JP2002212421A - Binder for glass flakes, glass flakes and polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide(PPS) resin molded article reinforced with glass flakes in which the adhesion of the glass flakes to the PPS resin is enhanced so that the article has high initial strength and excellent strength retention rate in hot water. SOLUTION: This PPS resin composition is manufactured by blending a PPS resin with glass flakes treated with a binder for glass flakes that comprises an aminosilane coupling agent, an epoxy resin and a urethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sizing agent for glass flakes, a glass flake treated with the sizing agent, and a polyphenylene sulfide (PPS) resin composition reinforced with the glass flakes. , PP
By combining the glass flake with the glass flake sizing agent, which has excellent adhesiveness to the S resin and is suitable as a glass flake sizing agent to be mixed with the PPS resin as a reinforcing material, and the glass flake to which the sizing agent is adhered, ,
The present invention relates to a PPS resin composition capable of obtaining a molded article excellent in initial strength and hot water strength retention.

[0002]

2. Description of the Related Art Since PPS resin is a thermoplastic resin having excellent heat resistance and chemical resistance, the PPS resin is used in electric and electronic parts, OA equipment, precision machinery, automobiles and the like by utilizing these excellent properties. Widely used as molding material. Conventionally, P
In using the PS resin, in order to further improve the excellent physical properties inherent in the PPS resin, a glass chopped strand is blended as a reinforcing material. However, in the case of using only glass chopped strands, there are problems such as warpage of molded products and insufficient abrasion resistance.To solve this problem, it is necessary to use glass flakes in combination. It has been proposed (JP-A-6-122824).

By the way, glass flakes are flaky glass having an aspect ratio (particle size / thickness) of about 2 to 1000, and have physical properties (eg, barrier properties, rigidity, tensile strength, bending strength, dimensional stability) of composite materials. , For prevention of warpage, etc.) for use in thermosetting resins and thermoplastic resins. In particular, when glass flakes are blended with a thermoplastic resin, the two-dimensional reinforcing effect of the glass flakes improves tensile strength, bending strength, bending elastic modulus, heat deformation temperature, dimensional accuracy, etc., and also has barrier properties. And a resin composition having excellent properties can be obtained. In a resin molded product reinforced with such glass flakes, the molding shrinkage in the direction of the resin flow and the molding shrinkage in the direction perpendicular to the resin flow are substantially equal, and the warpage of the molded product is extremely small.

At present, glass flakes supplied as products have a thickness of several μm and a size (particle size) of 10 to 4000.
It has a scale shape of μm and is in a dry state with a moisture content of 0.2% by weight or less. Most of the glass flakes are separated without adhering to each other and are very easily scattered.

[0005] Therefore, for the purpose of preventing the scattering and improving the adhesiveness between the resin and the glass flakes when mixed with the resin, generally, a sizing agent (sizing agent) is adhered to the glass flakes and adhered to each other. Granules are used.

Hitherto, silane-based coupling agents, urethane-based coupling agents, and epoxy-based coupling agents have been used as the sizing agent for glass flakes.

[0007]

However, conventional glass flakes using a sizing agent do not have sufficient adhesiveness to PPS resin. There is a drawback that its use is restricted.

The present invention solves the above-mentioned conventional problems, and
A glass flake sizing agent capable of obtaining a glass flake reinforced PPS resin molded article having excellent adhesion to S resin, high initial strength, and excellent hot water strength retention rate, and glass to which the sizing agent is adhered. An object of the present invention is to provide a flake and a PPS resin composition obtained by blending the glass flake.

[0009]

The sizing agent for glass flakes of the present invention is characterized by containing an aminosilane coupling agent, an epoxy resin and a urethane resin.

In the present invention, by using an aminosilane coupling agent, an epoxy resin and a urethane resin in combination, the adhesiveness of the glass flakes to the PPS resin can be remarkably enhanced. It is possible to provide a PPS resin molded product having excellent strength retention.

On the other hand, glass flakes treated with a sizing agent containing an aminosilane coupling agent and an epoxy resin but not containing a urethane resin have a higher PPS resin content than those of an aminosilane coupling agent alone or untreated glass flakes. Although the initial strength of the molded product is improved, the retention of hot water strength is low. Also, glass flakes containing an aminosilane coupling agent and a urethane resin and treated with a sizing agent that does not contain an epoxy resin cannot provide sufficient initial strength.

