Curable polyorganosiloxane composition, its uses, and hydrolyzable silane compound containing a benzimidazolidinone moiety

Abstract

The present invention provides a curable silicone composition that exhibits excellent corrosion resistance and uniformity, and a compound that can impart excellent corrosion resistance and uniformity to the curable silicone composition. The present invention also relates to a curable polyorganosiloxane composition comprising (A) a polyorganosiloxane having two or more silicon-bonded hydrolyzable groups per molecule, (B) a curing catalyst, and (C) a compound that contains a benzimidazolidinone moiety and a silicon-bonded hydrolyzable group per molecule, and to component (C).

Description

[Technical Field]

[0001] The present invention relates to a curable polyorganosiloxane composition, its uses, and a hydrolyzable silane compound containing a benzimidazolidinone moiety. [Background technology]

[0002] Among polyorganosiloxane compositions that harden at room temperature to form a rubber-like elastomer, those that undergo a hardening reaction upon contact with moisture in the air eliminate the hassle of weighing and mixing the main body (base polymer), crosslinking agent, catalyst, etc. immediately before use, and are free of the risk of compounding errors.In addition, they have excellent adhesive properties, so they are widely used as coating materials for the electrical and electronics industries, as well as sealing materials for construction.

[0003] As such coating materials, Patent Documents 1 and 2 describe room-temperature curable polyorganosiloxane compositions containing a polyorganosiloxane having alkoxy groups bonded to the terminal silicon atoms, an alkoxysilane, and a curing catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 62-252456 [Patent Document 2] Japanese Patent Application Publication No. 4-293962 Summary of the Invention [Problem to be solved by the invention]

[0005] As electrodes and wiring in LCDs (Liquid Display Panels) and PDPs (Plasma Display Panels) become increasingly miniaturized, corrosion and migration of the electrodes and wiring are becoming more common. This corrosion is thought to be caused by trace amounts of corrosive gases in the atmosphere, such as hydrogen sulfide and sulfuric acid, or by salt water. Therefore, there is a demand for coating materials that are highly effective in preventing corrosion of electrodes and wiring.

[0006] Room-temperature-curable polyorganosiloxane compositions containing polyorganosiloxanes having alkoxy groups bonded to terminal silicon atoms, alkoxysilanes, and curing catalysts, as described in Patent Documents 1 and 2, have the problem that the resulting coatings may have poor corrosion prevention (corrosion resistance). Furthermore, room-temperature-curable polyorganosiloxane compositions containing 1,2,3-benzotriazole, which is used as a rust inhibitor, have the problem of poor composition uniformity.

[0007] An object of the present invention is to provide a curable silicone composition that has excellent corrosion resistance and uniformity. Another object of the present invention is to provide a compound that can impart excellent corrosion resistance and uniformity to the curable silicone composition. [Means for solving the problem]

