JP3014140B2 - Polyarylene sulfide resin composition, bonding method using the same, and laminate - Google Patents

Description

The present invention relates to a polyarylene sulfide resin composition,
The method for bonding a polyarylene sulfide resin and a polyvinylidene fluoride resin using the same, and a laminate of a polyarylene sulfide resin and a polyvinylidene fluoride resin, particularly, a good adhesion between the polyarylene sulfide resin and the polyvinylidene fluoride resin. The present invention relates to a composition obtained, a method for bonding a polyarylene sulfide resin and a polyvinylidene fluoride resin using the same, and a laminate comprising a polyarylene sulfide resin and a polyvinylidene fluoride resin bonded well.

[Problems to be solved by conventional technology and invention]

Polyarylene sulfide resin such as polyphenylene sulfide resin has a high melting point, is a resin having heat resistance, chemical resistance, and high elastic modulus, but has poor impact resistance,
There is also a problem that it is easily deteriorated by ultraviolet rays.

For the purpose of improving such polyarylene sulfide resin, Japanese Patent Publication No. 2-382 discloses that (b) 70 to 99% by weight of α-olefin and α · β with respect to 100 parts by weight of polyarylene sulfide resin. A polyarylene sulfide resin composition comprising 0.5 to 50 parts by weight of an olefinic co-polymer comprising 1 to 30% by weight of a glycidyl ester of an unsaturated resin acid.

However, there is a problem in the above resin composition that the physical properties of the composition itself are not always sufficient.

On the other hand, fluorine-based resins such as polyvinylidene fluoride are excellent in chemical resistance, flexibility, weather resistance, sliding properties, electrical properties, stain resistance, etc., but have poor adhesion to other resin components. There is a problem of inferiority.

For the purpose of obtaining a material having higher performance by bonding such a polyarylene sulfide resin and polyvinylidene fluoride, the present inventors have made polyarylene sulfide and polyvinylidene fluoride, a metal, a ceramic, etc. A polyphenylene sulfide resin composition containing ultrafine particles and a method for bonding a polyarylene sulfide resin using the same to polyvinylidene fluoride have been proposed (JP-A-2-120364).

By the use of the above composition, adhesion between the polyarylene sulfide resin and polyvinylidene fluoride was achieved to some extent, but since the strength of the composition itself used as the adhesive was not necessarily sufficient, the polyarylene sulfide resin and Even if the adhesive force at the adhesive interface with vinylidene is high, the adhesive layer itself will be destroyed,
As a result, there is a problem that the adhesive strength is not always sufficient.

Therefore, an object of the present invention is to improve the adhesiveness between a polyarylene sulfide resin and polyvinylidene fluoride, and to improve the mechanical strength such as the tensile strength, tensile elongation, and impact strength of the adhesive composition itself and toughness. It is an object of the present invention to provide an improved resin composition having a high adhesive strength.

Another object of the present invention is to bond a polyarylene sulfide resin and a polyvinylidene fluoride resin with the above resin by using a resin having high mechanical strength such as tensile strength, tensile elongation and impact strength of an adhesive layer itself, and bonding. It is to provide a method of bonding with high strength.

Still another object of the present invention is to provide a molded product of a polyarylene sulfide resin and a molded product of a polyvinylidene fluoride resin by the above-mentioned bonding method, whereby the mechanical strength of the adhesive layer itself such as tensile strength, tensile elongation and impact strength is improved. An object of the present invention is to provide a laminate which is high in bonding strength and high in bonding strength.

[Means for solving the problem]

As a result of intensive studies in view of the above objects, the present inventors have found that a component obtained by mixing a polyarylene sulfide resin and polyvinylidene fluoride at a specific ratio has a specific ratio of α-olefin and α · β -A composition comprising a copolymer of a glycidyl ester of an unsaturated fatty acid and a polyarylene sulfide resin and a polyvinylidene fluoride resin has more mechanical properties, particularly tensile strength, tensile elongation,
The impact strength and the like have been improved, and furthermore, it has been found that if the polyvinylidene fluoride resin and the polyarylene sulfide resin are adhered to each other with this composition, the adhesive strength between the two does not cause large destruction in the adhesive layer. I arrived.