An aminosilane coupling agent in a sizing agent,
The content ratio of the epoxy resin and the urethane resin is such that the aminosilane coupling agent is 1 to the total solid weight of the sizing agent.
Preferably, the amount is 0 to 80% by weight, the epoxy resin is 5 to 50% by weight, and the urethane resin is 5 to 50% by weight.

The glass flake of the present invention is obtained by treating with such a sizing agent for glass flake of the present invention.

In this glass flake, the amount of the sizing agent attached is preferably 0.1 to 5.0 parts by weight in total of the aminosilane coupling agent, the epoxy resin and the urethane resin based on 100 parts by weight of the glass flake. .

[0015] The glass flakes of the present invention are preferably granulated by adhering a sizing agent.

[0016] The glass flakes of the present invention are preferably
It is suitable as a resin reinforcing material.

The PPS resin composition of the present invention comprises such a glass flake of the present invention, and the amount of the glass flake is 10 to 70 parts by weight based on 100 parts by weight of the PPS resin. Is preferred.

[0018]

Embodiments of the present invention will be described below.

The sizing agent for glass flakes of the present invention comprises an aminosilane coupling agent, an epoxy resin and a urethane resin as active ingredients. Usually, an aminosilane coupling agent, an epoxy resin and a urethane resin are used in a predetermined amount. It is prepared by adding and mixing with water at a concentration.

In the sizing agent for glass flakes according to the present invention, the aminosilane coupling agent, the epoxy resin and the urethane resin each contain 10 to 80% by weight of the aminosilane coupling agent with respect to the total solid content of the sizing agent. It is preferable that the compounding agent is contained in a proportion such that the epoxy resin is 5 to 50% by weight and the urethane resin is 5 to 50% by weight. If the amount of the aminosilane coupling agent or the epoxy resin is smaller than this ratio, the initial strength of the PPS resin molded product is insufficient, and if the amount of the urethane resin is small, the hot water strength retention of the molded product is insufficient. Become.

In general, the sizing agent for glass flakes of the present invention has an aminosilane coupling agent concentration of 0.1 to 1.5% by weight and an epoxy resin concentration of 0.0
5 to 1.5% by weight, urethane resin concentration 0.05 to 1.
It is prepared by adding and mixing so as to be 5% by weight.

In addition, the sizing agent for glass flakes of the present invention, besides the aminosilane coupling agent, the epoxy resin and the urethane resin, may be used as long as the object of the present invention is not impaired.
It may contain other additives such as an antifoaming agent, an antistatic agent or a surfactant.

The glass flakes of the present invention are those treated with the sizing agent of the present invention. If the amount of the sizing agent adhered is too small, the sufficient effect of the sizing agent cannot be obtained and even if the amount is too large. Because it is uneconomical, glass flake 100
It is preferable that the total amount of the active ingredient is attached to the parts by weight, that is, the total amount of the aminosilane coupling agent, the epoxy resin, and the urethane resin is 0.1 to 5.0 parts by weight.

The method of adhering the sizing agent to the glass flakes is not particularly limited, but using a horizontal vibrating granulator or the like.
A method is preferred in which the glass flakes are subjected to vibration granulation while spraying a sizing agent and then dried.

The glass flakes of the present invention are preferably granulated into granules by adhering a sizing agent from the viewpoint of handleability, but need not necessarily be granules. In the case of granular glass flakes, the average thickness is 0.5 to 20 μm and the average particle size is 10 to 2000 μm.
It is preferable that a sizing agent is adhered to glass flakes having a size of about 20 to 3000 μm to form granules.

The sizing agent for glass flakes and the glass flakes of the present invention are suitable as a sizing agent for glass flakes and a glass flake as a reinforcing material for PPS resins because of their excellent adhesion to PPS resin.
The resin is not limited to the PPS resin at all, and can be applied to a resin other than the PPS resin as long as the resin can similarly obtain high adhesiveness.

The PPS resin composition of the present invention is obtained by blending the glass flake of the present invention with a PPS resin. The amount of the glass flake is determined by the presence or absence of other reinforcing materials such as glass fiber. Depending on the compounding amount, etc., usually, 10
It is preferable that the amount be up to 70 parts by weight. If the compounding ratio is too small, a sufficient effect of improving properties due to the glass flakes cannot be obtained, and if too large, the moldability and other physical properties may be adversely affected.

