reacting a hydroxy group component containing 1,4-butanediol and polytetramethylene ether glycol. (8) The molding resin composition according to any one of the above.
(11) As the aromatic polyester (a), a polyester obtained by further reacting an acid component containing terephthalic acid, isophthalic acid and sebacic acid with a hydroxy group component containing 1,4-butanediol. The molding resin composition according to (10), containing C.
(12) The aromatic polyester (a) can be obtained by further reacting an acid component containing terephthalic acid, isophthalic acid and ε-caprolactone with a hydroxy group component containing 1,4-butanediol. The molding resin composition according to the above (10) or (11), which contains polyester D.
(13) The molding resin composition according to any one of (1) to (12), wherein the tackifier (b) is a rosin tackifier.
(14) The molding resin composition as described in (13) above, wherein the rosin tackifier is rosin diol.

  The molding resin composition of the present invention is excellent in adhesion to polyolefins, metals and PVC, and gasoline resistance. In particular, when a polyolefin having a polar group is used, the aromatic polyester and the polyolefin are not separated even after the molding resin composition of the present invention is melted for a long time, and the adhesiveness can be maintained.

Hereinafter, the present invention will be described in more detail.
The molding resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) has an aromatic polyester (a), a tackifier (b), and two or more hydroxy groups in one molecule. The polyol compound (c) and the polyolefin (d) are contained, and the content of the polyolefin (d) is 5 to 5 parts by mass with respect to a total of 100 parts by mass of the aromatic polyester (a) and the polyolefin (d). It is a resin composition for molding which is 40 mass parts.

<Aromatic polyester (a)>
The aromatic polyester (a) is not particularly limited, and any known aromatic polyester can be used without particular limitation, and among them, an aromatic polyester obtained from a condensation reaction between a fatty acid and a glycol is preferable.
Specific examples of the aromatic polyester (a) include an acid component containing terephthalic acid and / or isophthalic acid, ethylene glycol (hereinafter abbreviated as EG), polytetramethylene ether glycol (hereinafter PTMG). A hydroxy group component containing at least one selected from the group consisting of neopentyl glycol (hereinafter abbreviated as NPG) and 1,4-butanediol (hereinafter abbreviated as 1,4-BD). Aromatic polyesters containing polyester obtained by reaction are mentioned, and more specifically, aromatic polyesters containing polyesters A to D shown below are preferred.

  The polyester A is a polyester obtained by a condensation reaction using a mixture of terephthalic acid and isophthalic acid as an acid component and using a mixture of NPG and EG as a hydroxy group component. The viscosity of the polyester A at 190 ° C. is preferably 0.5 to 2 Pa · s, and more preferably 0.7 to 1.5 Pa · s.

  Similarly, the polyester B is a polyester obtained by a condensation reaction using a mixture of terephthalic acid and isophthalic acid as an acid component and using a mixture of PTMG and 1,4-BD as a hydroxy group component. The melt index (melt index) (hereinafter abbreviated as MI), which is a measure of the fluidity of the polyester B in the molten state, is preferably 10 or more at 200 ° C., more preferably 13-50. If the MI of the polyester B is within this range, the viscosity at the time of molding is kept low, and the heat resistance after molding is excellent, which is preferable. Here, the PTMG is not particularly limited as long as it is a polymer obtained by polymerizing 1,4-BD, and the number average molecular weight is preferably 2000 or more, and H-283 manufactured by Mitsubishi Chemical Corporation as a commercially available product. Can be used.

  The polyester C is a polyester obtained by a condensation reaction using a mixture of terephthalic acid, isophthalic acid and sebacic acid as an acid component and 1,4-BD as a hydroxy group component. The viscosity of Polyester C at 190 ° C. is preferably 200 to 700 Pa · s, and more preferably 400 to 600 Pa · s.

  The polyester D is a polyester obtained by a condensation reaction using a mixture of terephthalic acid, isophthalic acid and ε-caprolactone as an acid component and 1,4-BD as a hydroxy group component. The viscosity of Polyester D at 190 ° C. is preferably 100 to 300 Pa · s, and more preferably 150 to 200 Pa · s.

