JPH0741618A - Electrical / electronic parts comprising 3-methyl-1-butene polymer composition - Google Patents

Abstract

PURPOSE:To provide the subject electric or electronic part comprising a methylbutene polymer, a graft-modified methylbutene polymer and glass fibers, excellent in reflowability and electric characteristics, low in water absorbability, and useful for housings, etc. CONSTITUTION:The objective electric or electronic part comprises (A) 0-99.9 pts.wt. of 3-methyl-1-butene polymer comprising a 3-methyl-1-butene.1-butene random copolymer preferably containing >=70wt.% of the 3-methyl-1-butene, (B) 0.1-100 pts.wt. of a graft-modified 3-methyl-1-butene polymer containing 0.01-10wt.% of unsaturated carboxylic acid (derivative)-graft-modified units (preferably the polymer graft modified with maleic anhydride), and (C) 10-100 pts.wt. of glass fibers, the sum of the component A and B being 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric / electronic component made of a 3-methyl-1-butene polymer composition, and particularly to a housing having excellent reflow solderability and electric characteristics and a low water absorption rate. For electrical and electronic parts such as

[0002]

2. Description of the Related Art Materials for housings of electric and electronic parts are required to have excellent reflow solderability and electric characteristics and low water absorption. Conventionally, PPS or poly 4-methyl-1-pentene reinforced by blending glass fiber has been used as the material for the housing.

[0003]

However, the glass fiber reinforced PPS has relatively good reflow solderability, electrical characteristics and water absorption, but has a drawback in that burrs are liable to be formed during molding because of its poor moldability. Therefore, when it is formed into a thin-walled molded product, post-processing is difficult, and reflow solderability may be a problem. On the other hand, glass fiber reinforced poly-4-methyl-1-pentene has good electrical properties, water absorption and moldability, but has a problem in reflow solderability. Therefore, there is a strong demand for a material for a housing such as an electric / electronic component that has excellent reflow solderability and electrical characteristics, low water absorption, and excellent moldability.

Therefore, a first object of the present invention is to provide an electric / electronic component made of a resin composition having excellent reflow solderability and electric characteristics and having low water absorption.

Another object of the present invention is to provide a thin molded product,
For example, it is to provide an electric / electronic component made of a resin composition that does not cause burrs when molding a housing for electric / electronic components.

[0006]

Means for Solving the Problems The inventors of the present invention have high reflow solderability, excellent electric characteristics and water absorption, and excellent moldability. As a result of various studies aimed at obtaining electronic parts, 3-methyl-1-butene-based polymer, 3-methyl-1-butene-based polymer graft-modified with unsaturated carboxylic acid or its derivative, and glass fiber It was found that an electric / electronic component comprising a 3-methyl-1-butene-based polymer composition containing as a main component and a compounding amount of each component within a specific range can achieve the above object, I arrived.

That is, in order to solve the above-mentioned problems, the present invention provides (A) 3-methyl-1-butene polymers 0-9.
Graft-modified 3 containing 9.9 parts by weight of (B) at least one graft-modified unit selected from unsaturated carboxylic acids and derivatives thereof in the range of 0.01 to 10% by weight.
-Methyl-1-butene polymer 0.1 to 100 parts by weight,
And (C) 3-methyl-1 containing 10 to 100 parts by weight of glass fiber with respect to (A) + (B) = 100 parts by weight.
-To provide electric / electronic parts made of a butene-based polymer composition.

It is preferable that the content of 3-methyl-1-butene in the (A) 3-methyl-1-butene polymer is 70% by weight or more.

It is preferable that the (A) 3-methyl-1-butene random copolymer is a 3-methyl-1-butene / 1-butene random copolymer.

The above-mentioned (B) graft-modified 3-methyl-1-
The butene-based polymer is preferably 3-methyl-1-butene graft-modified with maleic anhydride.

