JP2000328042A - Sealing compound composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component room-temperature-storing sealing compound composition which has a high moisture-barrier property and a good shelf stability, cures immediately when heated and gives a cured product having good physical properties. SOLUTION: This composition comprises (a) a polyisobutylene compound having an alkenyl group, (b) a compound having at least two hydrosilyl groups within a molecule, (c) a platinum catalyst and (d) a compound which inhibits the hydrosilylation-promoting effect of the platinum catalyst at an ordinary temperature but not at an elevated temperature. Preferably, the component (d) is chosen from the group consisting of a thiophene compound, an isocyanide compound, a cyclic thioether compound, a cyclic azoether compound, an imino compound and a polymer which contains more than one sulfur, nitrogen or phosphorus atom-containing functional groups which form complexes with platinum atoms per molecule and has an average molecular weight of 1,000 to 200,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-part sealant composition which can be cured by heating, and in particular, a cured product of the composition of the present invention has low moisture permeability and is suitable for sealing electronic parts and the like which do not like moisture. It is suitable for.

[0002]

2. Description of the Related Art Silicone resins which cure with moisture in the air have been well known as sealant compositions. Silicone resin is excellent in heat resistance and cold resistance and has sufficient performance as a general-purpose sealant, and is widely used for construction, automobile machinery and the like. However, as can be seen from the fact that a silicone resin cures a thick film by atmospheric moisture, the cured product has a relatively high moisture permeability. For this reason, silicone resin has been insufficient for sealing a case or the like of a component that stores therein an electronic component whose performance is deteriorated or damaged by moisture.

[0003] The above-mentioned silicone resin has a hydrolyzable group bonded to a silicon atom and has a silicon atom-containing group which can be crosslinked by forming a siloxane bond (hereinafter referred to as "hydrolyzable silicon group"). ), And those using an oxyalkylene-based polymer or an isobutylene-based polymer as the molecular main chain are already known. Since these are cured at normal temperature by moisture to obtain a rubber-like cured product, they have been conventionally used. However, in any case, there is a problem that curing by moisture has low reactivity and requires a long time for curing. Further, the isobutylene-based polymer having a hydrolyzable silicon group has a lower moisture permeability than the oxyalkylene-based polymer or dimethylsiloxane-based polymer having a hydrolyzable silicon group, so that the moisture curability is very poor, and the There is a problem that the curability is poor. Therefore, 2
It had to be a liquid mixing type, but this was inconvenient.

Further, the conventional sealing material is insufficient as a sealing agent for preventing moisture from deteriorating from a member for accommodating an electronic component whose performance is deteriorated or damaged by moisture.
For example, the performance of an electrode portion of a solar cell, a satellite antenna, or the like is significantly reduced due to moisture in the air. Also, CdS / Cd
A solar cell or the like containing Te as a photovoltaic portion may generate harmful substances when exposed to moisture, and may pose a threat to the environment or the human body. Therefore, a sealant that completely blocks moisture in the air has been required. .

[0005]

As a rubber material having low moisture permeability, an isobutylene-based polymer has been conventionally proposed, and a method of forming a curable resin which can be cured by a desired method has been studied.

For example, by adding a hydrolyzable silane such as an alkoxysilane or an oxime silane to a polyisobutylene molecule to obtain a moisture-curable resin, or by imparting an acrylic group or a glycidyl group, a heat-curable resin or a photocurable Various methods have been disclosed for converting isobutylene resin into a curable resin by using various methods such as resin.

[0007] A method has also been disclosed in which silicon containing an alkenyl group is added to the molecule of polyisobutylene to obtain a curable resin that undergoes a hydrosilylation reaction with a hydrogen-containing silicon compound. Generally, the one-part type by the hydrosilylation reaction suppresses the activity of the platinum catalyst during storage by adding a reaction inhibitor to the composition, and when curing is desired, increases the catalytic activity by heating. Is achieved on the principle of starting. However, since polyisobutylene is a polymer and has few crosslinking points, an excellent cured product cannot be obtained unless the activity of the platinum catalyst is high.

Therefore, when the main chain is a one-component type of polyisobutylene, a combination of a conventionally known reaction inhibitor and a platinum catalyst is examined to optimize the balance between storage stability and curing time during heating. However, there is a disadvantage that the resin strength of the final cured product does not reach the original strength of polyisobutylene. In short, there is nothing satisfying the preservability, the curing time, and the final strength, and at present, it has not been put to practical use.

If the cured product has a low resin strength, it can withstand use in a static state when used as a sealing material.
It cannot be used for sealing high-pressure parts, high-temperature parts, or parts where vibration or impact is applied.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional curable resin composition, that is, (a) a polyisobutylene compound having an alkenyl group and ( b) a compound having at least two hydrosilyl groups in the molecule and (c) a platinum catalyst, and (d) a compound that suppresses the ability of the platinum catalyst to promote hydrosilylation at room temperature and does not suppress the ability at high temperatures. The purpose of the present invention is to provide a one-part sealant composition which can be cured by heating.

