JPS5923884A - Rust preventive resin composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having excellent rust preventiveness for copper base-metals as well in addition to ferrous metals in a compsn. composed of a resin and a volatile corrosion inhibitor, by incorporating the salt of benzotriazoles and an org. amine in the volatile corrosion inhibitor. CONSTITUTION:5-50pts. a volatile corrosion inhibitor consisting of the salt of benzotriazole or its deriv. and an org. amine (hereinafter expressed as the 1st volatile corrosion inhibitor) is kneaded with 100pts. a resin by weight, whereby a compsn. is obtd. A transparent rust preventive resin film exhibiting rust preventiveness to iron, copper and alloys thereof is obtd. from such compsn. The equivalent compsn. is also obtainable by incorporating 100pts. the resin, 2-50pts. the 1st volatile corrosion inhibitor, and about 2-50pts. the 2nd volatile corrosion inhibitor consisting of the salt of a benzoic acid, its deriv. or a fatty acid and an org. amine.

Description

[Detailed description of the invention] The present invention relates to the LJ rust-preventive resin composition.

Since iJL, in order to prevent rusting of semiconductor devices such as ICs and LSIs, printed circuit boards on which these are mounted, various relays, electronic and electrical devices such as Z:1 power 1, and metal ornaments. If these are coated with or impregnated with a volatile rust preventive agent, it is widely used to wrap them in rust preventive paper.

However, this rust preventive 81E has the disadvantage that it is opaque and cannot see through the contents, and has poor water resistance, so its rust preventive effect is not sufficient.

In order to solve these problems, transparent rust-preventive resin films have been proposed in which various high-molecular polymers contain volatile rust-preventive agents. For example, if the resin contains a volatile rust preventive agent consisting of a salt of cyclohexylamine or dicyclohexylamine and nitrous acid or benzoic acid, the resin will be completely anti-ζ1! i
Polymer resin films are known, including these ()
All of the rust-proofing resin films known since ancient times have θ+'f resistance against iron, but almost all have resistance against copper and its alloys by 31! It does not have i-character. Electronic/electrical equipment listed above: P1: Not only beams such as metal decorations, but also
Since it is composed of various metal materials such as copper and its alloys, it is almost impossible to prevent rust from forming using conventional rust prevention methods such as those described in -11.

On the other hand, it is already known that benzo I lyazole and its derivatives are effective as volatile rust preventive agents for copper and copper alloys. At the same time, when kneading with 4fi + fat at a high 6Vk degree, a complex chemical reaction occurs between the benzo-1 heliazole and the organic amine salt, resulting in loss of θ1 time resistance and the kneading itself becomes difficult. 1 t, making it impossible to obtain a uniform resin composition.

Furthermore, secondary processing such as film processing is also possible ■”ff1l
It is t.

The present invention is a rust-preventive tree JIl'? This was done to resolve the problem described in 1.
The purpose of this work is to develop a resin composition that has antirust properties against iron alone, iron alloys, iron alloys, and their alloys, and a method for producing the same.

The rust-preventive resin composition according to the present invention has a resin composition of 100rffi.
J? and 5 to 50 parts of a volatile rust preventive agent (hereinafter referred to as the first volatile rust preventive agent) consisting of a salt of hensitriazole or its derivative and a legged amine, and contains iron, ζ1 resistance against copper and these alloys! It is characterized by having i-character.

The benzo I lyazole derivatives used in the present invention include all derivatives already known to have antirust properties against copper, and a specific example thereof is tolyltriazole. In addition, as the organic amine that forms a salt with the benzo-1-lyazole or its derivative, aliphatic amines, alicyclic amines, heteroaromatic amines, etc. are preferably used, and specifically, for example, cyclohexylamine, dicyclo 1 g of hexylamine, isopropylamine, diethylamine, monoethanolamine, hexylamine, piperidine, and piperidine can be added.

The amount of the first volatile rust preventive to the resin is 100% of the resin.
L: 5 to 50 parts by weight, preferably 10 parts by weight per part of fi
~30 parts by weight. If the amount is too small, it will not have effective rust prevention properties, while if it is too large, it will be difficult to evenly contain it in the four parts. 7. It's very rude because it makes you feel inferior in sex. <I.

By using the first volatile rust preventive in this way, even when 2kff=14 with resin i, the prevention is 6nf 'fPJ I
The resulting resin i+ can be easily molded into containers, fillers, etc. without causing any undesirable reactions.