  The aromatic polyester (a) preferably contains at least two selected from the group consisting of the polyesters A, B, C and D, and contains the polyester A and the polyester B. Is more preferable. This is a molding resin composition obtained by containing polyester B excellent in flexibility, heat resistance, chemical resistance, oil resistance and stretchability, and polyester A having low viscosity and excellent moldability. This is because the viscosity at the time of molding is kept low and the solidified product after molding is given flexibility. For the same reason, the aromatic polyester (a) preferably contains the polyester A, polyester B, polyester C and / or polyester D.

The content ratio of the polyesters A, B, C, and D in the aromatic polyester (a) is 10 to 50% by mass of the polyester A and the polyester B with respect to the total mass of the aromatic polyester (a). It is preferable to contain 10 to 50% by mass, 0 to 30% by mass of the polyester C, and 0 to 30% by mass of the polyester D, 25 to 45% by mass of the polyester A, and 20 to 40 of the polyester B. It is more preferable that the polyester C contains 0 to 20% by mass, the polyester D is 0 to 25% by mass, the polyester A is 30 to 40% by mass, and the polyester B is 25 to 35% by mass. More preferably, the polyester C contains 0 to 15% by mass and the polyester D contains 0 to 20% by mass.
When the content ratio of the polyesters A, B, C and D is within this range, it is possible to give flexibility to the solidified product after molding while keeping the viscosity at the time of molding of the resulting resin composition for molding. The solidified product after molding is preferable because it is excellent in oil resistance and gasoline resistance. Furthermore, it is preferable because the curing time after molding is short and there is no need for curing.
Further, the composition of the present invention having such properties is excellent in heat shock resistance and can follow the expansion and contraction of the adherend during the heat cycle, and therefore can be used as a hot melt material for molding. preferable.

<Tackfire (b)>
As the tackifier (b), a conventionally known tackifier (tackifier) can be used, and specific examples thereof include a rosin tackifier, a terpene tackifier, and a petroleum resin tackifier.

  Examples of the rosin tackifier include esters of rosin acid and glycerin and pentaerythritol, which are mainly composed of abietic acid in pine jani and pine root oil, and hydrogenated products and disproportionates thereof. Preferable examples include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin, rosin ester (rosin diol) and the like.

  Examples of the terpene tackifier include those obtained by polymerizing natural terpenes contained in terpene oil and orange peel contained in pine, specifically, terpene resins, aromatic modified terpene resins, terpene phenol resins, Preferred examples include hydrogenated terpene resins.

Examples of petroleum resin tackifiers include aliphatic, alicyclic and aromatic resins made from petroleum. Specifically, C ₅ petroleum resins, C ₉ petroleum resins, and copolymer petroleums. Resins, alicyclic saturated hydrocarbon resins, styrene petroleum resins and the like are preferably exemplified.

  Among these, as the tackifier (b), it is preferable to use the rosin-based tackifier because the resulting composition has a low viscosity and is easy to be molded. The moldable resin composition to be used is more preferable because the stretchability, adhesion to polyolefin, metal and PVC are improved, and the balance between heat resistance and flexibility and gasoline resistance are improved. Specific examples of rosin diol include Pine Crystal D-6011, KE-615-3, and D-6240 (all manufactured by Arakawa Chemical Industries, Ltd.).

  Moreover, 1-50 mass parts is preferable with respect to the total 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d), and, as for content of the said tackifier (b), 10-40 mass parts is more. preferable. Within this range, the stretchability of the moldable resin composition obtained, the adhesion to polyolefin, metal and PVC are improved, and the balance between heat resistance and flexibility and gasoline resistance are improved.

<Polyol compound (c)>
The polyol compound (c) is a polyol compound having two or more hydroxy groups in one molecule, and functions as a compatibilizing agent for compatibilizing the aromatic polyester (a) and the tackifier (b). If it is not specifically limited, specifically, for example, ethylene glycol, propylene glycol, butanediol, polycarbonate diol, polycaprolactone, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol and the like can be mentioned. Polyether polyols such as polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene glycol; Down diene polyol, polyolefin polyol polyisoprene glycol; adipate polyol; polyhydric alcohols such polyester polyols such as castor oil; lactone polyol resorcinol, polyhydric phenols such as piston phenol can be used. Each of these polyols may be used alone or in combination of two or more.