According to ASTM D 1238, the load:
The melt flow rate (MFR) measured under the conditions of 2.16 kg and temperature: 320 ° C. is 0.1 to 100 g / 10.
A 3-methyl-1-butene polymer composition within the range of minutes is preferred.

The 3-methyl-1-butene polymer composition (hereinafter referred to as "composition used in the present invention") constituting the electric / electronic component of the present invention will be described in detail below.

The 3-methyl-1-butene polymer which is the component (A) of the composition used in the present invention is 3-methyl-1-butene.
It is a polymer containing butene as a main component, and is, for example, a homopolymer of 3-methyl-1-butene or a copolymer of 3-methyl-1-butene and another α-olefin. Other α
Examples of the olefin include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. Other α-
Among the olefins, 1-butene is preferable.

Further, the (A) 3-methyl-1-butene polymer has a melting point within a range capable of maintaining good reflow soldering property, and a composition useful as a housing material for electric / electronic parts is In that respect, it is usually 3-methyl-
It is preferably a polymer containing 70% by weight or more of 1-butene.

The (A) 3-methyl-1-butene-based polymer is variously determined depending on the use of the composition of the present invention, but the load is 2.16k according to ASTM D 1238.
It is preferable that the melt flow rate (MFR) measured under the conditions of g, temperature: 320 ° C. is usually within the range of 0.1 to 100 g / 10 minutes.

The graft-modified 3-methyl-1-butene polymer, which is the component (B) of the composition of the present invention, has the above-mentioned (A).
The base is a 3-methyl-1-butene-based polymer having the same or different composition or molecular weight as the 3-methyl-1-butene-based polymer.

Further, (B) graft-modified 3-methyl-1
Examples of the unsaturated carboxylic acid or a derivative thereof contained in the butene-based polymer as a graft modification unit include, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid, acrylic acid. An unsaturated carboxylic acid such as an acid or methacrylic acid, or a derivative thereof can be used. Examples of this derivative include acid anhydrides, imides, amides and esters of the above unsaturated carboxylic acids. Specific examples of the derivative of unsaturated carboxylic acid include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.
Among these, unsaturated dicarboxylic acid or its anhydride is preferable, and maleic acid or its acid anhydride is particularly preferable.

The (B) graft-modified 3-methyl-1-butene polymer can be prepared according to various conventionally known methods. For example, a method of melting and graft-copolymerizing a 3-methyl-1-butene-based polymer and at least one selected from unsaturated carboxylic acids and their derivatives, or a 3-methyl-1-butene-based polymer It can be carried out according to a method such as a method of dissolving in a solvent and adding at least one selected from unsaturated carboxylic acids and their derivatives to carry out graft copolymerization.

This (B) graft-modified 3-methyl-1-
In the preparation of a butene-based polymer, it is preferable to carry out the reaction in the presence of a radical polymerization initiator in order to efficiently graft-copolymerize at least one monomer selected from unsaturated carboxylic acids and their derivatives.

The radical polymerization initiator used is
Examples thereof include organic peroxides, organic peresters, and azo compounds. Among these radical polymerization initiators,
Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-
Butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
Organic peroxides such as 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

In the preparation of the (B) graft-modified 3-methyl-1-butene-based polymer, the proportion of the radical polymerization initiator used is usually 3-methyl-1-butene-based polymer 100.
It is in the range of 0.001 to 2 parts by weight with respect to parts by weight.

The graft copolymerization reaction is usually performed at 60
It is carried out at a temperature of ~ 350 ° C.

In the composition used in the present invention,
(B) The content of at least one kind selected from unsaturated carboxylic acids and their derivatives in the graft-modified 3-methyl-1-butene-based polymer, that is, the graft amount is (C) glass fiber and (B) described later. Adhesiveness with the graft-modified 3-methyl-1-butene polymer becomes good, a molded product having excellent mechanical strength can be obtained by molding the composition of the present invention, and further, reflow soldering property is excellent. From the point of obtaining the composition, 0.01 to 10% by weight,
The range of 0.1 to 5% by weight is preferable.

