JPH08183864A - Production of integral molding of abs resin molding with silicone rubber - Google Patents

Abstract

PURPOSE: To produce an integral molding improved in mold release, dimensional stability and production efficiency by integrating by adhesion a specified liquid addition-reaction-curable silicone rubber with an ABS resin molding wherein the adherend part is subjected to an ultraviolet treatment. CONSTITUTION: 100 pts.wt. silicone rubber is mixed with 0.1-10 pts.wt. at least one compound selected among the compounds of formulas I to V to obtain a liquid addition-reaction-curable silicon rubber. At least the adherend part of an ABS resin molding is irradiated with ultraviolet rays of a wavelength of 253.7nm or below for 5-100sec. This molding is integrated with the silicone rubber by adhesion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an integrally molded product of an ABS resin molded product and a silicone rubber, and particularly to an ABS (acrylonitrile-butadiene-styrene) resin molded product which requires a packing mechanism such as daily waterproofing. Body or a composition containing the resin as a main component (hereinafter, these are simply referred to as AB
The present invention relates to a method for producing various composite molded articles including an S-based resin molded body) and silicone rubber.

[0002]

2. Description of the Related Art Conventionally, for the production of a composite molded product of an ABS resin molded product and a silicone rubber, 1) an ABS resin molded product which exhibits adhesiveness by a chemical treatment such as primer coating or strong acid treatment. Or a method of adhering a silicone rubber thereto, or 2) an ABS resin molded product and an adhesion promoter for the resin such as an epoxy group, an alkoxy group, an anhydrous carboxy group or an acryloxyalkyl group in one molecule are added. There is also a method for adhering the self-adhesive silicone rubber, and 3) a molding method for structurally fitting and closely adhering the ABS resin molding and the silicone rubber to each other regardless of adhesion.

Regarding an integrally molded body formed by injection molding of plastic and silicone rubber, 4) "Integral molded body of polycarbonate resin and silicone rubber and method for producing the same" has been proposed (Japanese Patent Laid-Open No. 6-171021). However, 5) "Integral molded body of polypropylene resin and silicone rubber and method for producing the same" has also been proposed (see JP-A-6-71022 and JP-A-6-71023).

[0004]

However, in the above-mentioned conventionally known method for producing a composite molded article, the method 1) requires steps for primer coating, drying, and strong acid treatment, and the adhesive strength is not sufficient. In the method 2), the silicone rubber is a condensation type, so that the curing time of the rubber is long and the production efficiency is low, and the adhesion-imparting agent added to the silicone rubber is There is also a drawback that the mold releasability is poor in the mold molding because it easily adheres to the metal. Therefore, for this, a method is used in which the mold inner surface is coated with a fluororesin such as polytetrafluoroethylene. However, this processing has the drawback of being expensive and having a short life.

Further, in the above method 3), the ABS resin molded product and the silicone rubber are structurally fitted and adhered to each other, but the strength of the fitting and the adhesion depends on the structure of the fitting portion or the contact portion. The improvement in strength of this composite molded product is greatly restricted by design, and because of the flexibility of silicone rubber, the integration strength due to fitting and adhesion is much smaller than the adhesion strength according to 1) and 2) above. Further, this molding method has a disadvantage that the ABS resin portion and the silicone rubber portion are separately molded and then fitted together, so that the production efficiency is low.

Further, the above-mentioned method 4) is an integral molding of a silicone rubber with an aliphatic unsaturated group-containing polycarbonate, an aliphatic unsaturated group-containing polypropylene resin or a composition containing these resins. In order to obtain adhesive strength, polycarbonate and polypropylene must be modified, and even if this can be applied to ABS resin moldings, the material cost will be high and the material for obtaining the desired material properties will be In addition, the addition reaction-curable silicone rubber used in the above method 5) has a drawback that the molding conditions for obtaining adhesiveness are a temperature of 120 ° C. As described above, there is a drawback that the productivity becomes poor for 10 minutes or more, and the adhesive strength of the composite molded article bonded under these conditions is not sufficient.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method for producing an integrally molded body of an ABS resin molding and a silicone rubber, which solves the above disadvantages and drawbacks. At least a portion of the body to which the silicone rubber is adhered is previously subjected to UV treatment, and then the following (i) to (v)

[Chemical 6]

[Chemical 7]

Embedded image

[Chemical 9]

[Chemical 10] It is characterized in that a liquid addition reaction-curable silicone rubber prepared by blending at least one compound selected from the above is bonded and integrated with the molded body.