  Among these, it is preferable to use polycarbonate diol and polycaprolactone because the effect as a compatibilizer can be obtained in a small amount, and it is more preferable to use polycarbonate diol because of its high temperature and high humidity resistance.

  Moreover, 500-10000 are preferable, as for the average molecular weight of each polyol, 1000-10000 are more preferable, and 2000-10000 are still more preferable.

  The content of the polyol compound (c) is preferably 0.5 to 50 parts by mass and more preferably 1 to 20 parts by mass with respect to a total of 100 parts by mass of the aromatic polyester (a) and the polyolefin (d). 2 to 10 parts by mass is preferable. Within this range, the aromatic polyester (a) and the tackifier (b) are sufficiently compatible, and the physical properties (heat resistance, flexibility, gasoline resistance) of the polyester are not lowered.

Since the composition of the present invention contains the tackifier (b) and the polyol compound (c), as described above, the stretchability and the adhesion to polyolefin, metal and PVC are improved, and the heat resistance and flexibility are improved. In addition, the separation of the aromatic polyester (a) and the tackifier (b) that occurs at the time of melting is prevented, and the oil resistance, particularly gasoline resistance, is reduced when the tackifier (b) is added alone. It becomes.
This is considered to be because the tackifier (b) is preferentially taken into the amorphous part of the aromatic polyester (a) by adding the polyol compound (c).

<Polyolefin (d)>
The polyolefin (d) is not particularly limited, but specifically, for example, homopolymers of α-olefins such as ethylene, propylene, butylene, pentene, 4-methyl-1-pentene, and the like of these α-olefins. Examples thereof include two or more types of copolymers, or polyolefin resins composed of copolymers of these α-olefins and other copolymerizable monomers. These may be used alone or in combination of two or more.
Among these polyolefins, polyethylene is preferable because it is more excellent in gasoline resistance.

The polyolefin (d) preferably has a polar group.
In general, polyolefin has a low polarity, whereas the aromatic polyester (a) has a high polarity, so that the composition of the present invention is melted for a long time during or after the production of the composition of the present invention. In this case, the aromatic polyester (a) and the polyolefin (d) are separated, and even if they are stirred again, they cannot be sufficiently mixed and the adhesiveness may be lowered. On the other hand, when the said polyolefin (d) has a polar group, it does not isolate | separate, even after melt | dissolving for a long time, and adhesiveness can be maintained.
The polar group is not particularly limited, and specific examples include an epoxy group, a carboxy group, an acid anhydride group, an amino group, an isocyanate group, a hydroxy group, a nitro group, and a sulfone group. The polyolefin (d) may have only one of these functional groups or may have a plurality of types of functional groups.
The polar group is preferably at least one selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group, and more preferably an epoxy group, from the viewpoint of excellent adhesion to polar substances.
The polyolefin (d) preferably has an epoxy group and a carboxy group and / or an acid anhydride group.
The carboxy group is preferably a carboxy group derived from maleic acid, and the acid anhydride group is preferably a maleic anhydride group.

  The polyolefin having the polar group can be obtained, for example, by a method of copolymerizing an olefin and a polymerizable monomer having a polar group (for example, glycidyl methacrylate). Moreover, you may use a commercial item.

Content of the said polyolefin (d) is 5-40 mass parts with respect to a total of 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d). Since the composition of this invention contains polyolefin (d) in this range, it is excellent in the balance of the adhesiveness with respect to polyolefin, and the adhesiveness with respect to a metal and PVC, and is excellent also in gasoline resistance.
From the point which is excellent by these characteristics, as for content of the said polyolefin (d), 10-40 mass parts is more preferable with respect to a total of 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d), 20-20. More preferred is 40 parts by weight.

  Since the composition of the present invention contains the polyolefin (d) in a specific ratio, it can improve the adhesion to polyolefin while maintaining excellent properties such as adhesion to metals and PVC and gasoline resistance. it can. In particular, when the polyolefin having the polar group is used, the adhesiveness can be maintained without separation even after melting for a long time.

  The composition of the present invention is, as necessary, a range that does not impair the purpose of the present invention, and if necessary, a reinforcing agent, an anti-aging agent, an antioxidant, a filler, a plasticizer, a heat stabilizer, an ultraviolet absorber Other additives such as lubricants, waxes, colorants, crystallization accelerators, reinforcing fibers and the like may be blended.