The alkenyl group-containing polyisobutylene compound (a) of the present invention is a compound whose main chain component contains 50 mol% or more of isobutylene units as a monomer composition. Is a bifunctional moiety such as 1,4-bis (α-chloroisopropyl) benzene proposed by Kennedy or 1,
It is produced by an inifer method (US Pat. No. 4,276,394) in which a trifunctional component such as 3,5-tris (α-chloroisopropyl) benzene is used as an initiator / chain transfer agent, and BCL ₃ is used as a catalyst to cationically polymerize isobutylene. The isobutylene unit is preferably 50 mol or more of polyisobutylene, but in order to improve the low moisture permeability, high reactivity, storage stability and the like of the present invention, it is preferable that the isobutylene unit has a large amount,
The entire main chain of the component (a) may be formed from isobutylene units, and preferably 90% or more is isobutylene.

The monomer which can be copolymerized with isobutylene as a repeating unit other than isobutylene is one having 4 to 12 carbon atoms.
Olefins, vinyl ethers, aromatic vinyl compounds,
Examples include vinyl silanes and allyl silanes. Specific examples of the copolymer component of such a monomer include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, hexene, cyclohexene,
Aliphatic olefins such as vinylhexane, 5-ethylidene norbornene, indene and β-pinene; dienes such as cyclopentadiene and dicyclopentadiene; and styrenes such as styrene, α-methylstyrene and p-chlorostyrene. Can be.

The method of introducing an alkenyl group into the polyisobutylene of the component (a) can be roughly classified into a method of introducing an alkenyl group after polymerization of a main chain and a method of introducing an alkenyl group during polymerization. Examples of a method of introducing an alkenyl group after polymerization include, for example, converting a hydroxyl group at a terminal, main chain, or side chain into a group such as -ONa or -OK, followed by a reaction with a compound having an alkylene and a halogen atom, to thereby obtain a terminal alkenyl group. A polyisobutylene having groups is produced. Compounds having a halogen atom and an alkylene include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, chloropropene, chlorobutene, chloromethyl (meth) acrylate, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl ( Chloromethyl) ether, allyl (chloromethoxy) benzene, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

Methods for converting the terminal hydroxyl group of terminal hydroxy polyisobutylene into an oxymetal group include alkali metals such as Na and K; metal hydrides such as NaH;
Metal alkoxides such as OCH _3; caustic soda, a method of reacting with such caustic alkali such as caustic potassium.

The method of introducing an alkenyl group into polyisobutylene having a covalently bonded Cl group is not particularly limited. For example, a method of performing a Friedel-Crafts reaction of various alkenyl phenyl ethers with a Cl group, allyltrimethylsilane And a Cl group in the presence of a Lewis acid in the presence of a Lewis acid, and a Friedel-Crafts reaction between various phenols and a Cl group to introduce a hydroxyl group, and further use the above-mentioned alkenyl group introduction method in combination. There is a method.

As a method for introducing an alkenyl group during polymerization, for example, a compound having a halogen atom as an initiator and a chain transfer agent, and a compound having the halogen atom bonded thereto, and / or
Alternatively, a compound having a halogen atom, wherein the carbon atom to which the halogen atom is bonded is a tertiary carbon atom, and a cationic polymerizable monomer containing isobutylene is cationically polymerized using a Lewis acid as a catalyst. In making it, an allyl-terminated polyisobutylene production method by adding allyltrimethylsilane to the polymerization system,
Similarly, non-conjugated dienes such as 1,9-decadiene,
Alternatively, a method for producing polyisobutylene having an alkenyl group at an end of a main chain or a side chain by adding an alkenyloxystyrene such as p-hexenyloxystyrene to a polymerization system may be mentioned.

[0017] (a) In addition to the production method of the component above, the polymerization immediately after the polyisobutylene are reacted allylsilane, or alkenyl trimethylsilane TiCl ₄ was added to the polyisobutylene having a chloro group at both ends was simple interest generated To obtain a polymer having alkenyl groups at both ends (Japanese Patent Application Laid-Open No. 63-1050).
No. 05), a method of using a non-conjugated diene as a copolymer or a terminal stopper (Japanese Patent Application Laid-Open No. 4-288309), a method of converting a vinyl-type carbon-carbon unsaturated group into moisture-curable by a hydrosilylation reaction ( Tokiko 4-696
No. 59, JP-A-4-233916) and the like, and these methods may be used.

The component (b) of the present invention is not limited as long as it is a compound containing at least two hydrosilyl groups in the molecule. Here, one hydrosilyl group refers to one SiH group. Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups. As the component (b), conventionally known polyorganohydrogen is one of the preferable ones. In the polyorganohydrogensiloxane, SiH may be present at the terminal of the molecular chain or may be attached in the middle of the molecular chain. Further, the polysiloxane may be a cyclic body.

However, since the polyorganohydrogensiloxane alone is not highly compatible with the component (a),
It is preferable to use a compound obtained by bonding the above-mentioned hydrogen siloxane to a saturated hydrocarbon having 2 to 2,000 carbon atoms having high compatibility with the component (a). For details thereof, the technology described in Japanese Patent Application Laid-Open No. 8-127683 can be used.

The number of hydrosilyl groups contained in the component (b) may be at least two in one molecule.
2 to 15 are preferred, and 3 to 12 are particularly preferred. When the composition of the present invention is cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, curing is slow and poor curing often occurs. If the number of the hydrosilyl groups is more than 15, the stability of the curing agent (b) becomes poor, and after curing, a large amount of hydrosilyl groups remains in the cured product, causing voids and cracks. Becomes

The hydrosilylation reaction catalyst which is the component (c) of the present invention is a catalyst for crosslinking the components (a) and (b) by a hydrosilylation reaction, and usually comprises an organometallic complex of a platinum atom.

