JP2001019686A - Thiadiazole derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having extremely excellent rust-preventive effect on various metals, especially on electronic components, and useful as a rust-preventive agent for metals, treatment agent for treating metal surface or the like, water/oil-repelling agent or the like. SOLUTION: This compound is a compound of formula I (R is H, a 1-30C alkyl or 2-30C alkenyl, O may be inserted between the C-C bond in the group, the CH2 in the group may be substituted with OCO or COO, or the H in the group may be substituted with F or OH), e.g. a compound of formula II. A compound of formula I is obtained, for example, by esterifying (dehydrocondensation) 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole with a compound of the formula R-OH [e.g. F(CF2)8(CH2)3OH], as necessary in the presence of a catalyst (e.g. paratoluene'sulfonic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel thiadiazole derivative and its use.

[0002]

2. Description of the Related Art Conventionally, rust inhibitors for metals, particularly rust inhibitors for metals used in electronic parts, include imidazole derivatives,
Various nitrogen-containing compounds such as triazole derivatives or benzimidazole derivatives, various mercapto group-containing compounds,
Various inorganic compounds or mixtures of two or more thereof have been used. However, since conventional metal rust preventives do not provide a sufficiently satisfactory effect, a number of processes of performing rust preventive treatment after pretreatment such as washing with an acid or alkali after silver plating and further washing with water. Was needed.

[0003] In a soldering process of an electronic component, a portion where the flux should not come into contact is treated with a flux rising preventing agent. In a process of coating a part of the electronic component with a resin, a portion where the resin must not be coated is formed. Treatment with a resin adhesion inhibitor is performed. In these cases, if the electronic component contacting the processing agent is made of a metal, the component of the processing agent attached to the metal may cause corrosion or rust of the metal. In order to avoid this, it is necessary to rust-proof the surface of the electronic component before the treatment. That is, after the rust prevention treatment, a plurality of steps of further treating with a flux rising preventing agent and a resin adhesion preventing agent were required.

[0004] As a flux rising preventing agent or a resin adhesion preventing agent, a polyfluoroalkyl group (hereinafter referred to as R) is used.
^f group), particularly a perfluoroalkyl group (hereinafter referred to as “ ^f group”).
R ^F group) is used. For example, there is a compound having one or more R ^f groups (a typical compound is a polymer or copolymer of a (meth) acrylate ester having an R ^f group). The flux rise preventing agent is disclosed in JP-A-60-49859 and
-30,536 and the like. Examples of the resin adhesion preventing agent include JP-A-63-7229 and JP-A-3-25.
6310 and the like.

Conventionally, as the water and oil repellent, compounds containing R ^f groups, especially polymers or copolymers containing polymerized units having R ^f groups, have been widely used. However, compounds used in conventional water and oil repellents do not have a rust-preventive effect. For example, when a metal such as an electronic component is subjected to a water- and oil-repellent treatment, the rust-proof treatment must be performed in advance. It was necessary to perform a water / oil repellent treatment.

[0006]

SUMMARY OF THE INVENTION The present invention provides a novel compound useful as a metal rust preventive which solves the above-mentioned problems, a treating agent for treating a metal surface or the like containing the compound and a water / oil repellent. .

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on compounds which can be effective components of a metal rust preventive agent. As a result, a group of thiadiazole derivatives, which are novel compounds, have been found to be useful for various metals, especially electronic components. Have an extremely excellent rust-preventing effect on the present invention, and have reached the present invention. Also,
This thiadiazole derivative is useful as a treating agent for treating a metal surface or the like or a water / oil repellent. The present invention
The following inventions related to thiadiazole derivatives and uses thereof. A thiadiazole derivative represented by the following formula 1.

[0008]

Embedded image

R in the formula 1 is a hydrogen atom, having 1 to 30 carbon atoms.
An alkyl or alkenyl group having 2 to 30 carbon atoms, the carbon in the group - is between carbon bond may be inserted an oxygen atom, -CH ₂ in the radical - is -OCO- or -
COO- may be substituted, and a hydrogen atom in the group may be substituted with a fluorine atom or a hydroxyl group.