According to the present invention, it is possible to obtain an integrated molding having a sufficient adhesive strength, which can be bonded in a short time and has excellent releasability from a metal. By combining with the above, it is possible to manufacture a molded product having high dimensional accuracy with high production efficiency. This will be described in more detail below.

[0009]

The ABS resin used in the present invention is a synthetic rubber mainly composed of polybutadiene and acrylonitrile-
A mixture with a styrene polymer, a polymer obtained by graft-polymerizing acrylotolyl-styrene on polybutadiene, or a mixture thereof and another resin (for example, polycarbonate (PC), polyphenylene sulfide (PP)).
S), polybutylene terephthalate (PBT), PV
C, maleimide resin, PMMA, PA, etc.),
Further, these include those to which various additives such as flame retardant, deterioration inhibitor, reinforcing material, impact resistance improver, and extender are appropriately added.
It may be appropriately selected from known ones, and particularly from the viewpoint of increasing the molding temperature of the silicone rubber and increasing the production efficiency, it is preferable to use a heat-resistant grade. That is, although the general-grade ABS resin has a heat distortion temperature of 80 to 90 ° C, it is preferable to use a heat-resistant grade (heat distortion temperature of 90 to 100 ° C) or a superheat-resistant grade (100 to 120 ° C). Torayac-420 (heat distortion temperature 96 ℃), -440 manufactured by Toray Industries, Inc.
(Same 100 ℃), -450 (Same 105 ℃), -470 (Same 115 ℃),
Examples include JSR XT 09H (120 ° C) manufactured by Nippon Synthetic Rubber Co., Ltd.

The composition containing this resin as a main component may be appropriately selected from known ones according to the purpose of use of the product, but this composition is not particularly modified with an aliphatic unsaturated group. Examples thereof include alloys such as ABS / PC (polycarbonate). Among them, the alloy of ABS and PC is excellent in terms of mechanical strength and heat resistance improvement. If this alloy is used, the molding temperature of the silicone rubber can be increased and the production efficiency can be further increased. preferable. Examples of such substances include those shown in Table 1. Of these, JSR Excelloy CB-20 (heat distortion temperature 106 ° C) manufactured by Japan Synthetic Rubber Co., Ltd.,
CB40 (121 ℃) and CBIDG30 (130 ℃) are usually used.

[0011]

[Table 1]

[0012] The ABS resin molded product may be produced by a conventionally known molding method such as injection molding, extrusion molding, press molding, calender molding. This molded product is integrally molded with the silicone rubber molded product. Before being treated, it is subjected to UV treatment (UV treatment) in advance in order to enhance the adhesiveness with the silicone rubber. This UV treatment may be used for the purpose of increasing the adhesive strength of the surface of the polymer substance,
This can be done with a UV irradiation device, so UV
A spot irradiation device, a small UV irradiation device, a belt conveyor type UV processing device and the like can be mentioned. Among these, it is preferable to use a UV spot irradiation device that can be mounted on a molding machine even in the injection molding method.

The UV light source for irradiation is capable of generating a short wavelength of 253.7 nm or less due to the effect of surface modification, and a low pressure mercury lamp capable of generating particularly high energy is desirable. UV treatment conditions are low energy and it is difficult to obtain sufficient adhesive force in a short time, and when high energy and a long time are used, the surface of the ABS resin molded body is liable to be deteriorated and the appearance is likely to be poor, and the production efficiency is apt to be deteriorated. For example, when a low pressure mercury lamp of 4,000 Wcm ² with a spot diameter of 10 mm is used, it is preferable to set it within the range of 5 seconds to 100 seconds. The UV treatment may be applied to at least a portion of the ABS resin molded body to which the silicone rubber is adhered.

On the other hand, the silicone rubber used in the present invention is preferably a liquid addition reaction type silicone rubber which can be injection-molded with excellent production efficiency and does not require a pre-process such as roll kneading. Therefore, this is an organopolysiloxane containing vinyl groups and allyl groups as aliphatic unsaturated groups in the molecule, an organohydrogenpolysiloxane having at least two hydrogen atoms directly connected to silicon atoms, and platinum such as chloroplatinic acid. Although it is composed of a system catalyst, it does not have adhesiveness by itself, and therefore, an adhesion-imparting component for imparting adhesiveness to the addition reaction type silicone rubber and the ABS resin molded product is added to this. However, it is necessary to make it difficult to adhere to a mold or a mold used in injection molding or the like, and as such an adhesion-imparting component, the above-mentioned JP-A-6-172738. A compound having a hydrogen atom at least one of which is directly bonded to a silicon atom and a phenyl group, such as those described above in (i) to (v). Compound selected from

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15] The amount of the adhesiveness-imparting component added to the silicone rubber is 0.1 parts by weight or more and the adhesiveness is sufficient, and if it is 10 parts by weight or less, the separation from the mold is improved. It is preferably 0.1 to 10 parts by weight.