  The method for producing the composition of the present invention is not particularly limited, and the aromatic polyester (a), the tackifier (b), the polyol compound (c), the polyolefin (d), and various additives as necessary. Can be produced by mixing with a roll, a kneader, an extruder, a universal stirrer, or the like.

The composition of the present invention described above preferably has a viscosity at 190 ° C. of 10 to 500 Pa · s, more preferably 10 to 100 Pa · s, from the viewpoint of excellent moldability.
Moreover, it is preferable that it is a molding resin composition which can be discharge-molded on the conditions that a pressure is less than 5 MPa, Preferably it is 0.2-1.0 MPa, More preferably, it is 0.3-0.5 MPa. Here, the discharge molding is preferably performed in the range of 120 to 230 ° C, and more preferably in the range of 180 to 210 ° C. If it is this temperature range, stability of the molding resin composition used for the said discharge molding will improve, and also the viscosity at the time of a melt | fusing will be within the range mentioned above. Moreover, a pressure is a pressure at the time of discharging the said resin composition for a molding from a discharge outlet at the time of the said discharge molding.

  The composition of the present invention described above is excellent in adhesion to polyolefin, metal and PVC, gasoline resistance, stretchability and flexibility. In addition, it has low viscosity and excellent moldability. In particular, when a polyolefin having a polar group is used, the aromatic polyester and the polyolefin are not separated even after the molding resin composition of the present invention is melted for a long time, and the adhesiveness can be maintained.

  Since the composition of the present invention has the above-described excellent characteristics, it is useful as a sealant / waterproof protectant for ends of connectors / harnesses, etc. In order to protect against impact, vibration, moisture, etc., it is also useful as a filler embedded in the entire electric circuit.

  A method for producing a waterproof protective coating using the composition of the present invention is a method for producing a waterproof protective coating in which a waterproof protective coating is formed on the end of an electronic device using the molding resin composition of the present invention described above. A melting step for melting the molding resin composition of the present invention, and a discharge molding / application step for discharging or applying the molten molding resin composition after the melting step to the electronic device at a pressure of less than 5 MPa; It is a manufacturing method of the waterproof protective coating characterized by comprising. Here, the pressure at the time of discharge molding or application is preferably 0.2 to 1.0 MPa, and more preferably 0.3 to 0.5 MPa.

  The melting step is a step of melting the composition of the present invention, and specifically, a step of heating the moldable resin composition to 160 to 230 ° C., preferably 180 to 210 ° C. to melt.

The discharge molding / coating step is a step of discharging or applying the molding resin composition melted in the melting step to the end portion of the electronic device with a pressure of less than 5 MPa.
Specifically, the above-mentioned discharge molding is performed by using a hot melt gun, a hot melt applicator, and a molten resin composition for molding in a mold containing an electronic device end at a pressure of less than 5 MPa, preferably 1 to 4 MPa. It is the process of discharging using etc. and shape | molding in the said mold. Or it is the process of discharging by a hot melt gun and a hot melt applicator, and potting.
The application is a step of applying the molten molding resin composition to the end portion of the electronic device using a hot melt gun spray or the like at a pressure of less than 5 MPa, preferably 1 to 4 MPa.
In general injection molding, the pressure is as high as 40 to 120 MPa and the melting temperature is as high as 250 to 300 ° C., whereas if the method for producing a waterproof protective coating using the composition of the present invention is used, the pressure is 0.3 to Since it can be used at 0.5 MPa and a melting temperature of 180 to 230 ° C., it is very excellent.
Therefore, if the above-described manufacturing method is used, molding at such a low temperature and low pressure is possible. Therefore, as shown in FIGS. 1A to 1D, the polyolefin-coated conductor 2 having the peeling portion 1 is used. This is preferable because a manufacturing apparatus using the aluminum mold 3 and the rubber packing 4 can be used, and the cost for molding can be reduced. Specifically, in the shape of the mold shown in (C) (sealed with the aluminum mold 3 and the rubber packing 4), hot melt (HM) material is injected from the injection portion 5 (arrow direction), The HM material is passed through the injection path 6 and transferred to the HM molding mold 7. Thereafter, the HM material is molded with the HM molding mold 7 and removed from the mold, thereby forming a molded product having a molding portion 8 indicated by (D).
In addition, since it can be molded at low temperatures and low pressures, it can be molded without damaging electronic components on the substrate, so that the entire substrate can be waterproofed, and a one-part silicone resin composition, etc. In addition, since it is not necessary to cover the substrate and the electronic component with a case, the cost of the product can be reduced, which is preferable.