That is, the polyarylene sulfide resin composition of the present invention comprises (a) a polyarylene sulfide, (b) polyvinylidene fluoride, and (c) a copolymer of an α-olefin and a glycidyl ester of an α · β-unsaturated fatty acid. And the content of (b) is (a) + (b)
And the total content of (c) is 5 to 45% by volume, and the content of (c) is (a) + (b) + (c).
Is 5 to 35% by volume with the total of 100% being 100% by volume.

Further, the method for bonding the polyarylene sulfide resin and the polyvinylidene fluoride according to the present invention comprises:
It contains polyarylene sulfide, (b) polyvinylidene fluoride, and (c) a copolymer of an α-olefin and a glycidyl ester of an α · β-unsaturated fatty acid, and the content of (b) is the above ( a) + the sum of the above (b) is 100
A polyarylene sulfide having a volume percentage of 5 to 45 volume% and a content of the above (c) of 5 to 35 volume%, where the total of the above (a) + (b) + (c) is 100 volume%. The present invention is characterized in that a resin composition is used, and a joining portion of the two and the adhesive are melted at a temperature not lower than the melting point of polyarylene sulfide and not higher than 400 ° C., and are joined by the adhesive.

Further, the laminate of the polyarylene sulfide resin and the polyvinylidene fluoride resin of the present invention is characterized in that the molded article of the polyarylene sulfide resin and the molded article of the polyvinylidene fluoride resin are adhered by the above method.

 Hereinafter, the present invention will be described in detail.

The polyarylene sulfide (a) used in the present invention has a repeating unit represented by the general formula: Ar-S (where Ar is an aromatic residue and S is sulfur). Here, as the aromatic residue (-Ar-) in the above general formula, for example, (Where X is fluorine, chlorine, bromine and CH ₃ , and m is a positive integer of 1 to 4).

As a representative of the above-mentioned polyarylene sulfide resins, a general formula: The polyphenylene sulfide resin (PPS) represented by these is mentioned. Also. A resin obtained by copolymerizing the above-mentioned polyphenylene sulfide resin with about 10 mol% or less of another monomer can also be used. The resin is not cross-linked between the on-chain molecules, but may be partially cross-linked by a method such as heat treatment.

Such a polyphenylene sulfide resin is 30
The melt viscosity at 0 ° C. is 20 to 30,000 poise, preferably 100 to 15,000 poise. Its melting point is usually 2
80-290 ° C.

As such a polyphenylene sulfide resin, various grades such as those for injection molding and extrusion molding are manufactured, but are not particularly limited in the present invention.

Commercial products of the above polyphenylene sulfide,
For example, “Topren PPS” (trade name) manufactured by Topren Co., Ltd., “Polyphenylene Sulfide” manufactured by Asahi Glass Co., Ltd., “Shin-Etsu PPS” (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.,
"SUSTIL" (trade name) manufactured by Hodogaya Chemical Co., Ltd. and the like.

In the present invention, (b) polyvinylidene fluoride (PVD)
F) is a polymer obtained by polymerizing vinylidene fluoride (CH ₂ CFCF ₂ ), and is represented by a general formula: CH ₂ CF _{2 t} .

Polyvinylidene fluoride having the above molecular structure usually has a melt viscosity of 2 × 10 ³ to 2 × 10 ⁶ (210 to 270 ° C.) and a melting point of 160 to 180 ° C. As such polyvinylidene fluoride, various grades such as those for injection molding and extrusion molding are manufactured, but are not particularly limited in the present invention.

Commercial products of the above polyvinylidene fluoride include "KF Polymer" (trade name) manufactured by Kureha Chemical Industry Co., Ltd., "Neoflon PVDF" (trade name) manufactured by Daikin Industries, Ltd., and "SOLEF" manufactured by Solvay (Belgium). (Product name) and the like.

In the present invention, the polyvinylidene fluoride is added to 50
% Vinylidene fluoride copolymer can also be used. The vinylidene fluoride copolymer is a copolymer containing vinylidene fluoride and perfluoromonomers such as ethylene tetrafluoride and propylene hexafluoride as main monomers. The copolymer is not limited to a block or random copolymer, but may be a graft copolymer, and can be produced by irradiation or with a peroxide catalyst.

In the present invention, the component (C) is composed of α-olefin and α · β.
-Copolymers of unsaturated fatty acids and glycidyl esters.