The component (c) in the present invention is a catalyst for crosslinking the component (a) and the component (b) by a hydrosilylation reaction, and usually comprises a platinum atom organometallic complex. As the hydrosilylation catalyst, a conventionally known appropriate platinum catalyst can be used. Examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of platinum and ketones, complexes of platinum and vinylsiloxane, etc., and particularly preferred are Ashby's U.S. Pat.
No. 9601, a platinum-alcoholate complex described in Lamoreau No. 3220970, a platinum-olefin complex described in Kerstedt No. 3516946, a catalyst represented by Spire (Advanced Organic Chemistry, 17
Vol., P. 407, 1979).

In the present invention, the added amount of the platinum catalyst is as follows:
(A) Component (b) Usually 10 ppm to 100 ppm, preferably 30 ppm, based on the weight of the composition of the component.
To 70 ppm.

The component (d) in the present invention suppresses the ability of the component (c) to promote the hydrosilylation reaction at room temperature,
It is a compound that is not inhibited at high temperatures when the composition is heated.
By combining the components (d) and (c), a one-pack type heat-curable resin that can be stored at room temperature can be obtained.

As an example of the component (d), a thiophene compound, an isocyanide compound, a cyclic thioether compound, a cyclic azoether compound, an imino compound, and a sulfur-, nitrogen-, or phosphorus-containing functional group capable of forming a complex with a platinum atom are one molecule. Average molecular weight of 1,000 to 2
At least one member selected from the group consisting of 00,000 polymers can be mentioned.

Hereinafter, the component (d) will be described in detail. The thiophene compound exhibits excellent storage stability near room temperature without impairing the curability of the composition at high temperatures when added in a small amount. The first component (d) used in the present invention is a thiophene compound. As the thiophene compound, a thiophene compound represented by the following general formulas (1) and (2) is preferably used.

[T] _n (1)

In the formula, T represents a thiophene molecular skeleton, and n represents an integer of 1 to 4. Specifically, there are thiophene in a narrow sense and dithiophene, trithiophene, and tetrathiophene in which 2 to 4 unsubstituted thiophene skeletons are linearly bonded.

Ar-T-Ar '(2)

Here, T represents a thiophene molecular skeleton, and Ar represents
Represents an aryl group or an arylalkyl group, and Ar-
Represents an aryl group, an arylalkyl group or a hydrogen atom. Here, examples of the aryl group constituting the aryl group or the arylalkyl group include a phenyl group, a naphthyl group or a phenyl group or a naphthyl group having 1 to 3 alkyl groups, an alkoxy group, a halogen or a hetero atom-containing substituent. You. Examples of the arylalkyl group include those in which a benzyl group or a phenyl group constituting the benzyl group is the above-mentioned substituted phenyl group.

Specific examples of the thiophene compound include thiophene, bithiophene, terthiophene, benzothiophene, 2-methyl-benzothiophene and 2-methoxy-thiophene.
Thiophene derivatives such as benzothiophene, 2-bromo-benzothiophene, dibenzothiophene, 2,2′-methyl-dibenzothiophene, and 2,2′-dibromo-dibenzothiophene.

The second component (d) used in the present invention is an isocyanide compound. As the isone anide compound, a compound represented by the following general formula (3) is preferably used.

R ¹ -NC (3)

However, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group and an arylalkyl group. The alkyl group has 1 to 1 carbon atoms.
A straight-chain or branched alkyl group of 0 is preferred, and a branched tertiary alkyl group is particularly preferred. The cycloalkyl group is preferably a 5- to 8-membered cycloalkyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the arylalkyl group include a benzyl group.
Those in which the aryl group constituting these has an alkyl group, an alkoxy group, a halogen group or a heterocyclic-containing substituent as a substituent are also preferably used.

As these isocyanide compounds, commercially available products can be used, but those synthesized according to the method described in “Organic Functional Group Preparation (published by Academic Press, 1986, page 206)” can be used. Is preferred. (D)
Specific examples of the compound used as a component include ethyl isocyanide, isopropyl isocyanide, tertiary butyl isocyanide, 1,1,3,3-tetramethylbutyl isocyanide, cyclohexyl isocyanide, benzyl isone anide, 4-methyl-benzyl isocyanide, 4-chloro-benzylisone anide, phenyl isocyanide, 4-butyl-phenyl isocyanide, 4-chloro-phenyl isocyanide, 3-methoxy-phenyl isocyanide, 4-methoxy-phenyl isocyanide,
Isocyanide compounds such as 2,6-methyl-phenyl isocyanide are exemplified.

The third component (d) used in the present invention is a cyclic thioether compound or a cyclic azoether compound.
These compounds include the following general formulas (4) and (5)
The compound represented by is preferably used.

[0037]

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Wherein R ⁵ is a divalent hydrocarbon group having 3 to 18 carbon atoms, and n is an integer of 3 or more. The hydrocarbon group is preferably an alkylene group, and n is preferably from 3 to 8, particularly preferably from 4 to 6.

Specific examples of the cyclic thioether compound include 1,4,7,10-tetrathiacyclohexadecane (1
2-thiacrown-4), 1,4,7,10,13-pentathiacyclopentadecane (15-thiacrown-
5), 1,4,7,10,13,16-hexathiacyclooctadecane (18-thiacrown-6), dibenzo-18-thiacrown-6, dinaphth-12-thiacrown-4, zinc chloride Substitutes of the above thiocrown ether compounds such as hexyl-15-thiacrown-5 and the like.