A metal rust inhibitor comprising the above thiadiazole derivative. A treating agent for treating a metal article or an article having a metal part, comprising the thiadiazole derivative. A water / oil repellent containing the above thiadiazole derivative.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION R in the formula 1 is preferably the following groups. An alkyl or alkenyl group having 8 to 30 carbon atoms, a polyfluoroalkyl group or a polyfluoroalkenyl group having 2 to 30 carbon atoms, and an oxygen atom may be inserted between carbon-carbon bonds in the group. , -C in the group
The H ₂ —, —CFH— or —CF ₂ — moiety may be substituted with —OCO— or —COO—, and a hydrogen atom or a fluorine atom in the group may be substituted with a hydroxyl group.

As R, the number of carbon atoms having high hydrophobicity is 8 to 30.
Is particularly preferable, and an alkyl group having 8 to 30 carbon atoms having a linear or short side chain is particularly preferable, and a linear alkyl group having 10 to 20 carbon atoms is particularly preferable.

In particular, R is more preferably an R ^f group having a higher hydrophobicity than an alkyl group. That is, R is 60 in terms of the number of hydrogen atoms of the corresponding alkyl group.
% Or more, especially 80% or more of R ^f
Groups are preferred. Also, very few of the remaining hydrogen atoms may be replaced by chlorine atoms. The ^Rf group has 4 to 20 carbon atoms.
Is preferred.

R is an etheric oxygen atom, a hydroxyl group, --OC
It may have O- or -COO-. The etheric oxygen atom preferably exists between two carbon atoms to which a fluorine atom is bonded, and the number of etheric oxygen atoms is preferably 10 or less. Further, the hydroxyl group is preferably present at a carbon atom to which a fluorine atom is not bonded. Particularly, a hydroxyl group is present at a bonding terminal carbon atom or a carbon atom adjacent to the bonding terminal carbon atom (there is no fluorine atom bonded to these carbon atoms). It is preferred that they are bonded.

As R, a group represented by the following formula 2 is preferable. R ^a -W -... Formula 2 The symbols in Formula 2 have the following meanings. ^Ra : a C1-C29 polyfluoroalkyl group or a C1-C29 polyfluoroalkyl group having an etheric oxygen atom. W: an alkylene group having 1 to 29 carbon atoms or an alkylene group having 1 to 29 carbon atoms having a hydroxyl group.

As a method for synthesizing the thiadiazole derivative represented by the above formula 1 (hereinafter referred to as compound 1), for example, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole (where R is hydrogen Compounds that are atoms)
And a method of subjecting a compound represented by R-OH to an esterification reaction. In the esterification reaction (dehydration condensation), an acid catalyst such as paratoluenesulfonic acid may be present as a catalyst.

The present invention is also a metal rust inhibitor comprising Compound 1. The metal rust preventive has the effect of protecting the metal surface, suppressing its corrosion, and preventing the occurrence of rust and the like. The metal rust preventive composed of compound 1 can be used alone or in combination of two or more in various applications where such effects are required. The metal rust preventive of the present invention can be used in combination with other metal rust preventives.

The rust inhibitor for metals of the present invention can be used by adding it to a medium that comes into contact with metals. For example, it can be used by being added to an aqueous medium or a non-aqueous medium that comes into contact with a metal. Further, it can be used by being added to a metal coating agent such as a metal coating paint. In particular, by adding to a treating agent for a metal article or an article having a metal portion and using the treating agent, the risk of corrosion, alteration, rust, and the like of the metal caused by contact of the treating agent with the metal is reduced. The following metals are preferred as the metal to be treated.

The present invention is also a treating agent for treating a metal article or an article having a metal part, which comprises Compound 1. In particular, it is a treating agent for treating the surface of such an article. For example, there is a metal detergent obtained by adding Compound 1 to a metal detergent comprising an aqueous medium or a non-aqueous medium.

The metals to be treated include copper, aluminum, silver, iron, nickel, zinc, tin, lead, titanium, other metals or alloys of these metals. As will be described later, electronic parts are typical examples of the target article, and tin, lead alloys such as copper, copper alloy, aluminum, aluminum alloy, and solder used therein are preferable. Although not particularly limited as a metal article or an article having a metal portion, electronic components, especially printed wiring boards, capacitors,
Preferred are resistors, ICs, transistors, and other electronic and electrical elements.

As a treating agent for an electronic component, a flux rising preventing agent and a resin adhesion preventing agent are preferable. That is, as the above-mentioned treating agent, a flux rising preventing agent and a resin adhesion preventing agent containing Compound 1 or as an active ingredient for treating an electronic component or the like are preferable. By using these treatment agents, the above pretreatment can be omitted, that is, the flux rising prevention treatment and the resin adhesion prevention treatment can be performed without the pretreatment.