The PPS resin is not particularly limited, but has a melt viscosity of 500 to 20,000 poise.
(Measured by a flow tester at 300 ° C. and a load of 10 kgf) is preferred from the viewpoint of balance between strength and fluidity. Further, those having a number average molecular weight of 2,000 or more and a weight average molecular weight of about 10,000 to 60,000 are desirable from the viewpoint of the balance between fluidity and strength. Any of these may be used, and a copolymer with other components such as a graft type, a block type, and a random type or an alloy with an elastomer, a polymer, or the like may be used to the extent that the physical properties are not impaired.

Such a PPS resin composition of the present invention comprises:
By molding according to a conventional method, it is possible to effectively obtain the effect of improving various properties by blending the glass flakes without impairing the initial strength and the retention rate of hot water strength, and it can effectively obtain electric / electronic parts, OA equipment, It is possible to provide a PPS resin molded article which is suitable for a wide range of uses such as precision machines and automobiles and has both excellent initial strength and hot water strength retention.

[0030]

The present invention will be described more specifically below with reference to examples and comparative examples.

In the following, glass flakes having an average thickness of 5 μm and an average particle size of 600 μm were used. The melt viscosity of the PPS resin is 1000p
oise was used.

Example 1 Aminosilane coupling agent in water (Nihon Unicar Co., Ltd.)
"A100", an epoxy resin (phenol novolak type) and a urethane resin (ether type) were mixed to prepare a sizing agent for glass flakes having the composition shown in Table 1.

The sizing agent is applied to glass flakes by spraying such that the total adhesion amount of the aminosilane coupling agent, the epoxy resin and the urethane resin becomes the ratio shown in Table 1, and granulated. Average particle size 100
0 μm granular glass flakes were obtained.

A pellet is manufactured by kneading 67 parts by weight of the granular glass flakes together with 100 parts by weight of PPS resin at 320 ° C. to obtain a molded article having a predetermined shape by injection molding the pellet. The following initial strength and the retention rate of hot water strength after immersion in hot water at 120 ° C. for 200 hours (ratio of tensile strength after immersion in hot water to initial tensile strength) were examined. The results are shown in Table 1.

[Initial strength] Tensile strength: Measured according to ASTM-D638 Bending strength: Measured according to ASTM-D790 Izod impact value: Measured according to ASTM-D256

Comparative Examples 1 to 3 Granular glass flakes were obtained in the same manner as in Example 1 except that the effective components of the sizing agent and the amounts of the sizing agents shown in Table 1 were used. The strength and the hot water strength retention were examined, and the results are shown in Table 1.

In Comparative Example 3 using only the aminosilane coupling agent, the glass flakes did not granulate.

Comparative Example 4 The initial strength and the hot water strength retention of the molded article were examined in the same manner as in Example 1 except that untreated glass flakes (non-granular) were mixed with the PPS resin. It was shown to.

[0039]

[Table 1]

From Table 1, it can be seen that according to the present invention, a glass flake reinforced PPS resin molded article having excellent initial strength and hot water strength retention can be obtained.

[0041]

As described above in detail, according to the present invention, the adhesion and adhesion of the glass flake to the PPS resin can be remarkably increased, and the initial strength and the hot water strength can be maintained by using such a glass flake. A glass reinforced PPS resin molded article having an excellent rate can be obtained.

Claims (8)

[Claims] 1. A sizing agent for glass flakes comprising an aminosilane coupling agent, an epoxy resin and a urethane resin. 2. The method according to claim 1, wherein the content of the aminosilane coupling agent, the epoxy resin and the urethane resin is 10 to 80% by weight based on the total solid weight of the sizing agent, and the content of the epoxy resin is 5%. ~ 50
A sizing agent for glass flakes, characterized in that the amount of the urethane resin is 5 to 50% by weight. 3. Glass flakes treated with the sizing agent for glass flakes according to claim 1 or 2. 4. The sizing agent according to claim 3, wherein the total amount of the aminosilane coupling agent, the epoxy resin and the urethane resin is 0.1 to 5.0 parts by weight based on 100 parts by weight of the glass flakes. Glass flakes characterized by that. 5. The glass flake according to claim 3, wherein the sizing agent is adhered to form a granule. 6. The glass flake according to claim 3, wherein the glass flake is a reinforcing material of a polyphenylene sulfide resin. 7. A polyphenylene sulfide resin composition comprising the glass flake according to claim 3. 8. The polyphenylene sulfide resin composition according to claim 7, wherein the amount of the glass flake is 10 to 70 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin.