JP2003138044A - Pps resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding suitable for a ferrule of an optical connector, etc., not damaging melt fluidity of a resin composition, excellent in injection molding property, excellent in mechanical strength of the molding, and small in connection loss after repeated attaching and detaching. SOLUTION: This PPS resin molding is prepared by irradiating an ionized radiation to a molding formed by melting and forming a PPS resin composition which is prepared by compounding a melt mixture of PPS resin (A) introduced with a specific functional group X on the end or in the side chain of the molecule and an organic compound (B) having both a carbon-carbon double bond and an atomic group which can form a chemical bond with the functional group X introduced to the PPS resin, compounded with an inorganic filler (C) of which surface is treated with a silane coupling agent having a carbon-carbon double bond or a silane coupling agent having a carbon-carbon double bond and an inorganic filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a PPS resin molded product suitable for, for example, an optical fiber positioning component used for connecting optical fibers to each other.

[0002]

2. Description of the Related Art Generally, an optical connector is used for connecting optical fibers in optical communication, and an optical fiber positioning component such as a ferrule or a sleeve is used for the optical connector. Such optical fiber positioning parts require highly precise positioning of the axes of the optical fibers that are butted against each other, so that high dimensional accuracy is required and dimensional stability for long-term use is required. Is also required. At the same time, since the optical fiber positioning component is repeatedly attached and detached, sufficient mechanical strength and long-term durability are required.

Various polyphenylene sulfide resins (PPS resins) have been studied in order to meet such demands by using thermoplastic resins. For example, JP-A-64-6
3115 and Japanese Patent Laid-Open No. 12453/1993, P.
In a system in which an inorganic filler is blended with PS resin, an epoxy-based, mercapto-based, or vinyl-based silane coupling agent is added, or an inorganic filler pre-treated with these silane coupling agents is used. It is described that by doing so, mechanical strength and impact resistance are improved.
Further, in JP-A-3-140368, by using an inorganic filler treated with an epoxy silane coupling agent for a PPS resin having an amino group or an amide group, the wettability and adhesion of the PPS resin and the inorganic filler are disclosed. A method of improving the properties and increasing the mechanical strength is disclosed.

[0004]

[Problems to be Solved by the Invention] However, PPS
Addition of a silane coupling agent to a system in which an inorganic filler is blended with a resin, or only using an inorganic filler pretreated with a silane coupling agent, the effect of improving the adhesiveness between the resin and the inorganic filler interface is not sufficient. Therefore, in the case of the above ferrule, even in a system in which a large amount of inorganic filler such as spherical silica or whisker is mixed in the PPS resin, the mechanical strength required for the guide hole is obtained. The improvement effect of is not obtained. On the other hand, PPS that requires an amino group
In a system in which a modified PPS resin such as a resin is mixed with an inorganic filler treated with a specific silane coupling agent, high dimensional accuracy and a low linear expansion coefficient are required like the ferrule of the optical fiber. However, when the PPS resin is highly filled with an inorganic filler such as spherical silica or whiskers, the melt fluidity is remarkably reduced, and the filling property of the PPS compound into the mold becomes insufficient, resulting in a precise There was a problem that the molding process became difficult.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies on the above problems, and as a result, (A) a PPS resin having a specific functional group X introduced at a molecular end or a side chain, and (B)
A carbon-carbon double bond (C) is added to a molten mixture of an organic compound having a carbon-carbon double bond and a functional group X introduced into a PPS resin in the same molecule and an atomic group capable of forming a chemical bond under melt mixing. An inorganic filler surface-treated with a silane coupling agent having a bond, or a mixture of a silane coupling agent having a carbon-carbon double bond and an inorganic filler P
It has been found that when a PS resin composition is melt-molded and the molded product is irradiated with ionizing radiation, a PPS resin molded product excellent in strength and toughness can be obtained without impairing melt flowability and moldability.