Specific examples of the cyclic azoether compound include 1,4,7,10-tetraazacyclododecane (12-
Azacrown-4), 1,4,7,10,13-pentaazacyclopentadecane (15-azacrown-5),
1,4,7,10,13,16-Hexazaazacyclooctadecane (18-azacrown-6) and the like, as well as the above-mentioned cyclic thioethers, and substituted products can also be mentioned.

The fourth component (d) used in the present invention is an imino compound. As the imino compound, the following general formula (6)
The compound represented by is preferably used.

R ² -N = C (R ³ , R ⁴ ) (6)

Here, R ² is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group and an arylalkyl group. R ³ and R ⁴ each independently represent a hydrogen atom or an optionally substituted carbon atom of 1 to 1;
And a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group.

Specific examples of the imino compound include ethylideneaniline, benzylideneaniline, benzylidenebenzylaniline, benzylidenemethylamine, benzylidenebutylamine, α-methyl-benzylideneaniline, α
Schiff bases such as -phenyl-benzylideneaniline.

The fifth component (d) used in the present invention is a polymer having an average molecular weight of 1,000 to 200,000 having a plurality of functional groups capable of forming a complex with a platinum atom in one molecule.
Examples of the functional group include a complex-forming organic functional group having a sulfur atom, a nitrogen atom or a phosphorus atom, and examples thereof include a sulfide group, a secondary or tertiary amino group, a phosphine group, a thiophene group and an imino group.

As the sulfide group, a group represented by the general formula (7) is preferably used.

-R ⁶ -SR ⁷ (7)

Wherein R ⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably an alkylene group or an arylene group, and R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group. , An aryl group or a cycloalkyl group.

As the secondary or tertiary amino group, a group represented by the general formula (8) is preferably used.

-R ⁸ -N (R ⁹ , R ¹⁰ ) (8)

Wherein R ⁸ is a divalent hydrocarbon group having 1 to ⁸ carbon atoms, preferably an alkylene group or an arylene group;
⁹ and R ¹⁰ are a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group, an aryl group or a cycloalkyl group, but both R ⁹ and R ¹⁰ are not hydrogen.

As the phosphine group, a group represented by the general formula (9) is preferably used.

-R ¹¹ -P (R ¹² , R ¹³ ) (9) wherein R ¹¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably an alkylene group or an arylene group, and R ¹² and R ¹³ Is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group, an aryl group or a cycloalkyl group. These functional groups are usually introduced as side chains into the polymer.

The polymer constituting the main chain has a thiophene group and an imino group as functional groups, and a group in which one hydrogen atom bonded to a carbon atom in the thiophene compound and the imino compound is a bond to a polymer molecule. is there. These complexing functional groups are usually introduced as side chains into the polymer molecule.

The polymer constituting the main chain includes a carboquinol group (or a functional derivative thereof), a hydroxy group,
A polymer having a reactive functional group such as a halogen atom in a repeating unit is preferable, and the above-mentioned fifth component (d) can be easily produced by reacting a compound containing the above functional group with the functional group. it can.

Examples of such polymers include acrylic acid or methacrylic acid (or their functional derivatives)
And vinyl alcohol-based polymers having vinyl alcohol as a constituent monomer, styrene-based polymers having styrene having a reactive functional group such as halogen at the para-position, and phenolic resins. These may be homopolymers or copolymers obtained by copolymerizing appropriate comonomers. It is preferable to use an optimal combination of monomers for adjusting the balance between the solubility in the silicone composition and the curing temperature.

A polymer having a functional group capable of coordinating with a platinum atom by previously polymerizing a polymerizable monomer having a sulfide group or the like in a side chain, for example, an acryloyl monomer or a vinyl monomer, alone or together with another comonomer, may be prepared. As described above, a reactive monomer containing a functional group such as a sulfide group may be reacted with a polymer having a group capable of reacting with the reactive group. Examples of the latter are a sulfide compound having a carboxyl group-reactive polymer such as polyacrylic acid or a carboxyl group of acrylic acid and methyl acrylate, and a functional group reactive with the carboxyl group, for example, a bromomethyl group. There is a method of reacting with a tertiary amino compound or a phosphine compound. In this reaction, for example, a polar organic solvent such as dimethyl sulfide is used as a solvent, and 1,8-diaza (5,4,4) is used as a catalyst.
0) It proceeds easily by using bicycloundecene-7 or the like.

The amount of the component (d) is theoretically 2 equivalents to the platinum atom. If the amount is too small, a sufficient effect of suppressing the reaction cannot be obtained. If the amount is too large, curing at an appropriate temperature is difficult. Become. Usually, 1 to 5 equivalents, more preferably 1 to 3 equivalents are used per platinum compound. In the case of a polymer, the number of equivalents of the complex-forming functional group is calculated. Usually, it is preferable that 5% or more of the polymerization degree of the polymer (that is, 5% or more of the total number of repeating units) has a complex-forming functional group.

In the present invention, the above components (a) to (d) are blended as essential components, but the blending order is not particularly limited. For example, a method of preliminarily blending the components (c) and (d) to form a complex and then blending the components (a) and (b), a method of simultaneously blending the components (a) to (d), or the like is appropriate. Adopted.