(A) in the composition used in the present invention
The mixing ratio of the 3-methyl-1-butene-based polymer and the (B) graft-modified 3-methyl-1-butene-based polymer is such that the adhesion between these polymers and the (C) glass fiber described later is good. With respect to (A) 3-methyl-1-butene polymer (0 to 99.9 parts by weight), ((A) 3-methyl-1-butene-based polymer) can be obtained by molding the composition of the present invention to obtain a molded article having excellent mechanical strength. B) Graft-modified 3-methyl-1-butene polymer 0.1 to 100 parts by weight.

As the glass fiber which is the component (C) of this composition, any of the known glass fibers which are usually used as a resin component may be used. For example, the fiber diameter of (C) glass fiber is usually about 5 to 20 μm, and the surface treatment agent is preferably aminosilane or epoxysilane.

(C) in the composition used in the present invention
The blending ratio of the glass fiber is high in mechanical strength and elastic modulus of the molded product, particularly high in impact resistance, suitable for a housing for electric / electronic parts, and excellent in mechanical strength of a weld portion. Since it has fluidity, it is easy to form a thin-walled molded product, and in the range of 10 to 100 parts by weight with respect to (A) + (B) = 100 parts by weight, particularly 20 to 8 parts.
A range of 0 parts by weight is preferred.

The 3-methyl-1-butene-based composition used in the present invention is produced by (A) 3-methyl-1-butene-based polymer and (B) graft-modified 3-methyl-1-butene-based polymer. , And (C) the glass fibers are mixed in the above-mentioned mixing ratio, melt-kneaded by a conventionally known method, and the method of assembling or crushing can be performed. The mixing can be performed using, for example, a V-type blender, a ribbon blender, a Henschel mixer, a tumbler blender, or the like. The melt-kneading can be carried out, for example, with a single-screw extruder or a multi-screw extruder, a kneader, a Banbury mixer, or the like.

The MFR of the composition used in the present invention can be adjusted according to its application. This MFR
Is a load according to ASTM D 1238: 2.16k
g, temperature: the value measured under the condition of 320 ° C. is usually 0.
It is preferably in the range of 1 to 100 g / 10 minutes, and particularly preferably 1.0 to 80 g / 10 minutes.

If the MFR of the composition used in the present invention is too low, it becomes difficult to mold a thin-walled molded product, and the residual stress associated with the molding becomes large, causing deformation and stress cracking of the molded product. On the other hand, if the MFR is too high, the mechanical strength such as bending strength and impact resistance becomes low.

In addition, the composition used in the present invention contains various additives such as silane coupling agents, weather resistance stabilizers, heat resistance stabilizers, slip agents, nucleating agents, pigments and dyes which are usually added to polyolefins. The agent may be added as long as the object of the present invention is not impaired.

The present invention is based on the above-mentioned 3-methyl-1-
Provided are electric and electronic parts made of a butene-based composition. The type and shape of the electric / electronic parts are not particularly limited, but housings, substrates, mold resins, insulating plates, etc. for various electric / electronic parts are preferable. As an example of the electric / electronic component of the present invention, a front view of a network resistor is shown in FIG. 1 and a side view thereof is shown in FIG. The network resistance shown in the figure has many resistors in one housing 1 made of the 3-methyl-1-butene-based composition described above. For example, it is used as a pull-up or pull-down resistance of a microcomputer. To be In a flat hollow rectangular parallelepiped housing 1, a rectangular alumina substrate 2 is provided in the longitudinal direction, and on the alumina substrate 2, a resistance element 3 and a conductor 4 are provided.
A plurality of resistors connected to each other are continuously provided at right angles to the longitudinal direction of the alumina substrate 2. From the outside of the housing 1, the terminals 6 are connected to the conductors 4 of the respective resistors by the solder 5. The electric / electronic component of the present invention is the above-mentioned 3-methyl-1.
-Because it has a housing made of a butene-based composition, it has excellent processability during housing molding, high heat resistance such as reflow solderability, excellent electrical characteristics, and low water absorption.