More specifically, (A) a PPS resin having a functional group selected from the group consisting of an amino group, an epoxy group, a carboxyl group and an acid anhydride group at the molecular end or side chain, and (B) a general formula ( Organic compound of 1) RY (1) (wherein Y is an atomic group capable of forming a chemical bond with the functional group X of the PPS resin when melt-mixed, and R is a carbon- An inorganic filler surface-treated with a silane coupling agent having a carbon-carbon double bond in the molecule is added to a resin composition obtained by melt-mixing (representing a molecular chain having a carbon double bond). Alternatively, P formed by melt-kneading a silane coupling agent having a carbon-carbon double bond in the molecule and an inorganic filler
In a system in which a PS resin composition is melt-molded by injection molding or transfer molding and the molded product is irradiated with ionizing radiation, a large amount of inorganic filler such as glass fiber, spherical silica and whiskers is filled. Molded products with no deterioration in melt flowability and excellent mechanical strength and toughness can be obtained, and even when applied to the ferrule of a multi-core optical connector, the mechanical strength required for the guide hole can be obtained, and It was found that the connection loss can be reduced, and the present invention has been completed based on such findings.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Any PPS resin having a functional group such as an amino group, an epoxy group, a carboxyl group or an acid anhydride group introduced into the molecular end or side chain used in the present invention is known. It can be manufactured by the method. For example, a PPS resin having an amino group introduced into its side chain is disclosed in
-140368, Unexamined-Japanese-Patent No. 4-220462, Unexamined-Japanese-Patent No. 4-227636, Unexamined-Japanese-Patent No. 4-339.
859, JP-A-5-170915, etc., when an alkali metal sulfide and dihalobenzene are reacted in an organic solvent such as N-methylpyrrolidone, an amino group-containing dihalobenzene such as dichloroaniline is added. It can be produced by coexisting and polymerizing.

Regarding PPS resin having a carboxylic acid group or an acid anhydride group introduced into its side chain, Japanese Patent Application Laid-Open No. 5-17091.
As described in Japanese Patent Publication No. 5, a method of reacting the amino group-containing PPS resin with trimellitic acid dianhydride can be exemplified. Furthermore, PP having an epoxy group introduced into the side chain
Regarding the S resin, as described in JP-A-5-186594, a method of reacting an epoxy resin or epichlorohydrin with a PPS resin having an amino group introduced into the above side chain, or JP-A-6-217759. As described in the publication, a method of melt-kneading a PPS resin and glycidyl methacrylate in a biaxial mixer can be exemplified.

On the other hand, as a method of introducing an amino group at the molecular end, as described in JP-A-4-220462, a method of sealing the polymerization end with aminothiophenol or a bis ( A method of reacting with a disulfide compound such as 4-aminophenyl) disulfide can be exemplified. Further, as a method of introducing a carboxylic acid group at the molecular end, as described in JP-A-6-234887 and JP-A-7-48505, P
A method of melt-kneading a PS resin, a modifier having a carboxyl group such as thiomalic acid and a mercapto group, and a dithio compound having a carboxylic acid group at both ends such as 2,2′-dithiodipropionic acid in a biaxial mixer. And the like, and can be freely manufactured by a known method.

Modified PPS into which the above-mentioned specific functional group is introduced
The resin preferably has a linear molecular structure in terms of melt fluidity, tensile strength, breaking bending strain, etc., but for the purpose of improving various properties, a branched structure should be introduced within a range that does not impair the above properties. Is also possible. The molecular weight of the modified PPS resin is in the range of 100 to 1000 poise when expressed as the melt viscosity at 300 ° C. and a shear rate of 500 sec ⁻¹ from the viewpoint of ensuring the melt fluidity of the resin composition containing the inorganic filler. Those in the range of 150 to 800 poise are more preferable. Modified PP with melt viscosity in this range
The S resin is preferable because the melt fluidity is secured, the dimensional accuracy of the molded product is good, and the mechanical strength is excellent.