  In addition, molding of two-component urethane and epoxy requires heating and the like, and further curing takes about 15 to 120 minutes. On the other hand, when the composition of the present invention is used, the curing time after molding is naturally cooled. The process is preferably completed in several seconds to several tens of seconds, and can be removed from the mold within several minutes. Specifically, the use of the composition of the present invention is preferable because the injection time of the HM material for molding is completed in 10 seconds and the mold can be released from the mold within 1 minute by natural cooling. Furthermore, since there is no deformation after demolding and no curing is required, the productivity is also excellent.

Specific examples of the end of the electronic device include, for example, an end of a connector / harness, a connection portion of a cord and a cord, a substrate of an electronic device, etc., and the material thereof is metal, PVC, polyolefin or the like. There are many things.
Therefore, the waterproof protective coating formed on the end portion of the electronic device is excellent in adhesion to metal, PVC and polyolefin, such as the end portion of the connector / harness, the connection portion between the cord and the cord, the electronic This is preferable because it can be used for a substrate of an apparatus. In particular, in a harness used in an automobile in which moisture enters from a ground portion or the like, a waterproof protective coating manufactured by the above-described method is used for the molded portion 21 as shown in the harness 20 of FIG. For example, there is no need to cut the conducting wire 23 joined to the joining portion 22 through the molding portion 21 in the middle or to provide an atmosphere opening portion, so that the design is not restricted and the cost is low. It is preferable because of its excellent mass productivity.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Polyester A to D)
The polyester only needs to contain the target acid component and glycol component, as polyester A, Elitel UE3320 manufactured by Unitika, as polyester B, Hytrel 4057 manufactured by Toray DuPont, and as polyester C, Elitel UE3410 manufactured by Unitika. As polyester D, Elitel UE3800 manufactured by Unitika Ltd. was used. The molar ratio of the acid component and the glycol component of polyesters A to D is shown in Table 1 below.

(Examples 1-10 and Comparative Examples 1-5)
The components shown in Table 2 below were mixed using a kneader at the composition (parts by mass) shown in Table 2 to obtain each molding resin composition shown in Table 2.
Each measurement shown below was performed in each obtained resin composition for molding.
The results are shown in Table 2 below.

<Viscosity measurement>
The viscosity was measured according to JIS K7117-1. Using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the obtained molding resin composition was melted at 190 ° C. for 30 minutes, and then rotated using a No. 3 rotor, and the viscosity was measured at 10 rpm.

<Separation immediately after production and after aging>
About the resin composition for molding immediately after production, and the one obtained by cooling and solidifying the resin composition for molding aged by allowing it to stand at 200 ° C. for 72 hours, visually confirm the mixed state of each composition component, What was in the separated state was marked with “X”, and what was in a compatible state was marked with “◯”.

<Hardness (Shore D)>
The hardness (Shore D) was measured according to JIS Z2246-2000. The hardness of the obtained molding resin composition was measured using a D-type Shore hardness meter. A sample having a hardness of 100 or less was designated as “◯”.

<Flexibility>
The obtained molding resin composition was cooled and solidified, pressed to a thickness of 1 mm with a 140 ° C. press, cut into a 25 mm × 100 mm × 1 mm sheet, and used as a test piece.
This test piece was folded in half, and “◯” was given when the test piece did not break.

<Adhesiveness>
(1) Adhesiveness to PVC Adhesiveness to PVC was measured according to JIS K6256-1999. A PVC having a thickness of 3 mm (trade name: Tough Neil, manufactured by Takafuji Corporation) was cut into 25 mm × 150 mm to obtain a PVC test piece. The obtained molding resin composition is molded on a PVC test piece as shown in FIG. 3A using a mold, and the PVC test piece 30 and the molding resin composition 31 are peeled from each other. Then, a 180 degree peel test in which tensile stress was applied in two arrow directions shown in FIG. 3B was performed, and the maximum tensile stress when the PVC test piece 30 and the molding resin composition 31 started to peel was measured. The pulling speed was 50 mm / min.
In addition, when attaching a test piece to a testing machine, the PVC test piece 30 and the resin composition 31 for shaping | molding peeled, and what was not able to be measured was set to "x".