The purpose of the flux rising preventing agent is to prevent the flux from penetrating or adhering to portions where soldering is unnecessary when applying flux for soldering elements or the like to a printed wiring board. Used for etc. For example, a flux rising prevention agent is applied to a predetermined portion of the element mounting surface of the printed wiring board, particularly around the lead wire insertion hole, and the flux applied to the non-mounting surface (the surface where the lead wire is soldered) is inserted into the insertion hole. To prevent it from penetrating from the surface and rising to the mounting surface side.

On the other hand, the resin adhesion preventing agent is used for the purpose of preventing the resin from adhering to a portion where the resin is not to be adhered in a resin sealing or the like of an electronic component in advance. For example, when a capacitor element is sealed with an epoxy resin or the like, a resin adhesion preventing agent is applied to the lead wire portion in advance to prevent the epoxy resin from adhering to the lead wire portion.

As the flux rising preventing agent and the resin adhesion preventing agent, it is preferable to include a compound having an R ^f group, particularly an R ^F group, as described above. In particular, in compound 1, R
Is preferably a compound represented by the formula (2). The group represented by the formula 2 has a very high hydrophobicity, is less familiar with relatively hydrophobic substances such as flux and resin, and has a property of repelling it. The effect is exhibited.

Among the compounds 1, the compound having extremely high hydrophobicity can be used alone as a flux rising preventing agent or a resin adhesion preventing agent. Among the compounds 1, compounds in which R is a highly hydrophobic monovalent organic group such as an R ^f group have such properties.

The flux rising preventing agent and the resin adhesion preventing agent have a rust-preventing effect on metals in addition to the inherent effects of the agents. Therefore, without performing pretreatment for rust prevention, it is possible to impart a flux rising prevention effect, a resin adhesion prevention effect, and a rust prevention effect to the electronic component.

Compound 1 can also be used in combination with a conventional flux rising inhibitor or resin adhesion inhibitor. In this case, as the compound 1, not only the above-mentioned compound having a particularly high hydrophobic group but also a compound having a lower hydrophobicity may be used. For example, compound 1 where R is an alkyl group may be used. Such a compound 1 has high solubility in a solvent used for dissolving the flux rising preventing agent and the resin adhesion preventing agent, and has good compatibility with the flux rising preventing agent and the resin adhesion preventing agent.

The treating agent of the present invention, particularly the flux rising preventing agent and the resin adhesion preventing agent, are usually used after being dissolved in a solvent. As the solvent, a hydrocarbon solvent or a fluorinated solvent is preferred. The concentration of the compound 1 in the solvent is not particularly limited, but is preferably 1 ppm to 10% by weight,
Particularly, 10 ppm to 1% by weight is preferable. In the case of the treating agent having Compound 1 of the present invention as a sole component, a portion having a relatively high concentration in this range is employed, and 100 ppm to 100 ppm
10% by weight is preferred. When used in combination with a conventional treating agent, the concentration is preferably 10 ppm to 1% by weight, depending on the concentration of the conventional treating agent.

The present invention is also a water / oil repellent comprising Compound 1. Among the compounds 1, compounds having extremely high hydrophobicity have water / oil repellency and can be used as a water / oil repellent by themselves. Compound 1 can be used in combination with a conventional water / oil repellent.

The water / oil repellent of the present invention can impart water / oil repellency to various materials such as metals, resins and plastics. Further, since a plurality of steps of conventional rust prevention treatment and water / oil repellency treatment can be performed in one step, it is useful as a water / oil repellent for metal surface treatment. By treating the metal surface with the water and oil repellent of the present invention to form a thin film on the metal surface, it is possible to impart both a water and oil repellency effect and a rust prevention effect to the metal surface.

The water / oil repellent of the present invention can be applied to an object by any method. For example, the compound 1 is dissolved or dispersed in an organic solvent or water to form a treatment liquid, and the treatment liquid is applied to an object to be treated by a method such as dip coating, spray coating, foam coating, brush coating, and the like. Alternatively, a method of drying by heating. As a particularly simple method, a treatment solution in which Compound 1 is dissolved in a hydrocarbon-based solvent or a fluorinated solvent is applied to the treatment object, or the treatment object is immersed in the treatment solution, and then dried at room temperature. Is mentioned. By this method, a thin film containing Compound 1 is formed on the surface of the object.