[0008] That is, the present invention relates to the following [1] to [9]. [1] (A) A polyorganosiloxane having two or more hydrolyzable groups bonded to silicon atoms in one molecule and not having a benzimidazolidinone moiety; (B) a curing catalyst, and (C) A compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule. 1. A curable polyorganosiloxane composition comprising: [2] The curable polyorganosiloxane composition according to [1], wherein component (C) is a compound containing one or two benzimidazolidinone moieties, a siloxane chain, and a hydrolyzable group bonded to a silicon atom in one molecule. [3] The component (C) is represented by the following general formula (1), (2), or (3): [ka] [During the ceremony, A 1 is expressed by equation (4) or (5): [ka] (In formula (4), R 21 is a hydrogen atom or a hydrocarbon group) [ka] (In formula (5), R 22 and R 23 are each independently a hydrogen atom or a hydrocarbon group. is a group represented by X 1 represents an alkylene group which may be interrupted by -S-, an alkylene group which may be interrupted by -NH-, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 1 are each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 1 is a hydrolyzable group. [ka] [During the ceremony, A 2 and A 3 are each independently a group represented by formula (4) or (5), X 2 and X 3each independently represents an alkylene group which may be interrupted by -S-, an alkylene group which may be interrupted by -NH-, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 2 are each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 2 is a hydrolyzable group, R 3 are each independently a hydrocarbon group, L 1 is 0 or a number between 1 and 1,000. [ka] [During the ceremony, A 4 is a group represented by formula (4) or (5), X 4 and X 5 each independently represents an alkylene group which may be interrupted by -S-, an alkylene group which may be interrupted by -NH-, or an alkylene group which may be interrupted by a linear siloxane chain; R 4 are each independently a hydrocarbon group, R 5 are each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 5 is a hydrolyzable group, a is an integer of 1 or greater, and when a is an integer of 2 or greater, each A 4 , X 4 and R 4 are the same or different, b is an integer of 0 or 1 or more, and when b is an integer of 2 or more, each X 5 , R 4 and R 5 are the same or different, c is an integer of 0 or 1 or more, and when c is an integer of 2 or more, each R 4 are the same or different, a+b+c is an integer of 3 or more]. The curable polyorganosiloxane composition according to [1] or [2]. [4] The curable polyorganosiloxane composition according to any one of [1] to [3], further comprising one or more selected from the group consisting of (D) a crosslinking agent, (E) an adhesion promoter, and (F) a polyorganosiloxane having no silicon-bonded hydrolyzable groups. [5] A coating agent for electronic parts, which uses the curable polyorganosiloxane composition according to any one of [1] to [4]. [6] A metal surface treatment agent using the curable polyorganosiloxane composition according to any one of [1] to [4]. [7] A cured product obtained by curing the curable polyorganosiloxane composition according to any one of [1] to [4]. [8] An electronic part comprising the curable polyorganosiloxane composition according to any one of [1] to [4]. [9] (C) A compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule. [Effects of the Invention]

[0009] The present invention provides a curable silicone composition that exhibits excellent corrosion resistance and uniformity. Another object of the present invention is to provide a compound that can impart excellent corrosion resistance and uniformity to a curable silicone composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Term definition] The structural units of siloxane compounds are sometimes abbreviated as follows (hereinafter, these structural units are referred to as "M units" and "D units" respectively). H (sometimes called "units"). M :(CH3)3SiO 1 / 2 M H :(CH3)2HSiO 1 / 2 M V:(CH3)2(CH2=CH)SiO 1 / 2 D :(CH3)2SiO 2 / 2 D H :(CH3)HSiO 2 / 2 D V :(CH3)(CH2=CH)SiO 2 / 2 T :CH3SiO 3 / 2 Q :SiO 4 / 2 (tetrafunctional)

[0011] In this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0012] In this specification, viscosity is a value measured at 23° C. Specifically, it is a value measured under the conditions described in the examples.

[0013] In this specification, "(A) a polyorganosiloxane having two or more silicon-bonded hydrolyzable groups per molecule and no benzimidazolidinone moiety" is also referred to as "component (A)." The same applies to "(B) a curing catalyst," etc.

[0014] As used herein, the term "hydrocarbon group" refers to a group obtained by removing at least one hydrogen atom from a hydrocarbon molecule containing carbon atoms and hydrogen atoms, depending on the valence of the hydrocarbon group. The hydrocarbon group may be substituted with one or more substituents. Examples of the substituents include halogen atoms and cyano groups.

[0015] Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Examples of the monovalent hydrocarbon group having no aliphatic unsaturated bond include the above-mentioned monovalent hydrocarbon groups other than an alkenyl group.

[0016] The alkyl group is a linear or branched group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. The cycloalkyl group is a monocyclic or polycyclic group having 3 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The aryl group is an aromatic group containing a monocyclic or polycyclic group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The aralkyl group is an alkyl group substituted with an aryl group, and examples thereof include a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group. The alkenyl group is a straight-chain or branched group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, a 3-butenyl group, and a 5-hexenyl group.

[0017] The monovalent hydrocarbon group may be unsubstituted or substituted with a halogen or a cyano group. Examples of alkyl groups substituted with halogen include a chloromethyl group, a bromoethyl group, a chloropropyl group, a 3,3,3-trifluoropropyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. Examples of aryl groups substituted with halogen include a chlorophenyl group. Examples of alkyl groups substituted with a cyano group include a 2-cyanoethyl group.