Further, as described above, the resin composition containing the first volatile rust preventive agent is preferably used after being formed into a film. In other words, by packaging a product made of metal materials such as iron, copper, or alloys thereof, the rust preventive agent will be slowly released into the film. , this product does not cause fi'i over a long period of time.

However, according to the present invention, in addition to the above-mentioned volatile rust inhibitors, benzoic acid, derivatives thereof, or salts of No. 91 fatty acids and the organic amines (hereinafter referred to as second volatile rust inhibitors) are used. When a volatile rust inhibitor is used in combination, the 611i resistance against iron, copper, and their alloys is greatly increased.

Examples of the derivatives of benzoic acid include those having 1 or (, 12 or more) 1, for example, 21-benzoic acid, Dibenzoic acid and the like can be mentioned as dinitrates, but the invention is not limited to these exemplified derivatives.The above fatty acids are preferably saturated or unsaturated fatty acids having 6 to 20 carbon atoms. , Specific examples of IflJ include, but are not limited to, capric acid, caprylic acid, pelargonic acid, and the like.

Therefore, as a specific example of a preferable second volatile rust preventive agent,
Examples include cyclohexylammonium benzoate, dicyclohexylammonium benzoate, dicyclohexylammonium caprylate, diethylammonium dinitrhensoate, and the like.

The second 'Jl'j agent is also kneaded with the resin at an irb i'AL degree and is stable, and the first evaporation preventive agent is 8+!
Since there is no undesirable reaction between i and l'l, a homogeneous resin composition is prepared by kneading it with the first rust preventive (61 fat), and this b or , J'
,! , b i'2+', molding 1) Whiten 1. In the present invention, the anticorrosive (!L + AI) composition is the first
2 to 50 parts by weight of volatile rust preventive agent, preferably 1 mm 4.1
: l[lfl~;30 ili Rrfl! and the second
Evaporation prevention QC! iR'J 2~50 fQ fif
Contains 10 to 3 parts by weight. Particularly preferably, the total amount of the first and second volatile rust inhibitors is equal to I OO weight rfli (r, -
(1'75 to 50 parts by weight, and the weight ratio of the first and second rust preventives is 1:5 to 5:1.The rust preventive resin composition of the present invention When used as a film, depending on the application, the rust preventive agent may be 1% of the film.
It is practically preferable that the amount is 1 to 20 g per serving.

In the present invention, the first (and second) volatile rust preventive agent is added as an amine salt to the resin and kneaded.
) Rini, the first defense is 31! For the I agent, hensitoυapool or its derivative and the present amine may be added separately to 4AJ fat and kneaded, and for the second rust preventive agent, benzoic acid, etc. The derivative or fatty acid and the canned μ amine may be separately added to the 4111J finger and bundled into the lkon.This method also allows each component to be separated from each other during the kneading process without causing any undesirable reactions. At the same time as forming amine JIS, this amine salt is uniformly distributed in the resin.
be done.

In the present invention, the resin containing the above-mentioned vaporized flL rust preventive agent is not particularly limited, and various resins can be used. 11 old 1k during kneading and subsequent molding with
Comparatively low melting to suppress the problem! Preferably, a G:1 degree polyolefin resin is used so that it has a degree of VA7 and further has heat sealability when the resin composition is molded. Here, for polyolefin resin,
For example, polyethylene, vinyl chloride resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid (or its ester tJI) JMf? This shall include combinations, etc. Particularly volatile 1kaφ:! Preferably used are ethylene-vinyl monoacetate copolymers, ethylene-acrylic acid (or esters thereof) copolymers, etc., which have excellent compatibility with i.

The rust-preventive resin composition according to the present invention, the resin and the first
Melt the (and second) volatile anti-ti'i agent into the resin by appropriate means such as roll kneading. iυ by kneading at a temperature of 11 degrees or higher, Jln X';'
It is formed into shapes such as +, bellet 1-, etc., and is further formed into a film, etc., and is used for packaging products that require rust prevention.