In order to manufacture an integrally molded product of an ABS resin molded product and a silicone rubber according to the present invention, first, a molded product of an ABS resin is manufactured by an injection molding method or the like, which is UV-treated, and then this injection molding machine is used. A liquid addition reaction type silicone rubber composition containing the above-mentioned adhesion-imparting component may be charged or supplied into a press molding machine or the like, and injection molding may be performed. It is possible to obtain an integrated molded body having a sufficient integration strength. At this time, the temperature of the fixed side metal piece and the intermediate plate into which the ABS resin molded product is inserted or supplied are
In order to improve the dimensional accuracy of the molded product, it is desired to lower the heat distortion temperature of the ABS resin, preferably 5 ° C or more. However, if the temperature is too low, the flow of the resin deteriorates, and defects such as unfilling are likely to occur, so it is preferable to set the temperature within 60 ° C. In addition, the movable side metal piece and the movable side slide core are required to cure the addition type silicone rubber.
It is necessary to set the temperature to 100 ° C. or higher, and it is preferable to set a higher temperature in order to increase the production efficiency, that is, the curing speed. However, if the temperature difference between the fixed-side metal piece and the intermediate plate is too large, the dimensional accuracy may deteriorate, and problems such as burrs may occur, so the temperature difference is within 40 ° C, preferably within 20 ° C. Is good.
In the present invention, injection molding is particularly preferable from the viewpoint of shortening the molding time and handling.

[0016]

EXAMPLES Next, examples of the present invention and comparative examples will be given, but the present invention is not limited to the following examples. The molding machine used in this embodiment is a two-color injection molding machine (made by Arburg Co.) equipped with two injection machines, and each of the two injection machines is connected to the gates of two molds. The UV irradiator is a low-pressure mercury lamp (4,00
The light guide type (manufactured by Toshiba Lighting & Technology Co., Ltd.) equipped with 0 Wcm ² ) was used, and the injection end was connected to the cavity of the mold.

Example 1 FIGS. 1 to 3 are vertical sectional views of the mold used in this example. The mold is a fixed mold piece 1, an intermediate plate 2, a rotary movable mold. Mold piece 3 and movable side slide core 4
The temperature of the fixed mold piece 1 and the intermediate plate 2 is set to 90 ° C, and the temperature of the rotary movable mold piece 3 and the movable slide core 4 is set to 110 ° C.
The movable slide core 4 is movable from the position a to the position b (see FIG. 2). In this embodiment, ABS resin Toyolac 220 [trade name of Toray Industries, Inc.] (heat distortion temperature 100 ° C.) is put into an injection molding machine and melted in a temperature range of 210 ° C. to 240 ° C. After injection from the nozzle A5 through the gate A'7 into the cavity (1) 11,
It was cooled for about 20 seconds to obtain an ABS resin molded product.

Then, the mold is opened, and the ABS resin molding is irradiated with UV from a UV irradiator 9 having a UV light guide for about 30 seconds, and then the rotary movable mold piece 3 is attached.
After rotating the UV irradiation machine to the ABS resin molded body by rotating 180 degrees forward, the mold is closed, the mold is opened again, and the rotary movable mold piece 3 is rotated in the reverse direction by 180 degrees and the movable slide core 4 is rotated.
Was returned to the position of the ABS resin molded body, the mold was closed, and the movable slide core 4 was moved from the position a to the position b.

Next, the adhesion-imparting component having a SiH group and a phenyl group is the above-mentioned (i), and this is a liquid addition reaction type silicone rubber KE1940-30 [trade name of Shin-Etsu Chemical Co., Ltd.] 100 1 part by weight of silicone rubber was injected into cavity (3) 13 from nozzle B6 through gate B'8 at injection pressure of 300 bar and cured in about 150 seconds. ABS shown in FIG. Since a composite molded body composed of the resin-based molded body 14 and the silicone rubber molded body 15 was obtained, the molded state and the peel strength of this molded body were examined, and as shown in Table 2 below, the molded state was good (Table 2 is marked with ◯), and the peel strength is 4.0 kg.
It showed f / cm.