The sealant composition of the present invention basically comprises the above-mentioned components. If necessary, the sealant composition further improves the flow characteristics before curing, and improves the mechanical properties required for the rubber-like elastic body after curing. In order to provide, an inorganic filler in the form of fine powder can be added. As inorganic fillers, fumed silica, quartz fine powder, calcium carbonate, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesia, zinc oxide, zinc carbonate, and silanes, silazanes, Examples thereof include low-polymerization degree siloxanes, organic compounds, and the like, which are surface-treated.

Further, an organic solvent, a fungicide, a flame retardant, a plasticizer, a thixotropy-imparting agent, an adhesion-imparting agent, a curing accelerator, a pigment and the like can be added to the sealant composition of the present invention. Examples of the plasticizer include hydrocarbon compounds such as polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated polybutadiene, paraffin oil and naphthenic oil, chlorinated paraffins, phthalic acid such as dibutyl phthalate and di (2-ethylhexyl) phthalate. Non-aromatic dibasic acid esters such as esters, dioctyl adipate, dioctyl sebacate, esters of polyalkylene glycol,
Phosphoric esters such as tricresyl phosphate and the like can be mentioned.

Further, the sealing material composition of the present invention is excellent in storability at a temperature around room temperature and is rapidly cured by moderate heating. Therefore, if the sealing material composition of the present invention is used, it is possible to shorten a working process of a product using the same, reduce a product cost, extend a working time using the same, and furthermore, at a relatively low temperature. Because of its excellent curability, energy saving is possible. Further, the composition of the present invention can be used as a one-pack type, and there is no need for mixing and the like as in a two-pack type. Even in the case of using a two-pack type, since there is no hardening in the mixing chamber or the nozzle of the mixing / coating machine, the labor such as cleaning can be omitted.

The composition of the present invention can increase the final strength of the one-part thermosetting polyisobutylene-based curable resin by combining the components (c) and (d).
Of course, it is useful as an industrial sealing material without reducing storage stability and curing time. Therefore, it is suitable for a sealant in a place where moisture is disliked, such as electronic parts. Specifically, it is an in-vehicle outdoor electronic device, an electric device, a housing or a substrate of a control board, or the like.

The sealant composition of the present invention can be used as a sealant for shutting off moisture such as a sealant for a main body and a lid of a housing container and the like, a coating of an entire surface of an electronic substrate, potting for embedding components in a container, and the like. In addition, when used for such purposes, it shows its true value.

[0065]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples. The scope of the present invention is not limited by these examples. In Examples and Comparative Examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified.
The test items in the table were measured according to the following procedure.

[Preparation of Base Resin] The main chain has an average molecular weight of 1
EPION 403, which is a polyisobutylene having a molecular weight terminal added with a methyldialkoxysilane.
(Kanebuchi Chemical Industry Co., Ltd.) 100 parts, HMS-30 which is an organopolysiloxane containing hydrogen silane
1 (manufactured by Gelest) in an amount of 3 parts were mixed and sufficiently stirred.

[Example 1-3] Component (c) 2.0
% Of platinum was added to an isopropanol solution of chloroplatinic acid hexahydrate, and 2 equivalents of the thiophene compound shown in the table as the component (d) were added to prepare a thiophene complex of platinum.
30 ppm of this platinum complex was added to the previously prepared base resin to obtain a target resin composition.

Example 4-6 A platinum complex comprising the components (c) and (d) was synthesized according to the following procedure. In Example 4, about 0.16 tertiary butyl isocyanide was used.
In a two-necked flask equipped with a dropping funnel containing gram (about 0.02 mol), about 0.42 g (about 0.01 mol) of platinum chloride potassium salt and 1 mol% of tetrabutylammonium chloride are added. After the atmosphere was sufficiently purged with nitrogen, it was dissolved in 5 ml of pure water. After confirming that the reaction substrate in the system was dissolved, the isocyanide compound in the dropping funnel was slowly dropped at room temperature. Thereafter, the mixture was vigorously stirred for 1 hour at room temperature to react. After the completion of the reaction, washing was performed twice with 50 ml of pure water, and the obtained complex was separated by filtration. The filtered complex was dried at room temperature under vacuum overnight, and then recrystallized twice using ethanol. Yield: 57.4%, melting point: decomposed at 220 ° C., IR (KBr, cm ⁻¹ ): 22
29, 1635, 1460 (all NC characteristic absorption)

In the same manner as described above, as Example 5, a platinum complex using cyclohexyl isocyanide as the isocyanide compound was synthesized. Yield: 60.0%, melting point: decomposed at 220 ° C, IR (KB
r, cm ^-1 ): 2268, 1637, 1452 (all characteristic absorption of NC)

In the same manner as described above, as Example 6, a platinum anchor was synthesized using phenyl isocyanide as the isonanid compound. Yield: 40.9%, melting point: decomposed at 250 ° C., IR (KB
r, cm ^-1 ): 2276, 1637, 1450 (all characteristic absorption of NC)

A platinum complex using the isocyanide compound shown in the table thus synthesized was added to the above base resin.

[Examples 7-10] In a base resin,
15 ppm of a solution of chloroplatinic acid hexahydrate containing 0% of platinum in isopropanol was added, and immediately thereafter, 2 equivalents of the imino compound shown in the table were added, followed by sufficient stirring to obtain a target resin composition.

[Examples 11-13] To a solution of chloroplatinic acid hexahydrate containing 2.0% platinum in isopropanol was added benzylideneaniline as an imino compound to prepare a platinum complex. The amount of benzylideneaniline added was 1 equivalent in Example 11, 2 equivalents in Example 12, and 3 equivalents in Example 13 based on platinum atoms. Thereafter, 30 ppm of this platinum complex was added to the previously prepared base resin to obtain a target resin composition.