The water / oil repellent of the present invention can be used in combination with a foaming agent such as a surfactant, a stabilizer, a dispersant and the like, depending on the use.
The concentration of Compound 1 in the treatment liquid is preferably 1 ppm to 10% by weight, particularly preferably 10 ppm to 1% by weight.

[0033]

EXAMPLES Synthesis Examples (Examples 1 to 3) and Examples (Examples 4 to 7, 9)
The present invention will be specifically described with reference to Comparative Examples (Examples 8, 13, and 16).

Example 1 Synthesis of Compound A F (CF ₂ ) ₈ (C
H _{2) 3} OH and 30.0 g, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole (manufactured by Toyo Kasei Kogyo Co., Ltd.)
15.9 g, 150 g of toluene, and 0.66 g of paratoluenesulfonic acid monohydrate were charged and reacted for 7 hours while azeotropically dehydrating under reflux. After the completion of the reaction, the mixture was cooled to room temperature, 650 g of dichloromethane was added, and 400 ml of water was added.
g for 3 times. After distilling off dichloromethane under reduced pressure,
The crystals were recrystallized from 100 g of toluene and dried under reduced pressure to obtain 39.2 g (yield 94%) of a compound A represented by the following formula.

[0035]

Embedded image

¹ H-NMR (CDCl ₃ , TMS) σ (p
pm): 4.21 (t, J = 6.2 Hz, 2H);
89 (s, 2H), 2.03 (m, 4H), ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) σ (ppm):
−80.55 (t, J = 9.5 Hz, 3F), −113.
63 (t, 2F), -121.28 (s, 6F), -1
22.13 (s, 2F), -122.79 (s, 2
F), -125.60 (d, J = 13.4, 2F), IR: 1750 cm ^-1 (C = O).

Example 2 Synthesis of Compound B F (CF_Two)₈(CH_Two)_Three30.0 g of OH
To F (CF_Two)_Four(CH _Two)_TwoAfter changing to 16.3g of OH
Except that the compound B represented by the following formula
2.3 g (80% yield) were obtained.

[0038]

Embedded image

¹ H-NMR (CD ₃ COCD ₃ , TMS)
σ (ppm): 4.46 (t, J = 6.1 Hz, 2
H), 4.08 (s, 2H), 2.64 (t, t, J =
6.2, ¹⁹ Hz, 2H), ¹⁹ F-NMR (CD ₃ COCD ₃ , CFCl ₃ ) σ (pp
m): -80.82 (m, 3F), -113.18 (m
, 2F), -124.00 (m, 2F), -125.
55 (m, 2F), IR: 1750 cm ^-1 (C = O).

Example 3 Synthesis of Compound C 30.0 g of F (CF ₂ ) ₈ (CH ₂ ) ₃ OH in Example 1
Example 1 except that was changed to 11.5 g of H (CH ₂ ) ₁₂ OH
17.4 g of compound C represented by the following formula
(75% yield).

[0041]

Embedded image

¹ H-NMR (CD ₃ COCD ₃ , TMS)
σ (ppm): 4.08 (d, t, J = 1.2, 6.
5,2H), 4.02 (d, J = 1.5 Hz, 2H),
1.22 (s, 20H), 0.81 (d, d, J = 5.
5,6.5 Hz, 3H), IR: 1730 cm ^-1 (C = O).

Example 4 Compound A was prepared by mixing m-xylene hexafluoride with 1,1,1,2,2,3,4,5,5,5
-200 ppm of a solution of decafluoropentane dissolved in a mixed solvent having a volume ratio of 7: 3 (hereinafter referred to as solvent E) at 200 ppm, the solution was maintained at 40 ° C, and brass was silver-plated there.
A test piece of mx 2 cm x 1 mm was immersed for 1 minute, dried at 80 ° C for 3 minutes, and subjected to rustproofing.

In a corrosion gas tester (manufactured by KS Parts Laboratory), the temperature was 40 ° C., the humidity was 90% RH, and the hydrogen sulfide concentration was 3 pp.
The test piece treated as described above was exposed for a certain period of time (3 hours or 6 hours) in an atmosphere of m, left for 1 hour, and the solder wetting time and appearance were measured. Table 1 shows the results.

[Solder Wetting Time] According to JIS: C0053 (Environmental test method-Electrical / Electronic-Soldering test method (equilibrium method)), the solder temperature is 235.
C., immersion speed 2 mm / sec, immersion time 10 seconds, immersion depth 2 mm. This indicates that the shorter the solder wetting time, the less rust is generated on the surface, and the easier the next step such as the step of attaching metal parts.