Examples of the α-olefin include ethylene, propylene, butene-1, and pentene-1, and ethylene is preferably used. The glycidyl ester of α / β-unsaturated fatty acid is represented by the following general formula: (Wherein, R represents a hydrogen atom or a lower alkyl group). Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, with glycidyl methacrylate being particularly preferred. .

In the copolymer of the α-olefin and the glycidyl ester of an α · β-unsaturated fatty acid as described above,
Glycidyl ester of unsaturated fatty acid The copolymerization amount of glycidyl ester of α-β-unsaturated fatty acid is preferably about 3 to 20% by weight.

The copolymer (c) of the α-olefin and the glycidyl ester of α · β-unsaturated fatty acid as described above can be further copolymerized within a range of about 40% by weight or less and within a range not to impair the object of the present invention. Monomers such as vinyl ether, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, acrylonitrile, styrene and the like may be copolymerized.

As described above, the compounding ratio of (a) polyarylene sulfide, (b) polyvinylidene fluoride, and (c) a copolymer of an α-olefin and a glycidyl ester of an α · β-unsaturated fatty acid is as follows. (B) is 5 to 45% by volume, preferably 10 to 30% by volume, assuming that the total of the components (a) and (b) is 100% by volume. If (b) is less than 5% by volume, the adhesion to polyvinylidene fluoride is not sufficient, and the mechanical strength such as impact resistance is not sufficient. If the content exceeds 45% by volume, the strength of the composition obtained is reduced.

In addition, the compounding amount of the component (c) is the total resin component ((a) +
(B) + (c)) is 5 to 35% by volume, preferably 10 to 30% by volume, assuming 100% by volume. If the component (c) is less than 10% by volume, the strength of the resulting composition is not sufficient, and if it exceeds 35% by volume, the polyarylene sulfide and polyvinylidene fluoride become too small, and the properties of these resins are sufficiently exhibited. Disappears.

In the present invention, the mixing ratios of the various constituent components are indicated by volume%, but the volume% is a value determined based on the true specific gravity of each component.

In addition to the above components, the composition of the present invention may optionally contain silicone oil, molybdenum disulfide, a release agent, a lubricant, a heat stabilizer, a foaming agent, an inorganic filler, and the like.

Such a polyarylene sulfide resin composition of the present invention is produced by melt-kneading the above-mentioned various components and additives to be added as necessary at 285 ° C. to 310 ° C., preferably 290 ° C. to 300 ° C. be able to.

Next, a method for bonding a molded article of a polyarylene sulfide resin and a molded article of a polyvinylidene fluoride resin using the polyarylene sulfide resin composition of the present invention will be described.

First, the polyarylene sulfide resin composition was added to 30
Heat and melt at 0 ° C to 330 ° C, preferably 310 to 320 ° C. The melt may be applied to the joint surfaces of both molded bodies, joined and cooled. For example, a polyarylene sulfide resin composition is formed into a sheet,
Laying on a heating metal plate at 30 ° C, preferably 310-320 ° C,
From above, a molded body made of polyvinylidene fluoride (or polyarylene sulfide resin) and a molded body made of polyvinylidene fluoride resin (or polyarylene sulfide resin) are bonded together while heating them at 310 to 320 ° C. (The melted sheet surface of the composition) may be joined and fused. At this time, it is preferable to lay a sheet or the like of a fluororesin such as polytetrafluoroethylene on the metal plate.

The laminated structure thus obtained has a polyarylene sulfide resin layer and a polyvinylidene fluoride resin layer firmly adhered to each other, and a mechanical layer of the layer of the polyarylene sulfide resin composition of the present invention itself to be an adhesive layer. Since it has high strength, it has heat resistance, chemical resistance, high elastic modulus, and is also excellent in flexibility, weather resistance, sliding characteristics, electrical characteristics, contamination resistance, and impact resistance. .

(Operation)

The polyarylene sulfide resin composition of the present invention,
For a component obtained by mixing a polyarylene sulfide resin and polyvinylidene fluoride at a specific ratio, a copolymer of an α-olefin and a glycidyl ester of an αβ-unsaturated fatty acid is added at a specific ratio. Become.

When the polyvinylidene fluoride resin and the polyarylene sulfide resin are bonded to each other with this composition, the bonding strength between the two is large and the bonding layer is not broken.