When the 461 resin composition according to the present invention is formed into a film and used, the film optionally contains a volatile rust preventive agent. A second JA with Barry 1- property against the anti-corrosion inhibitor.
A multilayer film is obtained by laminating an IJltr layer and, on the other side, a third resin layer that can control the vaporization of the volatile rust preventive agent. Of course, it may be a film in which only the second or third resin layer is laminated. The second resin is not particularly limited as long as it has a barrier property that substantially prevents the vapor of the volatile rust preventive agent from permeating, but in particular, it may be an ethylene-vinyl resin, an iQ combination resin, or an ionomer resin layer 1. Preferably, the fingers of the tree are used. Also,
As the third printing j111, while controlling the vapor of the vaporizable chemical used, the i! Preferably, the content of υJ polyethylene is 4M and the vinyl carbonate content is preferably 19% by weight.
A vinyl co-117 composite resin having a working strength of less than 1/2" is preferably used. Polyethylene resin can also be used as a second resin depending on the type of rust preventive agent.
It can also be used as a third resin.

In the present invention, the kneading temperature of the resin and the rust preventive agent is preferably low in order to prevent volatilization of the rust preventive agent.
A temperature of 80 to 120"C is employed.Also, it is preferable that the temperature when molding the resin composition of the present invention into a film or the like is similarly low, but for example, in the case of extrusion molding, the temperature is X & degree is usually 80 to 120° for C1 and C2 for the intermediate resin layer containing an anti-q-1 agent.
For the second and third resin layers, C1 and C2 are about 100 to 150 degrees Celsius, and C3 is about 130 to 170 degrees Celsius.

As in 1 to 12, in the present invention, vaporization resistance 3+
Since a salt consisting of benzotriazole or a derivative thereof and an organic amine is used as the additive, the rust preventive will not cause any undesirable reaction even when mixed with the resin at the melting temperature of the resin, and will not cause any undesirable reaction to the film, etc. It has excellent moldability. Furthermore, molded products such as films made from the resin composition of the present invention have a rust resistance of 1 (1-) against iron, copper, and their alloys, and a brightness of 0 i1. , heat-sealability deteriorates, so it can be used for electronic/electrical items made of various metals 4A fi+ 1.! items and decorations 9
Suitable for rust-proof packaging of single items, etc. Particularly, according to the present invention, in addition to the first anti-811i agent, a second anti-811i agent consisting of benzoic acid, a derivative thereof, or a salt of a fatty acid and the organic amine is used! The 4b1 resin composition containing the i-agent has superior rust prevention properties against iron, copper, and their alloys.

Examples of the present invention are listed below. In addition, in the following, part means ill music part.

Example 1 Cyclohexylammonium Henze-1-25 Ichikawabe and ethylene-vinyl acetate copolymer (Mitsui Polychemical Co., Ltd.
Iil PI907, vinyl acetate content 19jn R96
, MI = 15g/10min> i o o Hu 1 m is ll at a temperature of 100 ° C with an IO ind open roll.
Chang! It was molded into 3 square pellets.

As the second 4A+ fat, an ionomer resin (Himilan 1702 manufactured by Mitsui Polygemical II'2, ion zinc, M I = 15 710 minutes) was used. As the resin 1 of No. 83, an ethylene-vinyl acetate copolymer (Mitsui Polygemical Co., Ltd., IP-0607, convex) vinyl acid content 6% by weight, MI = 25 g/10 min) was used, and a rust preventive agent described in "2" was added. It is co-extruded with Beret L- by a three-layer inflation extrusion device with a diameter of 100 mm, and both the inner and outer layers are 251 mm in diameter.
! A mold-proof bag (41) with a folded diameter of 80 mg and made of a three-layer film with a rust-inhibiting agent-containing layer of 50 μm was prepared.

``In the second article, a 40 ma diameter extruder was used to extrude the first resin containing the anti-8i'j agent, and a 25++ mil extruder was used to extrude the second and third resins, respectively.
111 of the first polymer extruder! The degree is C,=]00'C
, C, = 100°c, C3 = 120"C, and the second and third resin presses 1" of one machine? XA degree is C, = 130'
C, C2 - 150°C, Gui/11 degree is 130°
c Toshinoko.

Examples 2 to 4 In the same manner as in Example 1, using the volatile rust preventive shown in the table and the same resins as in Example 1, coextrusion was carried out using a 3JfA inflation extrusion device, and each resin l-thick The same laminated film as in Example 1 was produced.