As the organic compound of the general formula (1), PP
When the functional group X introduced into the S resin is an amino group, Y may be an organic compound having an epoxy group, a carboxylic acid group, or an acid anhydride group, such as glycidyl methacrylate, allyl glycidyl ether, and methacrylic acid. , Crotonic acid, undecylenic acid, succinic acid monomethacrylate, phthalic acid monomethacrylate, maleic anhydride, tetrahydrophthalic anhydride and the like. In addition, PPS
When the functional group X introduced into the resin is an epoxy group, Y may be an organic compound having a carboxylic acid group, an acid anhydride group or an amino group, such as methacrylic acid, crotonic acid, undecylenic acid and amber. Examples thereof include acid monomethacrylate, phthalic acid monomethacrylate, allylamine, diallylamine, 4-aminostyrene, maleic anhydride, and tetrahydrophthalic anhydride. Further, when the functional group X introduced into the PPS resin is a carboxyl group or an acid anhydride group, it is sufficient to select an organic compound in which Y is an epoxy group, an amino group or a hydroxy group, such as glycidyl methacrylate and allyl glycidyl. Ether, allylamine,
Examples include diallylamine, aminostyrene, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol monomethacrylate and the like.

The PPS resin having the functional group X introduced and the organic compound of the general formula (1) are melt-mixed by known melt-mixing using a single-screw melt extruder, a twin-screw mixer, a pressure kneader, a Banbury mixer or the like. Machine, for example, in a twin-screw mixer, L / D is melt-mixed at a barrel temperature of 300 to 350 ° C. by using a device having a mixing zone of 30 or more, and a discharge strand is cooled and cut. It is possible to obtain pellets of a reaction mixture of a PPS resin having a functional group introduced therein and an organic compound.

The molar ratio of the functional group X in the PPS resin is preferably 1 to 20 mol%, more preferably 2 to 10 mol%. When the molar ratio of the functional group X is 1 mol% or more, sufficient adhesion can be obtained at the interface between the PPS resin and the inorganic filler, and when it is 20 mol% or less, the crystallinity of the PPS resin is ensured and the heat resistance is high. It is excellent and preferable. The mixing ratio of the PPS resin introduced with the specific functional group and the organic compound of the general formula (1) may be appropriately set with reference to the stoichiometric ratio according to the molar ratio of the functional group X in the PPS resin.

Here, spherical silica is preferable as the inorganic filler, and it is also possible to use glass fiber, carbon fiber, aramid fiber and the like together. In addition, Japanese Patent Laid-Open No. 2001-264
As disclosed in Japanese Patent No. 581, it is also effective to use whiskers in a tetrapot shape together.

On the other hand, examples of the silane coupling agent having a carbon-carbon double bond in the molecule for the surface treatment of the inorganic filler include vinylsilane such as vinyltrimethoxysilane and N, N-diallylamino. Allyl silanes such as propyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane can be exemplified,
Among these, allyl silanes and acrylic silanes are particularly effective in improving the adhesion between the PPS resin and the inorganic filler.

In order to uniformly coat the entire surface of the inorganic filler with the above-mentioned silane coupling agent, the silane coupling agent is contained in the inorganic filler in an amount of 0.1 to 5% by weight, more preferably 0. It is necessary to treat at a ratio of 5 to 3% by weight. As the treatment method, PPS having a functional group introduced
A method of adding an inorganic filler to a pellet of a reaction mixture of a resin and an organic compound represented by the general formula (1) when melt-kneading, a silane coupling agent or a solution obtained by diluting a silane coupling agent with an organic solvent is used. A method of spray coating an inorganic filler at room temperature or at a high temperature, adding a silane coupling agent to an acetic acid aqueous solution having a concentration of about 0.1 M, and adding the inorganic filler into the slurry to form a slurry at room temperature to 6
Examples include a method in which after stirring at a temperature of about 0 ° C. for several hours, filtration is performed to collect the inorganic filler, and the mixture is stirred and dried in a thermostat at 100 to 120 ° C. Among these, the method is preferable because the surface of the inorganic filler can be treated with the silane coupling agent uniformly and surely.

As ionizing radiation, γ rays, accelerated electron beams,
X-rays and the like can be exemplified. Among them, accelerated electron beams are particularly excellent in terms of processing speed, and the acceleration voltage may be adjusted appropriately according to the thickness of the molded product. The irradiation dose of ionizing radiation is preferably 30 to 1000 kGy, and 50 to 500 kGy.
Is a more preferable range. Irradiation of 30 kGy or more can obtain a sufficient adhesion effect at the interface between the PPS resin and the inorganic filler, and irradiation of 1000 kGy or less is preferable because the mechanical strength of the molded product can be secured.