[Examples 14-24] (Example 14) Polymethacrylic acid (0.86 g, 10 mmol) having a number average molecular weight of about 10,000 was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenylsulfite (2. 22 g, 11 mmol) and diazabicyclo- (5,4,0) -undecene-7 (1.67 g, 1
(1 mmol) was heated at 50 ° C. for 24 hours. After completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer having a sulfide group. (The recovery rate is 90%.) The introduction rate of the sulfide group is 98% based on the amount of the carboxylic acid in the polymer. (Calculated from 1HNMR based on the integral ratio of methine broton in the polymer side chain and the integral ratio of methyl group proton in the polymer main chain.) . The obtained polymer ligand was dissolved in tetrahydrofuran, 2 equivalents of chloroplatinic acid were added to the sulfide group of the polymer, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

Example 15 Number average molecular weight: about 50,000
Of poly (parachloromethylstyrene) (1.52 g, l
0 mmol) was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenyl sulfide (2.22) was dissolved.
g, 11 mmol) and diazabicyclo- (5,4,0)
-Undecene-7 (1.67 g, 11 mmol) was added and heated at 50 ° C for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer ligand having a sulfide group. (Recovery rate 78%, sulfide group introduction rate 98%: The measurement method is the same as in Example 1 and the same hereinafter). The obtained polymer is dissolved in tetrahydrofuran, and 3 equivalents of chloroplatinic acid are added to the sulfide group, and
The target platinum complex was prepared by heating at 0 ° C. for 3 hours.

Example 16 Number average molecular weight: about 10,000
Phenol resin (1.00 g, 10 mmol) was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenyl sulfide (2.22 g, 11 mmol) and diazabicyclo- (5,4,0) -undecene-7 were dissolved.
(1.67 g, 11 mmol) was added and heated at 50 ° C. for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer ligand having a sulfide group. (Recovery rate 90%, sulfide group introduction rate 81
%). The obtained polymer was dissolved in tetrahydrofuran, and a sulfide group and 4 equivalents of chloroplatinic acid were added.
For 3 hours to prepare the target platinum complex.

Example 17 Polymethacrylic acid having a number average molecular weight of about 2,000 was dissolved in dimethylformamide.
2-bromomethylthiophene and diazabicyclo- (5,
(4,0) -undecene-7 was added at 50 ° C for 24 hours.
Heated for hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover the corresponding polymer ligand. (Yield 99%, conversion 98%: confirmed by 1H NMR). Dissolve the obtained polymer ligand in tetrahydrofuran,
The target platinum complex was prepared by adding a thiophene group in a polymer side chain and 2 equivalents of chloroplatinic acid and heating at 40 ° C. for 3 hours.

(Example 18) N, N'-
Using dimethylaminoethyl methacrylate as a reaction solvent and ethanol and azobisisobutyronitrile as a polymerization initiator, polymerization was carried out at 60 ° C. for 3 hours. After polymerization,
The reaction solution was poured into a large amount of diethyl ether to obtain a polymer ligand having a dimethylamino group in the corresponding side chain (number average molecular weight: about 15,000). Thereafter, the obtained polymer ligand is dissolved in tetrahydrofuran, and a dimethylamino group in a polymer side chain and an equivalent amount of chloroplatinic acid are added.
The target platinum complex was prepared by heating at 0 ° C. for 3 hours.

Example 19 Using paraformylstyrene as a monomer, chlorobenzene as a reaction solvent, and azobisisobutyronitrile as a polymerization initiator, the reaction was carried out at 60 ° C. for 8 hours.
Polymerization was carried out for hours. After completion of the polymerization, the reaction solution was poured into a large amount of methanol to obtain a polymer having a formyl group in a side chain (number-average molecular weight: about 9000). Next, the obtained polymer was dissolved in dimethylformamide, 2 equivalents of aniline was added to the formyl group in the side chain of the polymer, and the mixture was heated at 50 ° C. for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer ligand having an imine group in the corresponding side chain. (Yield 90%, conversion 88%: 1H
Confirmed by NMR). Thereafter, the obtained polymer ligand was dissolved in tetrahydrofuran, an equivalent amount of chloroplatinic acid was added to the imino group of the polymer side chain, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

Example 20 Number average molecular weight: about 10,000
Was dissolved in dimethylformamide, and the solution obtained by adding 4-bromomethylphenyl isocyanide and diazabicyclo- (5,4,0) -undecene-7 was heated at 50 ° C. for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover the corresponding polymer ligand. (Yield 67%, conversion 91% confirmed by 1H NMR). The obtained polymer ligand was dissolved in tetrahydrofuran, an equivalent amount of chloroplatinic acid was added to the isocyanide group of the polymer side chain, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

Example 21 Number average molecular weight: about 10,000
Was dissolved in dimethylformamide, and a solution obtained by adding 4-bromomethylphenyl-dimethylphosphine and diazabicyclo- (5,4,0) -undecene-7 was heated at 50 ° C. for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover the corresponding polymer ligand. (Yield 67%, conversion 91%: 1HN
Confirmed by MR). The obtained polymer ligand was dissolved in tetrahydrofuran, an equivalent amount of chloroplatinic acid was added to the phenyl-dimethylphosphine group in the polymer side chain, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