[0018] A divalent hydrocarbon group is a group obtained by removing one hydrogen atom from the above-mentioned monovalent hydrocarbon group. The divalent hydrocarbon group is preferably an alkylene group. The alkylene group is a linear or branched group having 1 to 18 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a 2-methylethylene group, and a tetramethylene group. The divalent hydrocarbon group may be unsubstituted or substituted with a halogen or a cyano group.

[0019] [Curable Polyorganosiloxane Composition] The curable polyorganosiloxane composition (hereinafter also referred to simply as "composition") contains (A) a polyorganosiloxane having two or more hydrolyzable groups bonded to silicon atoms in one molecule and having no benzimidazolidinone moiety, (B) a curing catalyst, and (C) a compound having, in one molecule, a benzimidazolidinone moiety and one or more members selected from the group consisting of hydrolyzable groups bonded to silicon atoms and siloxane chains.

[0020] The composition has excellent corrosion resistance and uniformity, as well as excellent heat resistance, reliability (heat cycle resistance), etc. The corrosion resistance is preferably resistance to corrosive gases such as hydrogen sulfide gas and sulfuric acid gas, or salt water, and is particularly preferably resistance to sulfur or salt water.

[0021] [(A) Polyorganosiloxane having two or more silicon-bonded hydrolyzable groups per molecule and no benzimidazolidinone moiety] Component (A) is a polyorganosiloxane having two or more silicon-bonded hydrolyzable groups per molecule, and serves as the base polymer in the composition.

[0022] In this specification, "polyorganosiloxane" refers to a component having a siloxane bond (-Si-O-Si) and at least two silicon atoms per molecule. Component (A) has at least two silicon atoms per molecule, preferably at least three silicon atoms per molecule, and particularly preferably ten or more silicon atoms per molecule.

[0023] Component (A) does not have a benzimidazolidinone moiety. Specifically, component (A) does not have a benzimidazolidinone moiety, which will be described later. Therefore, component (A) does not fall under the category of component (C), which will be described later.

[0024] <Hydrolyzable group> Examples of hydrolyzable groups include -OR', -OCOR', -ON=CR'2, -NR'2, -NHR', halogen atoms, etc. In these formulas, R' is an alkyl group.

[0025] The hydrolyzable group is preferably -OR' (i.e., an alkoxy group). R' is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. Therefore, the hydrolyzable group is particularly preferably a methoxy group or an ethoxy group.

[0026] <Structure of component (A)> The structure of component (A) is not particularly limited as long as it has an average of two or more hydrolyzable groups bonded to silicon atoms per molecule. Component (A) is typically represented by general formula (5): (R a ) s (R 6 ) t SiO (4-s-t) / 2 (5) (In the formula, R a is a hydrolyzable group; R 6 is a monovalent hydrocarbon group having no aliphatic unsaturated bonds; s is an integer from 1 to 3; t is an integer of 0 to 2, provided that s+t is 1 to 3. The molecule has at least two units represented by the formula:

[0027] Component (A) is represented by the following general formula (6): (R a ) 3-p R 6 p Si-O-(Si(R 6 ) r (R a ) 2-r O) n -SiR 6 q (R a )3-q ···(6) (In the formula, R a are each independently a hydrolyzable group, R 6 are each independently a monovalent hydrocarbon group having no aliphatic unsaturated bonds, p and q are each independently 0, 1, or 2; Each r is independently 0, 1, or 2; The linear polyorganosiloxane is preferably a linear polyorganosiloxane represented by the formula (where n is a number that provides a viscosity at 23° C. of 100 mPa·s to 500,000 mPa·s).

[0028] R 6 is preferably an alkyl group or an aryl group.

[0029] From the viewpoint of controlling physical properties such as refractive index, R 6 At least a part of R may be an aryl group such as a phenyl group. 6 In view of ease of availability, polyorganosiloxanes in which all r are methyl are preferred. It is also preferred that r is 2. In other words, component (A) is preferably a linear polyorganosiloxane in which at least one hydrolyzable group exists only at each end of the molecule.

[0030] Therefore, component (A) has R at both ends. a 3-m R 6 m SiO 1 / 2 It is blocked by units, and the intermediate unit is R 6 2SiO 2 / 2 The linear polyorganosiloxane unit (wherein R a is a hydrolyzable group, and R 6 is a monovalent hydrocarbon group having no aliphatic unsaturated bonds, and m is 0, 1 or 2).