(2) Adhesiveness to metal Two copper plates having a width of 30 mm, a length of 150 mm, and a thickness of 0.8 mm were folded in half at a location of 75 mm in length, and the two copper plates and the obtained resin composition for molding (all 4 (B) is formed as shown in FIG. 4A, and the copper plate 40 and the molding resin composition 41 are separated from each other with respect to the two copper plates 40 as shown in FIG. 180 ° C. peeling test in which tensile stress was applied in the two arrow directions shown in FIG. 2), and the maximum tensile stress when the copper plate 40 and the molding resin composition 41 were peeled off was measured. The pulling speed was 50 mm / min.
The metal adhesiveness of the obtained molding resin composition is “◯” when peeled off at a maximum tensile stress of 50 N / 25 mm or more, and when attaching the test piece to the tester, the copper plate 40 and the molding resin composition 41 Was peeled off and could not be measured was designated as “x”.

(3) Adhesiveness to polypropylene (PP) PP adhesiveness (initial) was measured in the same manner as the adhesiveness to PVC, except that a corona surface-treated polypropylene (manufactured by Shin-Kobe Electric Machinery Co., Ltd .: PP-N-BN) was used. did. Moreover, PP adhesiveness (heat-and-moisture resistance) was measured in the same manner for a test piece prepared in the same manner as in the PP adhesiveness (initial) test and aged at 80 ° C. and 95% for 96 hours.
In addition, when attaching a test piece to a testing machine, a polypropylene (PP) test piece and the resin composition for shaping | molding peeled, and what was not able to be measured was set to "x".

<Moldability>
The PVC coated cord was molded using an aluminum mold and rubber packing manufacturing apparatus shown in FIG.
(1) Moldability Using a hot melt applicator, the molding resin composition obtained was injected at an air pressure of 0.4 MPa, and the injection time until molding into a prescribed shape was measured. A sample having an injection time of 10 seconds or less was marked with “◯”.
(2) Demoldability Using the above mold, after the obtained molding resin composition was injected, the time until demolding from the mold was measured so as not to deform the shape was measured. Those that could be removed from the mold within 1 minute after injection were indicated as “◯”.

<Gasoline resistance>
The resulting cooled and solidified product of the molding resin composition was immersed in gasoline at 25 ° C. for 72 hours, and the presence or absence of whitening of the composition surface was observed. The case where whitening did not occur was indicated as “◯”, and the case where whitening occurred was indicated as “x”.

Each component shown in Table 2 is as follows.
-Olefin hot melt: 777, manufactured by Kaetsu Co., Ltd.-Polypropylene: M142E, manufactured by Idemitsu Kosan Co., Ltd.-Low density polyethylene: G807, manufactured by Sumitomo Chemical Co., Ltd.-Polyethylene having an epoxy group: Bondfast 7L, manufactured by Sumitomo Chemical Co., Ltd.-Epoxy group And polyethylene having a maleic acid group: Admer SF-715, manufactured by Mitsui Chemicals, Ltd. Rosin tackifier: Pine Crystal KE-6011, manufactured by Arakawa Chemical Industries, Ltd. Petroleum resin tackifier: Alcon P-125, Arakawa Chemical Industries, Ltd. -Polycarbonate diol: Plaxel CD220, manufactured by Daicel Chemical Industries-Anti-aging agent: Irganox 1010, manufactured by Ciba Specialty Chemicals

As is apparent from the results shown in Table 2, the olefin-based hot melt (Comparative Example 1) had low PVC adhesion, metal adhesion, and gasoline resistance. Further, the molding resin composition having a low polyolefin (d) content (Comparative Example 2) and the molding resin composition not containing the polyolefin (d) (Comparative Example 5) had low PP adhesiveness. Further, the viscosity of the molding resin composition (Comparative Example 3) having a large content of the polyolefin (d) having an epoxy group was too high. Further, the molding resin composition (Comparative Example 4) having a high polyolefin (d) content had low PVC adhesion, metal adhesion, and gasoline resistance.
On the other hand, the molding resin compositions (Examples 1 to 10) of the present invention have relatively low viscosity, high flexibility, and excellent PVC adhesion, metal adhesion, PP adhesion, moldability, and gasoline resistance. It was.