[0018]

EXAMPLES Tables 1 to 3 show the specific functional groups X of the PPS resins used in the molded articles of Examples 1 to 5 and Comparative Examples 2 to 4, and mol% of X, respectively. A PPS resin having a specific functional group X used in the molded articles of Examples 1 to 5 and Comparative Examples 2 and 3;
The respective organic compounds shown in Tables 1 to 3 were also mixed at the weight ratios shown in Tables 1 to 3 with a biaxial mixer (45 mmΦ, L
/ D = 32), the mixture is melted and mixed at a barrel temperature of 320 ° C. and a screw rotation speed of 100 rpm, the discharged strand is cooled in a water tank, and the strand is cut to obtain pellets of a reaction mixture of a PPS resin and an organic compound. It was

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

Next, as a filler to be added to the resins used in the molded articles of Examples 1 to 5 and Comparative Examples 1 to 4, two maximum values of 0.5 μm and 5 μm in the particle size distribution were obtained. A spherical silica having fused silica as a component was selected. In the case of Comparative Example 3, the surface treatment was not performed and used as it was. However, in other cases, the silane coupling agents shown in Tables 1 to 3 were used and the surface treatment was performed by the following method.

(Method for surface treatment of filler) A silane coupling agent is slowly dropped into a 5% acetic acid aqueous solution until the content of the silane coupling agent becomes 5%. Stir for about 1 hour until the aqueous solution of the silane coupling agent becomes transparent.
To the transparent silane coupling agent aqueous solution, add the same amount of fused silica as the aqueous solution and stir well. Finally,
Dry well in a constant temperature bath at 80 ° C.

The pellets obtained by mixing and reacting the PPS resin and the organic compound obtained as described above and the spherical silica surface-treated with a silane coupling agent at a ratio of 30:70 (weight ratio) at room temperature. After premixing with a tumbler at
Using a twin-screw mixer (45 mmφ, L / D = 32), the mixture was melt-mixed at a barrel temperature of 320 ° C. and a screw rotation speed of 25 rpm, the discharged strand was cooled in a water tank, and the strand was cut to form a pellet of the PPS resin composition. Obtained. However, in Comparative Example 1, the PPS resin having no specific functional group was used as it was, and in Comparative Example 4, the PPS resin in which the organic compound was not mixed and reacted was used.

The PPS in which the above-mentioned specific functional group is introduced
The melt viscosity of the resin was measured by using a capillary rheometer under the conditions of 300 ° C. and a shear rate of 500 sec ⁻¹ , and there was no particular problem in the range of 500 to 600 poise. In addition, the spiral flow of the PPS resin composition containing true spherical silica was measured by using an injection molding machine with a mold clamping force of 40 tons manufactured by Nissei Plastic Industry Co., Ltd. at a resin temperature of 320 ° C., a mold temperature of 135 ° C. and an injection pressure of 1000 kg / The flow length (mm) in cm ² was measured, but in the range of 60 to 110 mm, there was no particular problem.

After molding the above-mentioned PPS resin composition pellets using an injection molding machine with a mold clamping force of 30 t to prepare a ferrule for 4-core connection, an electron beam with an accelerating voltage of 2 MeV is applied to the ferrule. A fixed amount of irradiation was performed to obtain a molded product sample for performance evaluation. However, in Comparative Examples 1 and 2, unirradiated ones were used as molded product samples for performance evaluation.

For each of the prepared molded article samples,
The mechanical strength and connection loss were measured to evaluate the performance. The ferrule has a mechanical strength of 0.1 m by inserting one end of a guide pin made of stainless steel with a length of 8 mm into the guide hole and applying a load to the position of 1 mm from the other end of the guide pin.
The guide pin was pressed and deformed at a speed of m / sec, and the load when the guide pin hole was broken was evaluated. Regarding the connection loss of the ferrule, the transmission loss was measured for each of 10 optical connectors for the initial one and after 1000 cycles of attachment / detachment, and the average value was obtained. Then, when the change between the initial stage and after 1000 cycles of attachment and detachment was repeated within 0.3 dB, it was judged as good.