Although the reason why such an effect is obtained is not necessarily clear, the polyarylene sulfide resin composition of the present invention itself has excellent mechanical strength and impact resistance, and the polyarylene sulfide resin and polyvinylidene fluoride are used. This is considered to be because the adhesiveness to both is good, so that even if a tensile force or an impact is applied, the adhesive layer itself is peeled off at the interface without breaking, and the adhesive strength is large.

〔Example〕

 The present invention is described in more detail by the following examples.

In addition, the raw material resin used in each Example and Comparative Example is as follows.

[1] Polyarylene sulfide ・ Polyphenylene sulfide resin PPS: [Toplen T-4 manufactured by Topren Co., Ltd., melting point 28
0 ° C] [2] Polyvinylidene fluoride PVDF: [SOLEF “SOLEF”, melting point 177 ° C] [3] Copolymer of α-olefin and glycidyl ester of α · β-unsaturated fatty acid ・ Ethylene-methacrylic acid Glycidyl copolymer E-GMA: [Bond First BF manufactured by Sumitomo Chemical Co., Ltd.
-E "] Examples 1 to 6 and Comparative Examples 1 to 7 Polyphenylene sulfide polymer (PPS), polyvinylidene fluoride (PVDF), and ethylene-glycidyl methacrylate copolymer (E-GMA) at the ratios shown in Table 1 )
And 320 using a Weisenberg-type resin mixing device (2 mm gap between rotating plate and fixed plate, disk diameter 12 cm, internal volume 10 cc).
The mixture was extruded at a temperature of ° C., and the extrudate was re-extruded for sufficient mixing to obtain a polyarylene sulfide resin composition. The volume ratio of the raw material resin is based on the true specific gravity of the ethylene-glycidyl methacrylate copolymer (1.
00) and calculated with polyphenylene sulfide = 1.34 and polyvinylidene fluoride = 1.78. The mixing was performed with the total amount of resin being about 5 cc.

The polyarylene sulfide resin composition thus obtained was formed into a sheet having a thickness of 0.4 mm or 0.3 mm by a heat press.

A test piece was cut out from a 0.4 mm sheet with a dumbbell having an effective length of 20 mm and a width of 10 mm, and the tensile strength and the tensile elongation were measured using the test piece. The results are shown in Table 1.

An adhesive strength evaluation test was performed using a sheet having a thickness of 0.3 mm.

 The adhesive strength evaluation test was performed by the following method.

First, a molded product of a polyphenylene sulfide polymer and a polyvinylidene fluoride are prepared in advance, and the diameter of the tip is 6 mm and the length is 6-9 mm.
The rod-shaped material of cm was taken out, and the tip portion was a bonding portion, and other portions near the tip were gripped portions in various physical property tests.

Next, a sheet of 5 mm in diameter is cut out from a sheet of 0.3 mm, a thin polytetrafluoroethylene (PTFE) sheet is placed on a heated metal plate having a smooth surface, and the above-mentioned 0.3 m thick sheet is placed thereon.
An m sheet (with a diameter of 5 mm) is placed and fused in a molten state to the tip of a polyvinylidene fluoride rod. At this time, the surface temperature of the metal plate was 300 to 330 ° C. After confirming the fusion of the tip and the adhesive, stick the phenylene sulfide polymer rod and the tip of the polyvinylidene fluoride rod fused with the adhesive resin,
Each joint was heated using an air burner, and after confirming that the tips were fused together, they were brought into contact with each other and lightly pressed to fuse them.

The bonding strength between the polyvinylidene fluoride resin thus bonded and the polyphenylene sulfide polymer was measured, and the state of peeling was observed. The results are shown in Table 1.

In addition, it is preferable that the adhesive is substantially on the same straight line.However, if the length of the melting portion at the tip is long or the pressing force is too strong, a flow occurs at the melting portion and a test piece for a test cannot be prepared. Care must be taken when bonding.

(1) Tensile strength: Measured according to JIS K7113.

(2) Tensile elongation: Measured according to JIS K7113.

(3) Impact strength: 3.75mm and 5.3m thick according to JIS K7110
Measured as data equivalent to m test pieces.

(4) Adhesive strength: Tensilon UTM3 type, tensile speed
Measured by measuring the tensile strength at 4 mm / min and dividing this strength by the fracture surface area (bonding area). Note that anisotropy occurs in the flow of the resin during the production of the adhesive, and there is a case where the circular adhesive is deformed into an elliptical shape at the time of bonding, so that the fracture surface area is approximately a circle or an ellipse. Calculated.