(A) of FIG. 1 is a figure which shows the conducting wire before shaping | molding, (B) is a figure which shows the shape (mold single side | surface) of a mold, (C) is a figure which shows the shape of the mold at the time of shaping | molding (D) is a figure which shows the shape of a molded article. FIG. 2 is a view showing a harness sealed with the molding resin composition of the present invention. 3A and 3B are a perspective view and a cross-sectional view, respectively, showing adhesiveness with PVC. 4A and 4B are a perspective view and a cross-sectional view, respectively, showing adhesiveness with a metal (copper plate). FIG. 5 is a diagram showing a current harness. FIG. 6 is a view showing a connector of the current product.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Peeling part 2 Polyolefin coating lead 3 Aluminum mold 4 Rubber packing 5 Injection part 6 Injection path 7 Mold for HM molding 8 Molding part 20 Harness 21 Molding part 22 Joint part 23 Conductor 30 PVC test piece 31 Molding resin composition 40 Copper plate 41 Resin composition for molding 50 Harness 51 Caulking portion 52 Joining portion 53 Conductor 54 Atmospheric release portion 60 Connector 61 Molding portion 62 Joining portion 63 Conducting wire

Claims (14)

An aromatic polyester (a), a tackifier (b), a polyol compound (c) having two or more hydroxy groups in one molecule, and a polyolefin (d),
The molding resin composition whose content of the said polyolefin (d) is 5-40 mass parts with respect to a total of 100 mass parts of the said aromatic polyester (a) and the said polyolefin (d).   The molding resin composition according to claim 1, wherein the polyolefin (d) has a polar group.   The molding resin composition according to claim 2, wherein the polar group is at least one selected from the group consisting of an epoxy group, a carboxy group, and an acid anhydride group.   The molding resin composition according to claim 1, wherein the polyolefin (d) has an epoxy group and a carboxy group and / or an acid anhydride group.   The molding resin composition according to claim 3 or 4, wherein the carboxy group is a carboxy group derived from maleic acid, and the acid anhydride group is a maleic anhydride group.   The content of the tackifier (b) is 1 to 50 parts by mass with respect to 100 parts by mass in total of the aromatic polyester (a) and the polyolefin (d). Molding resin composition.   The content of the polyol compound (c) is 0.5 to 50 parts by mass with respect to a total of 100 parts by mass of the aromatic polyester (a) and the polyolefin (d). The resin composition for molding as described in 2.   The molding resin composition according to any one of claims 1 to 7, wherein a viscosity at 190 ° C is 10 to 500 Pa · s.   The aromatic polyester (a) is at least selected from the group consisting of an acid component containing terephthalic acid and / or isophthalic acid, and ethylene glycol, polytetramethylene ether glycol, neopentyl glycol and 1,4-butanediol. The resin composition for molding according to any one of claims 1 to 8, which is a polyester obtained by reacting a hydroxy group component containing one kind. As the aromatic polyester (a), polyester A obtained by reacting an acid component containing terephthalic acid and isophthalic acid and a hydroxy group component containing ethylene glycol and neopentyl glycol;
An acid component containing terephthalic acid and isophthalic acid, and a polyester B obtained by reacting a hydroxy group component containing 1,4-butanediol and polytetramethylene ether glycol are contained. The molding resin composition according to any one of the above.   The aromatic polyester (a) further contains polyester C obtained by reacting an acid component containing terephthalic acid, isophthalic acid and sebacic acid with a hydroxy group component containing 1,4-butanediol. The molding resin composition according to claim 10.   As the aromatic polyester (a), a polyester D obtained by further reacting an acid component containing terephthalic acid, isophthalic acid and ε-caprolactone with a hydroxy group component containing 1,4-butanediol. The resin composition for molding according to claim 10 or 11, which is contained.   The molding resin composition according to any one of claims 1 to 12, wherein the tackifier (b) is a rosin tackifier.   The resin composition for molding according to claim 13, wherein the rosin tackifier is rosin diol.

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