Example 22 Number average molecular weight: about 14,000
Of methacrylic acid and methyl methacrylate (composition ratio: 4: 6, 0.95 g, 10 mmol) was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenylsulfide (2.22 g, 1 lmmol) and diazabicyclo- (5,4,0) -undecene-7 (1.67
g, 11 mmol) was heated at 50 ° C. for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover the corresponding polymer ligand. (Polymer recovery 99%, ligand introduction 94% (38% introduction for 40% carboxylic acid function, thus 28% ligand introduction from the whole polymer): 1NM
R was calculated from the integral ratio of the methine proton in the polymer side chain and the integral ratio of the methyl group proton in the polymer main chain). The obtained polymer ligand was dissolved in tetrahydrofuran, a chloroplatinic acid equivalent to the thiophene group in the polymer side chain was added, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

(Example 23) N, N'-
Dimethylaminoethyl methacrylate (0.47 g, 3
mmol) and methyl methacrylate (0.70 g, 0.7
(mmol) Polymerization was carried out at 60 ° C. for 3 hours using 5 ml of ethanol as a reaction solvent and azobisisobutyronitrile (3 mol%) as a polymerization initiator. After the polymerization, the reaction solution was poured into a large amount of diethyl ether to obtain a methyl methacrylate copolymer-type polymer ligand having a dimethylamino group in a side chain (number-average molecular weight: about 11,000, unit composition ratio: 3: 7). (Calculated from the integral ratio of the proton of the dimethylamino group in the side chain and the integral ratio of the methyl group broton in the main chain by 1H NMR.) The obtained polymer ligand was dissolved in tetrahydrofuran, and the equivalent of the dimethylamino group of the polymer was obtained. Was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

(Example 24) Number average molecular weight: about 14,000
Of poly (methacrylic acid-methyl methacrylate) copolymer (composition ratio 2: 8, 0.95 g, 10 mmol) was dissolved in 5 ml of dimethylformamide, and 4-bromomethylphenyl-dimethylphosphine (2.34 g, 11 mm
ol) and diazabicyclo- (5,4,0) -undecene-7 (1.67 g, 11 mmol).
Heated at ° C for 24 hours. After the completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer ligand having a phosphine group. (Recovery rate 67%, introduction rate of phosphine ligand to polymer carboxylic acid 94% (introduction rate of 19% based on the whole polymer). The obtained polymer was dissolved in tetrahydrofuran, and 2% based on phenyl-dimethylphosphine group. An equivalent amount of chloroplatinic acid was added and heated at 40 ° C. for 3 hours to prepare a target platinum complex.

[Comparative Example 1-4] 30p of a solution of chloroplatinic acid hexahydrate containing 2.0% of platinum in isopropanol
pm and 100 equivalents (Comparative Examples 1 and 2) or 10 equivalents (Comparative Examples 3 and 4) of the reaction inhibitor described in the table were added to prepare a platinum complex, which was similarly added to the base resin.

[Comparative Example 5-6] 30p of a solution of chloroplatinic acid hexahydrate containing 2.0% of platinum in isopropanol
The platinum complex was prepared by adding 2 equivalents of the compounds shown in the table with pm to the platinum atom and added to the base resin.

[Comparative Examples 7-8] The base resin prepared in Example 1 was mixed with 30 ppm of a chloroplatinic acid hexahydrate containing 2.0% platinum in isopropanol solution and platinum atom as a reaction inhibitor. Then, 5 equivalents (Comparative Example 7) and 10 equivalents (Comparative Example 8) of benzylideneaniline were added to obtain a platinum complex. 30 ppm of these platinum complexes were added to the above base resin.

[Comparative Examples 9-12] 30 ppm of a platinum complex prepared for the following was added to the base resin. (Comparative Example 9) Polymethacrylic acid (0.86, 10 mmol) having a number-average molecular weight of about 300,000 was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenylsulfide (2.22 g, 11 mmol) and diazabicyclo- (5,4 , 0) -undecene-7 (1.67 g, 11
(mmol) was heated at 50 ° C. for 24 hours.
After completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer having a sulfide group. (Recovery rate 95
%, Sulfide group introduction rate 90%). The obtained polymer was dissolved in tetrahydrofuran, a chloroplatinic acid equivalent to the sulfide group of the polymer was added, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

Comparative Example 10 Polymethacrylic acid oligomer having a number average molecular weight of about 800 (0.86 g, 10 mmol)
l) was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenylsulfide (2.22 g, 11 mm
ol) and diazavinclo- (5,4,0) -undecene-7 (1.67 g, 11 mmol).
Heated at ° C for 24 hours. After completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer having a sulfide group. (Recovery rate 90%, introduction rate of sulfide group 98
%). The obtained polymer was dissolved in tetrahydrofuran, an equivalent amount of chloroplatinic acid was added to a sulfide group, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

(Comparative Example 11) Number average molecular weight: about 10,000
Of polymethacrylic acid (0.86 g, 10 mmol) was dissolved in 5 ml of dimethylformamide. Propargyl alcohol diluted with tetrahydrofuran at 0 ° C
Then, a 6N hexane solution of normal butylchitium was slowly added dropwise to the solution to synthesize a lithium salt of propargyl alcohol. This solution was returned to room temperature, added to the above polychloromethylstyrene, and heated at 80 ° C. for 12 hours. After completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer having a propargyl group.
(Recovery rate 90%, introduction rate of propargyl group 98%). The obtained polymer was dissolved in tetrahydrofuran, a propargyl group and an equivalent amount of chloroplatinic acid were added, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