Example 2 Using the molding apparatus and mold used in Example 1, the temperature of the fixed mold piece 1 and the intermediate plate 2 was 120 ° C., the rotary movable mold piece 3 and the movable slide core 4 were made. The temperature of 150 ℃
Set to ABS / PC resin / JSR Excelloy CBIDG30
(Heat distortion temperature 130 ℃) [Product name of Nippon Synthetic Rubber Co., Ltd.]
Is put into an injection molding machine and melted in a temperature range of 230 to 280 ° C. This molten material is injected from the nozzle A5 through the gate A′7 into the cavity (1) 11 for about 5 seconds and then cooled for about 15 seconds. To obtain an ABS / PC molded body. Then, Example 1
This molding was irradiated with UV from the UV irradiator 9 for about 30 seconds, the rotary movable mold piece 3 was returned to its original position, and then the mold was closed.

Then, the movable side slide core 4 is moved from the position a to the position b, and the liquid addition reaction type silicone rubber containing the adhesion-imparting component used in Example 1 is injected into the cavity (3) 13 at an injection pressure of 300 bar. From nozzle B6 to gate B '
After being injected through 8 and cured in about 60 seconds, a composite molded body consisting of the ABS / PC molded body 14 and the silicone rubber molded body 15 shown in FIG. 4 was obtained. When the strength was examined, the results shown in Table 2 below were obtained.

Example 3 The ABS resin used in Example 1 and the silicone rubber added with the adhesion-imparting component were composite-molded in the same manner as in Example 1 to produce the waterproof packing integral lid shown in FIG. Then
When the physical properties of this product were examined, it showed a high peeling strength and could withstand sufficient use, and no water leakage or peeling of the packing was observed even after standing in water for 100 hours. In addition,
In the figure, 17 is an ABS resin molded product and 16 is a silicone rubber molded product.

Example 4 The ABS / PC resin (19) and silicone rubber (18) used in Example 2 were composite-molded in the same manner as in Example 2 and shown in FIG.
When the packing integrated lid for lunch box shown in Fig. 4 was manufactured and the physical properties of this product were examined, it showed that the peeling strength was strong enough to withstand use, and that the packing did not peel even after 1,000 times of washing with an automatic dishwasher. I was not able to admit.

Examples 5 to 8 The adhesion-imparting components used in Example 1 were each prepared as described in (ii) above.
When the molding state and the peel strength were examined in the same manner in place of (v) to (v), the molding state was good (marked with ○ in Table 3) and the peel strength was also as shown in Table 3 below.
It was over 4.0 kgf / cm.

Comparative Example 1 The composite molded body shown in FIG. 4 was produced in the same manner as in Example 1. In this case, when UV irradiation was not performed, there was no problem in the resin molding state, but this molded body was used. As shown in Table 2 described later, the peeling strength was 0.3 kgf / cm, which was poor.

Reference Example 1 The composite molded body shown in FIG. 4 was prepared in the same manner as in Example 1. In this case, the UV irradiation time was extended from 30 seconds to 150 seconds. As shown in Table 2, the adhesive surface was whitened, but the peel strength of the molded body was 4.0 kgf / cm, which was good as in Example 1.

Reference Example 2 The same as Example 1 except that the temperatures of the fixed-side mold piece and the intermediate plate in Example 1 were changed to 100 ° C., and the temperatures of the rotary movable-side mold piece and the movable-side slide core were changed to 150 ° C. When the composite molded body shown in FIG. 4 was produced by the same method, cloudiness and warpage occurred on the surface of the ABS resin molded body, but this molded body had a peel strength as shown in Table 2 below. Was as good as 4.1 kgf / cm.

Reference Example 3 The composite shown in FIG. 4 was treated in the same manner as in Example 1 except that the silicone rubber used in Example 1 had the adhesiveness-imparting component increased from 1 part by weight to 15 parts by weight. When a molded product was produced, this product had a high peeling strength as shown in Table 2 described later, but was not released from the mold.
10 out of 1,000 were defective.

Comparative Example 2 The silicone rubber in Example 1 is added to the silicone rubber, but the adhesion-imparting component contains SiH groups but does not have phenyl groups.

Embedded image (Vi) 1 part by weight was used, and the composite molded body shown in FIG. 4 was produced in the same manner as in Example 1. The composite molded body was exfoliated as shown in Table 2 below. The strength was low, and the mold was poorly released.

Comparative Example 3 A composite molded body shown in FIG. 4 was prepared in the same manner as in Example 2 except that the UV irradiation in Example 2 was not carried out, and this is shown in Table 2 below. Thus, the resin was in a good molding state, but the peel strength decreased to 0.5 kgf / cm.

Reference Example 4 A composite molded body shown in FIG. 4 was prepared in the same manner as in Example 2 except that the UV irradiation time in Example 2 was extended from 30 seconds to 150 seconds. Although there was a disadvantage that the surface became white, the peel strength was good at 4.1 kgf / cm as shown in Table 2 below.