[Appearance Evaluation Criteria] 1: Rust is generated on the entire surface, 2: Rust is generated on almost the entire surface, 3: Rust is generated partially, 4: Rust is generated slightly, 5: No corrosion occurs.

[Examples 5 to 8] The same test was carried out using Compound B, Compound C, and benzotriazole (hereinafter, referred to as Compound D) instead of Compound A or those not added. Table 1 shows the results. From these results, it was confirmed that the compound of the present invention has high rust prevention performance.

[0048]

[Table 1]

[Example 9] [F (CF ₂ ) ₈ CH
0.2% by weight of a copolymer (hereinafter referred to as copolymer X) obtained by polymerizing a monomer mixture of ₂ CH ₂ OCOCH ： CH ₂ ]: [cyclohexyl methacrylate] at a molar ratio of 8: 2. , And Compound A were dissolved in 200 ppm, and the same rust prevention treatment and exposure test as in Example 4 were performed, and the solder wetting time and appearance were measured. Table 2 shows the results.

[Examples 10 to 13] The same test as in Example 9 was carried out on compound B, compound C, compound D or those without addition of compound A. Table 2 shows the results.

[0051]

[Table 2]

The addition of Compound 1 did not show any decrease in the performance as a flux rising inhibitor or a resin adhesion inhibitor. Compound 1 was confirmed to have high anticorrosion performance. In addition, compound 1 is used as copolymer X
It was confirmed that even when added, the rust prevention performance was kept high, and there was no effect on the flux rising performance and the resin adhesion prevention performance.

Example 14 Compound A was placed in solvent E at 500 p.
pm was dissolved therein, and a test piece obtained by applying silver plating to brass was washed with methanol, soaked at 20 ° C. for 1 minute, and then dried at room temperature for 3 hours. The contact angle of the test piece with ion-exchanged water and n-hexadecane was measured. The larger the contact angle with ion-exchanged water, the higher the water repellency, and the larger the contact angle with n-hexadecane, the higher the oil repellency. The results are shown in Table 3.

[Examples 15 and 16] The same test as in Example 14 was carried out using Compound B in place of Compound A or untreated. Table 3 shows the results.

[0055]

[Table 3]

It was confirmed that the water / oil repellent containing the compound A and the compound B had a high rust preventive effect and a high water / oil repellent effect.

[0057]

The novel thiadiazole derivative of the present invention has a high rust-inhibiting effect by itself and is therefore a very excellent compound particularly as a rust inhibitor for metals. This metal rust inhibitor exhibits excellent performance as a treating agent such as a flux rising inhibitor or a resin adhesion inhibitor. In addition, it has a water repellent and oil repellent effect as well as a rust preventive effect, and can be used as a water repellent and oil repellent for treating metals.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Ryota Tokukura Inventor F-term (reference) in 3-2-10 Chigasaki, Chigasaki-shi, Kanagawa Prefecture 4C036 AD08 AD20 AD26 AD27 4H020 BA07 BA26

Claims (5)

[Claims] 1. A thiadiazole derivative represented by the following formula 1. Embedded image R in Formula 1 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, and an oxygen atom may be inserted between carbon-carbon bonds in the group. And -CH _2- in the group may be substituted with -OCO- or -COO-, and a hydrogen atom in the group may be substituted with a fluorine atom or a hydroxyl group. 2. The compound according to claim 1, wherein R in the formula 1 is a group shown below.
2. The thiadiazole derivative according to item 1. R: an alkyl group or an alkenyl group having 8 to 30 carbon atoms,
A polyfluoroalkyl group or polyfluoroalkenyl group having 2 to 30 carbon atoms, the carbon in the group - may be the carbon-carbon bond has been inserted an oxygen atom, -CH in group ₂
The —, —CFH— or —CF ₂ — moiety may be substituted with —OCO— or —COO—, and a hydrogen atom or a fluorine atom in the group may be substituted with a hydroxyl group. 3. A rust inhibitor for metals comprising the thiadiazole derivative according to claim 1 or 2. 4. A treating agent for treating a metal article or an article having a metal portion, comprising the thiadiazole derivative according to claim 1 or 2. 5. A water / oil repellent comprising the thiadiazole derivative according to claim 1 or 2.