[0032]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Further, the evaluation of the moldability, reflow solderability and electrical characteristics in the following examples and comparative examples was performed by the following methods.

(1) Moldability A thin-walled case (length 9 mm, width 14 mm, height 7 mm, thickness 0.4 mm) was molded by the injection molding method, and the appearance of burrs was visually observed and evaluated according to the following criteria. did. ○ …… No burr × …… Burr exists

(2) Reflow solderability With respect to the thin case obtained by the above injection molding, far infrared reflow soldering device (MJ-R4 manufactured by JARD Co., Ltd.)
000) was used to observe the appearance and the reflow solderability was evaluated according to the following criteria. ○: No change △: Deformation ×: Perforation due to melting

(3) Electrical characteristics A square plate having a thickness of 2 mm is molded by an injection molding method, and JIS K6 is used.
According to 911, the dielectric constant and dielectric loss tangent at 1 GHz were measured.

Example 1 <Production of Maleic Anhydride Graft-Modified 3-Methyl-1-butene-Based Polymer> 3-Methyl-1-butene / 1-butene copolymer (1-butene content: 4. 4% by weight, MFR:
1.0 g / 10 minutes) to 100 parts by weight of maleic anhydride, 1.4 parts by weight of 2,5-dimethyl-2,5-di (t
ert-butylperoxy) hexyne-3 0.07 parts by weight, tetrakis [methylene-3 (3,5-di-ter)
t-butyl-4-hydroxyphenyl) propionate] methane (Ciba Geigy Ltd., Irganox 10)
10) 0.10 part by weight and 0.05 part by weight of hydrotalcite (manufactured by Kyowa Kagaku Co., Ltd.) were mixed with a Henschel mixer, then fed to an extruder and reacted at 320 ° C. while melt-kneading, Maleic anhydride modified 3-methyl-1-
A butene polymer was obtained. Maleic anhydride modified 3 obtained
-Methyl-1-butene polymer (hereinafter referred to as "MAH-PM
B)) and the amount of maleic anhydride grafted were measured to find that MFR: 500 g / 10
Min, maleic anhydride graft amount: 1.0 g / 100 g of polymer.

<Production of Composition> 94.6 parts by weight of 3-methyl-1-butene / 1-butene copolymer (1-butene content: 5.2% by weight, MFR: 4.6 g / 10 minutes) In contrast, 5.4 parts by weight of MAH-PBM and 40.5 parts by weight of glass fiber (GRS34 manufactured by Asahi Glass Co., Ltd.), and tetrakis [methylene-3 (3,5-di-tert].
-Butyl-4-hydroxyphenyl) propionate]
Methane (Ciba Geigy Corporation, Irganox 101)
0) 0.20 parts by weight, tetrakis (2,4-di-ter)
0.20 parts by weight of t-butylphenyl) 4,4-biphenylene diphosphonite (Sand Co., Ltd., P-EPQ), and hydrotalcite (Kyowa Chemical Co., Ltd.)
After mixing 05 parts by weight with a Henschel mixer, the mixture was supplied to an extruder and melt-kneaded at 320 ° C. to obtain a 3-methyl-1-butene-based polymer composition. The blending amount at this time is shown in Table 1.

Next, using this 3-methyl-1-butene polymer composition, a thin case (length 9 mm, width 14 mm, height 7 mm, thickness 0.4 m) was prepared by injection molding.
m) and the square plate were respectively molded, and subjected to measurement or evaluation of moldability, reflow solderability and electrical characteristics. The results are shown in Table 2.

(Example 2) In producing a composition, 1-
Butene content: 10.3% by weight, MFR: 11 g / 10
3-Methyl-1-butene / 1-butene copolymer was used in the same manner as in Example 1 except that the same amount of 3-methyl-1-butene / 1-butene copolymer was used.
A butene polymer composition was prepared. Next, using this 3-methyl-1-butene-based polymer composition, a thin case and a square plate were respectively molded, and subjected to measurement or evaluation of moldability, reflow solderability and electrical characteristics. The blending amount and the evaluation or measurement result are shown in Table 1 and Table 2, respectively.