(Comparative Example 12) Number average molecular weight: about 11,000
Poly (methacrylic acid-methyl methacrylate) copolymer (composition ratio: 0.2: 9.8, 0.98 g, 10 mmol)
l) was dissolved in 5 ml of dimethylformamide, and 2-bromomethylphenylsulfide (2.22 g, 11 mm
ol) and diazabicyclo- (5,4,0) -undecene-7 (1.67 g, 11 mmol).
Heated at ° C for 24 hours. After completion of the heating, the reaction solution was poured into a large amount of methanol to recover a polymer having a sulfide group. (Recovery rate 97%, ligand introduction rate 99% (1.9% introduction rate for 2% carboxylic acid functional group): 1 NM
R was calculated from the integral ratio of the methine proton in the polymer chain and the integral ratio of the methyl group proton in the polymer main chain). The obtained polymer was dissolved in tetrahydrofuran, an equivalent amount of chloroplatinic acid was added to a sulfide group, and the mixture was heated at 40 ° C. for 3 hours to prepare a target platinum complex.

(Comparative Example 13) 15 ppm of a solution of chloroplatinic acid hexahydrate containing 2.0% platinum in isopropanol was added to the base resin without adding the component (d). Since this composition immediately reacted, it was stirred immediately after the addition, and the following curing experiment was performed.

(Curing Experiment) The resin compositions obtained in the above Examples and Comparative Examples were filled in a capacity of 2 mm × 100 mm × 150 mm, and were heated and cured in a thermostat at 100 ° C. The sample was cured in 15 minutes was rated as 、, the one cured in 30 minutes was rated as Δ, and the one that was not cured in 30 minutes was rated X.

(Storage stability) 50 g of the composition was weighed and placed in a glass test tube and sealed with a rubber stopper. The mixture was allowed to stand still for 3 days in a constant temperature layer at 40 ° C. to check whether or not gelation occurred. The gelation was evaluated as ×, the viscosity increased as Δ, and the one that did not change from the initial state was evaluated as ○.

(Measurement of Physical Properties of Cured Product) Tensile strength and elongation of cured products of the compositions obtained in the above Examples and Comparative Examples were measured. Tensile strength and elongation were measured according to JIS-K-630.
This was performed by punching and cutting into a No. 3 rubber dumbbell mold conforming to 1. The results are shown in the table. In the table, the unit of the tensile strength is MPa, and the elongation is%.

[0096]

[Table 1]

[0097]

Industrial Applicability The present invention relates to a one-part room-temperature storage composition which can be used as a sealant having low moisture permeability. Therefore, it is useful as a sealant in cases where electronic components or the like whose performance is deteriorated or damaged by moisture are housed inside.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/29 C08K 5/29 5/3467 5/3467 5/45 5/45 5/56 5/56 C08L 23/22 C08L 23/22 25/18 25/18 29/04 29/04 C 33/02 33/02 61/06 61/06 83/05 83/05

Claims (10)

[Claims] 1. A polyisobutylene compound having an alkenyl group, (b) a compound having at least two hydrosilyl groups in a molecule, (c) a platinum catalyst, and (d) a platinum catalyst.
A sealant composition comprising a compound that suppresses the ability of a platinum catalyst to promote hydrosilylation at room temperature and does not suppress the ability at high temperatures. 2. The component (d) contains one molecule of a thiophene compound, an isocyanide compound, a cyclic thioether compound, a cyclic azoether compound, an imino compound and a sulfur, nitrogen or phosphorus atom-containing functional group capable of forming a complex with a platinum atom. Average molecular weight of 1,000 to 200,0
The sealing material composition according to claim 1, wherein the sealing material composition is at least one member selected from the group consisting of 00 polymers. 3. The thiophene compound represented by the general formula [T] _n or Ar—T—Ar ′ (where T is a thiophene molecular skeleton, Ar is an aryl group or an arylalkyl group, and Ar ′ is an aryl group or an aryl group). The composition according to claim 2, which is an alkyl group or a hydrogen atom. 4. The composition according to claim 2, wherein said isocyanide compound is represented by the general formula R ¹ -NC, wherein R ¹ is a hydrocarbon group having 1 to 18 carbon atoms. 5. The cyclic thioether compound represented by the general formula (R ⁵ —S) _n (where R ⁵ is a divalent hydrocarbon group having 3 to 18 carbon atoms, and n is an integer of 3 to 8). 3. The composition of claim 2 as indicated. 6. The cyclic azoether compound has a general formula (R ⁵ —N) _n (where R ⁵ is a divalent hydrocarbon group having 3 to 18 carbon atoms, and n is an integer of 3 to 8). 3. The composition of claim 2 as indicated. 7. The imino compound represented by the general formula R ² —N ＝ C (R ³ , R ⁴ ) (where R ² is an unsubstituted or substituted hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ Is each independently a hydrogen atom or an unsubstituted or substituted hydrocarbon having 1 to 12 carbon atoms). 8. The method according to claim 1, wherein the functional group bonded to the polymer is a sulfide group, a secondary or tertiary amino group, a phosphine group,
The composition according to claim 2, which is a thiophene group or an imino group. 9. The composition according to claim 8, wherein the polymer is an acrylic polymer, a vinyl alcohol polymer, a styrene polymer or a phenol resin. 10. The composition according to claim 1, wherein the amount of the component (d) is 1 to 5 equivalents per platinum.