[0031] It is particularly preferred that component (A) be one in which p and q in formula (6) are 0 or 1, that is, one having two or more hydrolyzable groups at each of the molecular terminals.

[0032] The viscosity of component (A) is preferably 10 mPa·s to 500,000 mPa·s, and particularly preferably 150 mPa·s to 100,000 mPa·s, at 23° C. When the viscosity of component (A) is within this range, saltwater resistance and uniformity tend to be better.

[0033] Component (A) can be a commercially available product, or a polyorganosiloxane into which a hydrolyzable group has been introduced by a known reaction.

[0034] Component (A) may be one kind of component or a combination of two or more kinds of components.

[0035] [(B) Curing catalyst] Component (B) is a curing catalyst. Component (B) promotes the hydrolytic condensation of component (A), component (C) containing a silicon-bonded hydrolyzable group, and the optional crosslinking agent (D). Examples of component (B) include metal catalysts, organic acid catalysts, inorganic acid catalysts, and base catalysts. It should be noted that the organic acid catalysts, inorganic acid catalysts, and base catalysts do not contain metal atoms.

[0036] Examples of the metal catalyst include metal carboxylates and organometallic compounds. Examples of metals contained in the metal catalyst include titanium, zirconium, tin, aluminum, iron, manganese, and zinc.

[0037] The metal carboxylate is not particularly limited as long as it is a carboxylic acid compound containing the above metal, and preferred examples of the metal carboxylate include iron octoate, manganese octoate, zinc octoate, tin naphthate, tin caprylate, and tin oleate.

[0038] The organometallic compound is not particularly limited as long as it is an organic compound containing the above-mentioned metal. The organometallic compound is preferably an organotitanium compound, an organozirconium compound, an organotin compound, an organoaluminum compound, or the like.

[0039] Examples of the organic titanium compound include tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, diisopropoxytitanium bis(ethylacetoacetate), 1,3-propanedioxytitanium bis(ethylacetoacetate), and the like.

[0040] Examples of the organic zirconium compound include zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrapropoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxyzirconium, tributoxyzirconium acetylacetonate, and tributoxyzirconium stearate.

[0041] Examples of organotin compounds include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, dioctyltin dilaurate, and dimethyltin dineodecanoate.

[0042] Examples of the organoaluminum compound include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, and triethoxyaluminum.

[0043] Examples of the organic acid catalyst include compounds having a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Preferred examples of the organic acid catalyst include acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and alkylphosphoric acid.

[0044] Examples of inorganic acid catalysts include hydrochloric acid and sulfuric acid.

[0045] Examples of basic catalysts include amine compounds such as ammonia, triethylamine, and diethylamine; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and guanidyl compounds such as tetramethylguanidine, guanidyl group-containing silanes, and guanidyl group-containing siloxanes.

[0046] Component (B) is preferably a metal catalyst. Metal catalysts are easily dissolved or dispersed in the composition, contributing to the promotion of a uniform reaction. Metal catalysts contain little foreign matter, contributing to the formation of a transparent cured product of the composition. Component (B) is particularly preferably an organotitanium compound.

[0047] Component (B) may be one kind of component or a combination of two or more kinds of components.

[0048] [(C) Compounds containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule] Component (C) is a compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule. Component (C) is a hydrolyzable silane compound containing a benzimidazolidinone moiety.

[0049] When component (C) contains a silicon-bonded hydrolyzable group, the crosslinking reaction with other components proceeds, thereby enabling the effects of the present invention to be efficiently achieved.

[0050] <Benzimidazolidinone moiety> The benzimidazolidinone moiety is a group in which one or more hydrogen atoms have been removed from benzimidazolidinone (also known as 2(1H)-benzimidazolone, 2-hydroxybenzimidazole, or 1,3-dihydro-2H-benzimidazol-2-one) represented by the following structural formula.