Each of the tests (1) to (3) was performed three times, and the average of the measured values of the upper two times was obtained and used as the measurement result.

As is clear from Table 1, the polyarylene sulfide resin composition of the present invention has an adhesive strength between polyphenylene sulfide polymer and polyvinylidene fluoride of 40 kgf /
cm ² or more, and the physical properties of the composition itself were good. The adhesive strength in the range of the present invention from Table 1 (polyvinylidene fluoride 5 to 45% by volume, ethylene-glycidyl methacrylate copolymer 5 to 35% by volume) is about 30.
It is estimated that there is more than kgf / cm ² .

On the other hand, the composition of Comparative Example 1 in which the polyphenylene sulfide polymer was used alone did not adhere to polyvinylidene fluoride and contained a copolymer of α-olefin and glycidyl ester of α · β-unsaturated fatty acid. The compositions of Comparative Examples 2 to 6, which did not have sufficient adhesive strength with polyvinylidene fluoride and polyphenylene sulfide polymer, particularly those containing 50% by volume or more of polyvinylidene fluoride caused interfacial peeling. Furthermore, the composition of Comparative Example 7 in which the ratio of polyvinylidene fluoride was large had insufficient bonding strength with polyvinylidene fluoride and polyphenylene sulfide polymer.

〔The invention's effect〕

As described in detail above, the polyarylene sulfide resin composition of the present invention has a specific ratio of α-olefin and α with respect to a component obtained by mixing a polyarylene sulfide resin and vinylidene polyfluoride at a specific ratio.・ Β-
A copolymer with an unsaturated fatty acid glycidyl ester is added.

When the polyvinylidene fluoride resin and the polyarylene sulfide resin are bonded to each other with this composition, the bonding strength between the two is large and the bonding layer is not broken.

By such a polyarylene sulfide resin composition of the present invention, polyvinylidene fluorides having excellent properties such as chemical resistance, weather resistance, sliding properties, and electrical properties can be obtained. Thus, it can be laminated on a polyarylene sulfide resin having a weak point, and this laminate is suitable for outdoor use.

Further, the laminate of the present invention is suitable for various industrial materials, particularly, structural materials, electronic materials, and the like.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C09J 133/14 C09J 133/14 181/02 181/02 (56) References JP-A-2-120364 (JP, A) JP JP-A-4-372658 (JP, A) JP-A-4-3772659 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 81/00-81/10 C09J 181/00-181 / 10 B32B 27 / 08,27 / 28,27 / 30 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A method comprising the steps of: (a) polyarylene sulfide; (b) polyvinylidene fluoride; and (c) a copolymer of an α-olefin and a glycidyl ester of an α · β-unsaturated fatty acid. The content of b) is (a) + (b)
And the total content of (c) is 5 to 45% by volume, and the content of (c) is (a) + (b) + (c).
A polyarylene sulfide resin composition, wherein the total amount of the polyarylene sulfide resin is 5 to 35% by volume, where the total of the components is 100% by volume. 2. The polyarylene sulfide resin composition according to claim 2, wherein the polyarylene sulfide is polyphenylene sulfide. 3. The polyarylene sulfide resin composition according to claim 1, wherein the glycidyl ester of the α.β-unsaturated fatty acid is selected from glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Or a polyarylene sulfide resin composition, characterized in that it is of two or more types. 4. A method for bonding a molded article of a polyarylene sulfide resin and a molded article of a polyvinylidene fluoride resin, wherein (a) polyarylene sulfide, (b) polyvinylidene fluoride, and (c) α -A copolymer of an olefin and a glycidyl ester of an α-β-unsaturated fatty acid, wherein the content of (b) is 5 to 45% with the total of (a) + (b) being 100% by volume. % By volume, and the content of (c) is 5 to 35% by volume based on the total of (a) + (b) + (c) being 100% by volume, using a polyarylene sulfide resin composition. And melting the joining portion of the two and the adhesive at a temperature of not less than the melting point of polyarylene sulfide and not more than 400 ° C., and joining with the adhesive. 5. A laminate obtained by bonding a molded article of polyarylene sulfide resin and a molded article of polyvinylidene fluoride resin by the method according to claim 4.