Comparative Examples 1 and 2 in which the molded article was not irradiated
Also, in Comparative Example 3 in which fused silica which is not surface-treated as a filler is used and Comparative Example 4 in which an organic compound is not mixed and reacted with PPS resin, the connection loss is large after 1000 times attachment / detachment, and long-term reliability is obtained. It lacked sex. However, as in Examples 1 to 5, as the PPS resin, a PPS resin having an amino group, an epoxy group, a carboxylic acid group, or an acid anhydride group at a molecular end or a side chain was used, and organic compounds were mixed and reacted. A resin mixture containing spherical silica surface-treated with a silane coupling agent having a carbon-carbon double bond in the molecule is used, and after irradiation after molding, the mechanical strength is excellent and the connection is improved. Regarding the loss, the change between the initial stage and after 1000 cycles of attachment / detachment is excellent within 0.3 dB. Particularly, as the silane coupling agent for the surface treatment of the filler, the one using acrylic type or allyl type as in Examples 1 to 4 has a very small transmission loss of 0.2 dB or less after being attached and detached 1000 times, and Also, the mechanical strength of the guide hole portion is excellent at 700 kg or more.

[0029]

As described above, according to the present invention,
Even in a system in which a large amount of an inorganic filler is blended in a PPS resin, it has a unique effect that it does not impair the melt flowability of the resin composition and has excellent injection moldability, excellent molded product strength, and small connection loss. It has a great utility value in the field of ferrules of optical connectors.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 81/02 C08L 81/02 G02B 6/38 G02B 6/38 (72) Inventor Toshifumi Hosoya Sakae, Yokohama City, Kanagawa Prefecture Sumitomo Electric Industries Co., Ltd. Yokohama Works, Ltd. (72) Inventor Kenichiro Otsuka 1 Taya, Sakae Ward, Yokohama City, Kanagawa Sumitomo Electric Co., Ltd. Yokohama Works F-term (reference) 2H036 QA18 4F073 AA32 BA32 BA47 BA52 BB02 CA42 4J002 CN011 DJ017 EF046 EH076 EL026 EL036 EL146 EN026 FB107 FD017 FD206 GM00 GQ00 4J030 BA02 BD01 BD08 BF09 BF19 BG10

Claims (6)

[Claims] 1. A PPS resin in which a specific functional group X is introduced at the terminal or side chain of a molecule, and (B) a carbon-carbon double bond and a functional group X introduced in a PPS resin in the same molecule. (C) An inorganic filler surface-treated with a silane coupling agent having a carbon-carbon double bond or a carbon-carbon double bond is added to a molten mixture of an organic compound having an atomic group capable of forming a chemical bond. The PPS resin composition obtained by blending the silane coupling agent and the inorganic filler is melt-molded,
A PPS resin molded product characterized by being irradiated with ionizing radiation. 2. The PPS resin according to claim 1, wherein the functional group X of (A) is a functional group selected from the group consisting of an amino group, an epoxy group, a carboxyl group and an acid anhydride group. Molding. 3. The PPS resin molded article according to claim 1 or 2, wherein the organic compound (B) is an organic compound represented by the general formula (1). R-Y ... General formula (1) (where Y is an atomic group capable of forming a chemical bond with an amino group, an epoxy group, a carboxyl group, an acid anhydride group when melt-mixed, and R is a carbon- Represents a molecular chain having a carbon double bond) 4. The PPS according to claim 1, wherein the silane coupling agent is allyl silane or / and acrylic silane.
Resin molded product. 5. The ratio of the inorganic filler to the total resin is 64.
The PPS resin molded product according to any one of claims 1 to 4, wherein the PPS resin molded product is from about 80 wt%. 6. (A) a PPS resin having a specific functional group X introduced at the terminal or side chain of the molecule, and (B) a carbon-carbon double bond and a functional group X introduced into the PPS resin in the same molecule. A step of melt-mixing an organic compound having an atomic group Y capable of forming a chemical bond to obtain a reaction mixture of a PPS resin and an organic compound; and (C) silane coupling having a carbon-carbon double bond in the reaction mixture. Inorganic filler surface-treated with an agent or a silane coupling agent having a carbon-carbon double bond and an inorganic filler are kneaded by a melt mixing method, and PP
A method for producing a PPS resin molded article, comprising: a step of obtaining an S resin composition; a step of melt-molding the PPS resin composition; and a step of irradiating the molded article with ionizing radiation.