[0051] [ka]

[0052] The benzimidazolidinone moiety is preferably a monovalent group obtained by removing a hydrogen atom from the secondary amino group (NH group) of unsubstituted or substituted benzimidazolidinone, or a monovalent group obtained by removing a hydrogen atom from the primary amino group (NH group) of unsubstituted or substituted 5-amino-2-benzimidazolidinone. Specifically, the benzimidazolidinone moiety is preferably a group represented by the following formula (4) or (5). In addition, the group R in formula (4) 21 As shown in the formula (5), one secondary amino group of the benzimidazolidinone may be unsubstituted or substituted. 22 and R 23 As shown in the formula (I), one or two secondary amino groups of the 5-amino-2-benzimidazolidinone may be unsubstituted or substituted.

[0053] [ka] (In formula (4), R 21 is a hydrogen atom or a hydrocarbon group)

[0054] [ka] (In formula (5), R 22 and R 23 are each independently a hydrogen atom or a hydrocarbon group.

[0055] <Hydrolyzable group bonded to silicon atom> The hydrolyzable group bonded to the silicon atom is as described above in component (A).

[0056] <Other groups> Component (C) may contain other groups. Examples of such groups include alkylene groups optionally interrupted by -S-, alkylene groups optionally interrupted by -NH-, alkylene groups optionally interrupted by linear or cyclic siloxane chains, and siloxane chains. When component (C) contains a siloxane chain, the compatibility of component (C) with other components in the composition can be improved. This allows the effects of the present invention to be more efficiently achieved. Here, "an alkylene group optionally interrupted by -S-" means that the C-C bond in the alkylene group is either interrupted by one -S- or is not interrupted. The same applies to "an alkylene group optionally interrupted by -NH-" and "an alkylene group optionally interrupted by linear or cyclic siloxane chains."

[0057] <Siloxane chain> The siloxane chain can be linear, branched, cyclic, or a combination thereof. 7 R 8 O 2 / 2 ] units (preferably D units), [SiR 9 O 3 / 2 ] units (preferably T units) and [SiO 4 / 2 ] (Q unit), where R 7 , R 8 and R 9 are each independently a hydrocarbon group. 7 , R 8 and R 9 and R when it is a hydrocarbon group. 1 For example, [SiR 7 R 8 O 2 / 2 ] units, and can take a linear structure consisting of only [SiR 7 O 3 / 2 By including the [SiR] unit, a branched or cyclic structure can be obtained, and by including the Q unit, a three-dimensional network structure can be obtained. 7 R 8 O 2 / 2 ] units, [SiR 9 O3 / 2 A finite number of combinations of [SiR] units and Q units include at least two bond sites, but the site where the siloxane skeleton is bonded to another group may be located in any part of each unit constituting the siloxane skeleton. 7 R 8 O 2 / 2 ] units form a cyclic structure, the group R 7 or R 8 can be bonded to other groups. For example, a group having a cyclic siloxane skeleton is [SiR 7 R 8 O 2 / 2 ] at least two groups R of a cyclic siloxane consisting of four units 7 is a bond to a hydrocarbon group such as an ethylene group, the following structure is preferred. [ka] (In the formula, the wavy line portion represents the portion bonding to the silicon atom to which the hydrolyzable group is bonded, the benzimidazolidinone portion, and the optionally present group (for example, the carbon atom of the alkylene group).)

[0058] The siloxane chain is preferably a divalent or higher group because it can function as a spacer (linking group) between the benzimidazolidinone moiety and the hydrolyzable silyl group, or as a spacer between two benzimidazolidinone moieties.

[0059] Other groups include X 1 ~X 3 Examples include:

[0060] Component (C) preferably contains one or two benzimidazolidinone moieties per molecule, and particularly preferably contains one or two benzimidazolidinone moieties, a siloxane chain, and a hydrolyzable group bonded to a silicon atom per molecule.

[0061] Component (C) is preferably a compound represented by general formula (1), (2) or (3).

[0062] <Compound represented by general formula (1)> The compound represented by general formula (1) is as follows: [ka] [In the ceremony, A 1 , X 1 , R 1 is as described above.

[0063] The compound represented by general formula (1) is a compound containing one benzimidazolidinone moiety, a hydrolyzable group bonded to a silicon atom, and optionally a siloxane chain in one molecule.