(Example 3) In producing a composition, 1-
Butene content: 5.0 wt%, MFR: 16 g / 10 min of 3-methyl-1-butene / 1-butene copolymer was used, and the compounding amount was changed as shown in Table 1. A 3-methyl-1-butene-based polymer composition was prepared in the same manner as in Example 1 and subjected to measurement or evaluation of moldability, reflow solderability and electrical characteristics. Table 2 shows the blending amount and the evaluation or measurement result.

Comparative Example 1 3-Methyl-1-butene-1
A composition was prepared in the same manner as in Example 1 except that PPS (Toprene Co., T-1) was used instead of the butene copolymer, and the compounding amount was changed as shown in Table 1. It was prepared and subjected to measurement or evaluation of moldability, reflow solderability and electrical characteristics. The compounding amount and evaluation or measurement result
It shows in Table 2.

Comparative Example 2 3-Methyl-1-butene-1
-A 4-methyl-1-pentene polymer (RT18, Mitsui Petrochemical Industry Co., Ltd.) was used in place of the butene copolymer, and the compounding amount was changed as shown in Table 1, except that
A composition was prepared in the same manner as in Example 1 and subjected to measurement or evaluation of moldability, reflow solderability and electrical characteristics.
Table 2 shows the blending amount and the evaluation or measurement result.

[0043]

[0044]

[0045]

The electric / electronic component comprising the 3-methyl-1-butene polymer composition of the present invention has a housing having reflow solderability, electrical characteristics, low water absorption, and the like. During molding, it has high fluidity at the molding temperature and excellent moldability.

[Brief description of drawings]

FIG. 1 is a front view showing a structure of a network resistor which is an example of an electric / electronic component of the present invention.

FIG. 2 is a side view showing a structure of a network resistor which is an example of the electric / electronic component of the present invention.

[Explanation of symbols]

 1 Housing 2 Alumina Substrate 3 Resistor 4 Conductor 5 Solder 6 Terminal

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hirojiro Suga, Inventor, Hirojiro Suga, 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Masayuki Okabe, Kazu-gun, Kuga Kimachi Waki 6-1-2 Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Toshihiro Aine 6-2 Waki, Waki-cho, Kaku-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Invention Person Kenji Iwata 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A (A) 3-methyl-1-butene polymer 0
To 99.9 parts by weight, (B) a graft-modified 3-methyl-1-butene system containing 0.01 to 10% by weight of at least one graft-modified unit selected from unsaturated carboxylic acids and derivatives thereof. 0.1 to 100 parts by weight of polymer, and (C) 3-methyl-1-butene polymer composition containing 10 to 100 parts by weight of glass fiber with respect to (A) + (B) = 100 parts by weight. Electrical and electronic parts made up of. 2. The 3-methyl-1-butene-based polymer according to claim 1, wherein the content of 3-methyl-1-butene in the (A) 3-methyl-1-butene polymer is 70% by weight or more. -Electrical / electronic parts made of a butene-based polymer composition. 3. The 3-methyl-1-butene random copolymer according to claim 1, wherein the (A) 3-methyl-1-butene-based polymer is a 3-methyl-1-butene / 1-butene random copolymer. Electric / electronic parts made of a polymer composition. 4. The (B) graft-modified 3-methyl-1-
The butene-based polymer is 3-methyl-1-butene graft-modified with maleic anhydride, and the electrical / electrical properties of the 3-methyl-1-butene-based polymer composition according to claim 1. Electronic components. 5. A load according to ASTM D 1238:
The melt flow rate (MFR) measured under the conditions of 2.16 kg and temperature: 320 ° C. is 0.1 to 100 g / 10.
An electric / electronic component comprising the 3-methyl-1-butene polymer composition according to claim 1, which is in the range of minutes.