Reference Example 5 The same as Example 2 except that the temperatures of the fixed-side mold piece and the intermediate plate in Example 2 were changed to 140 ° C., and the temperatures of the rotary movable mold piece and the movable-side slide core were changed to 160 ° C. When the composite molded body shown in Fig. 4 was prepared in the same manner, the molded resin was also cloudy on the surface and warped. However, as shown in Table 2 below, the peel strength was 4.3 kgf. /cm
And was good.

Reference Example 6 The composite molding shown in FIG. 4 was carried out in the same manner as in Example 2 except that the silicone rubber used in Example 2 had the adhesion-imparting component increased from 1 part by weight to 15 parts by weight. When a body was produced, the peel strength was strong as shown in Table 2 below, but the release from the mold was 1,0
9 out of 00 were defective.

COMPARATIVE EXAMPLE 4 Silicone rubber in Example 2 was added to the silicone rubber as an adhesion-imparting component containing an SiH group but not having a phenyl group. When the composite molded body shown in FIG. 4 was manufactured by the same method as that of No. 2, the peel strength was low as shown in Table 2 below, and the release from the mold was also defective.

Comparative Examples 5 to 8 In Comparative Example 1, the adhesion imparting components were changed to those shown in the above (ii) to (v), and the molding state and peeling strength were examined in the same manner. The results are shown in Table 3 below. Thus, the same result as in Comparative Example 1 was obtained.

[0036]

[Table 2]

[Table 3]

[0037]

INDUSTRIAL APPLICABILITY The present invention relates to a method for producing an integrally molded body of an ABS type resin molded body and a silicone rubber. According to this method, the mold releasability from the mold is good and the ABS type resin molded body is Since it is possible to obtain an integrally molded product with silicone rubber having sufficient adhesive strength with high dimensional accuracy and high production efficiency, a composite of a highly functional ABS resin molded product that requires a packing function such as daily life waterproofing and silicone rubber. The advantage is that a molded body can be obtained easily and at low cost.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of an injection molding die used in Examples and Comparative Examples of the present invention.

FIG. 2 is a vertical cross-sectional view of the injection mold of FIG. 1 in use.

FIG. 3 is a longitudinal sectional view showing another state of use of the injection mold of FIG.

FIG. 4 is a perspective view showing composite molded bodies obtained in Examples and Comparative Examples of the present invention.

FIG. 5 is a perspective view of a waterproof packing integrated lid for transceiver obtained in Example 3 of the present invention.

FIG. 6 is a perspective view of a lunch box packing integrated lid obtained in Example 4 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Fixed-side mold piece 2 ... Intermediate plate 3 ... Rotary movable-side mold piece 4 ... Movable-side slide core 5 ... Nozzle A 6 ... Nozzle B 7 ... Gate A'8 ... Gate B'9 ... UV irradiator 10 … UV light guide 11… Cavity part (1) 12… Cavity part (2) 13… Cavity part (3) 14,17,19… Plastic molding 15,16,18… Silicone rubber molding

[Procedure amendment]

[Submission date] February 15, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

On the other hand, the silicone rubber used in the present invention is preferably a liquid addition reaction type silicone rubber which can be injection-molded with excellent production efficiency and does not require a pre-process such as roll kneading. Therefore, this is an organopolysiloxane containing vinyl groups and allyl groups as aliphatic unsaturated groups in the molecule, an organohydrogenpolysiloxane having at least two hydrogen atoms directly connected to silicon atoms, and platinum such as chloroplatinic acid. Although it is composed of a system catalyst, it does not have adhesiveness by itself, and therefore, an adhesion-imparting component for imparting adhesiveness to the addition reaction type silicone rubber and the ABS resin molded product is added to this. reduction is necessary, but this is necessary to assume that hardly adhere to the mold or a mold used in injection molding, noted down as such adhesion imparting component
Compounds (i) to (v)

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15] The amount of the adhesiveness-imparting component added to the silicone rubber is 0.1 parts by weight or more and the adhesiveness is sufficient, and if it is 10 parts by weight or less, the separation from the mold is improved. It is preferably 0.1 to 10 parts by weight.

Claims (1)

[Claims] 1. A molded article made of an ABS resin is subjected to UV treatment at least on a portion to which a silicone rubber is adhered, and then the following (i) to (v): Embedded image Embedded image [Chemical 4] Embedded image Of an ABS resin-based molded product and a silicone rubber, wherein a liquid addition reaction-curable silicone rubber containing at least one compound selected from the above is bonded and integrated with the molded product. Method.