2 Example 5 900 parts by weight of dicyclohexylamine was impregnated into 8100 parts by weight of the same ethylene-vinyl acetate copolymer (P1907) as described above (this was referred to as component A). Separately, add 7 parts by weight of benzoic acid to L'7-P'il;
't'l'! Vinyl copolymer (P1907) 540 (
The mixture was kneaded with a 90°C open roll and pelletized (this is referred to as component B).

These A and B components were tri-blended and 4o neck extrusion 1
ffitec and C is 100'C, C is 90'C?
It was extruded at XA degree to form pellets 1-C.

Next, cyclohexylamine l of benzo-1-lyazole
a, j 1 s o city B't fall' - written Hellet C700 weight port 11 and the said Edylene-vinyl acetate t
370 parts by weight of li combined (P 1907) and 90'c
Mixed in an open roll 6. To the east, it was set as D.
Regarding the in m part, dicyclohexylammonium benzoate-1.7 electron Far +++ to Schiff 12 of Henzotriazur. 1-zylamine J4i! 8 market volume j'
! l('C-containing.

3 Using this Beret L-D and the same second and third resins as in Example 1, three blown extruded films were obtained in the same manner as in Example 1.

The rust prevention properties of each film obtained as described above are shown in the table together with the moldability of the resin composition.

Comparative Example 1 In the same manner as in Example 1, benzotriazole was used as a volatile rust preventive and kneaded with the resin at a temperature of 100°C. Pelletized in the same manner as in Example 1, and
Coextrusion was carried out using a layer inflation extrusion device to produce a laminated film having the same resin layer thickness as in Example 1. However, as shown in the table, this film had poor rust prevention properties against iron.

Comparative Example 2 When henzotriazur and cyclohexylammonium benzoate were used as volatile rust preventive agents and rolled with the same resin as in Example 1 at a temperature of 100°C, the prevention was 1!
The I punishment caused a reaction and I was able to practice lJ and it was 4r.

Comparative Examples 3 to 6 4 In view of Comparative Example 2, ethylene-vinyl acetate copolymer Mitsui Polychemical A (g) was used as the resin! IuP3307,i
"il + acid vinyl content 33% market weight, MI = 30g/10
Roll kneading was carried out at a temperature of 70°C using the volatile rust preventive agent shown in the table. Although the reaction of the rust preventive during kneading could be suppressed, in the same coextrusion as in Example 1, the Goo temperature was 130°C and 1[G], so the rust preventive reacted and the film I couldn't.

The 111-proof properties of the films of each comparative example obtained as described below are shown in the table.

The method for evaluating the rust-preventing power of the bag is as follows.

1. Cold rolled steel plate specified in JIS G 3141.
Cut into 5 x 60 x 80 squares, and JIS I+ 3
75x the grass P14 anti specified in 103] 3x1.5+
gm, polished and cleaned each test piece according to the method specified in Section 3 of JIS Z 023G,
After sealing it in the container bag, put it in a wet/11 container (
For iron, JIS Z
Copper was examined visually for discoloration using the method specified in Section 3 of 0236. In the case of copper, if no discoloration was observed by visual inspection, it is indicated by ○.

The table also shows evaluations of moldability of resins containing volatile rust inhibitors. If roll kneading or extrusion is difficult (it is possible to carry out, it is indicated by ○, and if it is not possible due to the reaction of the rust preventive agent, it is indicated by x).

As is clear from the table, the bag obtained with the resin N of the present invention and the composite material exhibited poor rust prevention against both iron and copper, whereas the resin composition of the comparative example , Except for Comparative Example 1, kneading or extrusion was not possible, and the prevention of $ui +! I couldn't give it a rating of 1. Although the resin composition of Comparative Example 1 could be formed into a film, it showed almost no effective rust prevention against iron.

7 460-

Claims (1)

[Scope of Claims] +11 Iron characterized by containing 21 parts of resin 1 (lOU) and 5 to 50 parts by weight of a volatile rust preventive agent consisting of a salt of hensitriazole or a derivative thereof and an organic amine;
A resin composition that has antirust properties against copper and alloys thereof. (2) Volatile rust preventive agent 2 consisting of 100 parts by weight of resin, a salt of benzo-1-lyazole or its derivative, and organic amine
~50 parts by weight, benzoic acid, its derivative or J Fat IIJ
Volatile anti-ri' consisting of salt of j acid and organic amine: Agent 2
Moth-proof against iron, copper and their alloys, characterized by containing ~50% by weight 13! Rust-preventive resin f, II composition having i properties.