[0064] A 1 is expressed by equation (4) or (5): [ka] [ka] [In the formula, R 21 , R 22 and R 23 is as described above. It is a group represented by the formula:

[0065] R 21 is a hydrogen atom or a hydrocarbon group. 21 When R is a hydrocarbon group, it is preferably an alkyl group, and particularly preferably a methyl group. 21 is preferably a hydrogen atom or a methyl group.

[0066] R 22 and R 23 are each independently a hydrogen atom or a hydrocarbon group. 22 and R 23 is R 21 Therefore, R 22 and R 23are preferably each independently a hydrogen atom or a methyl group.

[0067] Also, A 1 may be a group represented by the following formula (4-1) or (5-1). [ka] [ka]

[0068] X 1 X is an alkylene group which may be interrupted by -S-, an alkylene group which may be interrupted by -NH-, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain. 1 may be an alkylene group which may be interrupted by -S-, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain. 1 The structure represented by the formula 1 (i.e., a benzimidazolidinone moiety represented by formula (4) or (5)) and a hydrolyzable silyl group (i.e., a group: -SiR 1 3) is a moiety that acts as a spacer for the group represented by X 1 The structure of the alkylene group in X may be linear, branched, cyclic, or a combination thereof, and is preferably linear. 1 The alkylene group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.

[0069] R 1 are each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 1 R is a hydrolyzable group. Here, the hydrolyzable group is as described in component (A). 1 When R is a hydrocarbon group, it is preferably an alkyl group. 1 is preferably a hydrolyzable group.

[0070] <Compound represented by general formula (2)> The compound represented by general formula (2) is as follows: [ka] [In the ceremony, A 2 , A 3 , X 2 , X 3 , R 2 , R 3 , L 1 is as described above.

[0071] The compound represented by general formula (2) is a compound containing two benzimidazolidinone moieties, a hydrolyzable group bonded to a silicon atom, and optionally a siloxane chain in one molecule. 1 When is 1 or more, the compound represented by general formula (2) is a compound containing two benzimidazolidinone moieties, a siloxane chain, and a hydrolyzable group bonded to a silicon atom in one molecule.

[0072] A 2 and A 3 is A 1 X 2 and X 3 is X 1 Also, R 2 is R 1 From the viewpoint of hardening, all R 2 is preferably a hydrolyzable group. 3 is a hydrocarbon group when R 1 is synonymous with.

[0073] L 1 is (R 3 )2SiO 2 / 2 is the repeating number of the siloxane chain consisting of units. 1 is 0 or a number from 1 to 1,000, preferably 0 or a number from 1 to 300, and particularly preferably 0 or a number from 1 to 150.

[0074] <Compound represented by general formula (3)> The compound represented by general formula (3) is as follows: [ka] [In the ceremony, A 4 , X 4 , X 5 , R 4 , R 5 , a, b, and c are as defined above.

[0075] The compound represented by general formula (3) is a compound containing one or more benzimidazolidinone moieties, a hydrolyzable group bonded to a silicon atom, and an alkylene group interrupted by a cyclic siloxane chain in one molecule. That is, the compound represented by general formula (3) is a compound containing X 4 and X 5 form an alkylene group, which is interrupted by cyclic siloxanes bounded by a, b, and c.

[0076] A 4 is A 1 It is synonymous with R. 4 is a hydrocarbon group when R 1 Also, R 5 is R 1 From the viewpoint of curability, in general formula (3), all of R 5 is preferably a hydrolyzable group.

[0077] X 4 and X 5 is X 1 X 4 and X 5 is preferably an uninterrupted alkylene group. 4 and X 5 The alkylene group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.

[0078] a is an integer of 1 or more. From the viewpoint of corrosion resistance, a is preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2. When a is an integer of 2 or more, each A 4 , X 4 and R 4 are preferably the same.

[0079] b is 0 or an integer of 1 or more. When b is an integer of 1 or more, the compound represented by general formula (3) contains a hydrolyzable group bonded to a silicon atom. From the viewpoint of curability, b is preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2. When b is an integer of 2 or more, each X 5 , R 4 and R 5 are preferably the same.

[0080] c is an integer of 0 or greater than or equal to 1. From the viewpoint of ease of synthesis and handling, c is preferably an integer of 0 or greater than or equal to 1, and particularly preferably an integer of 0 or greater than or equal to 1, and particularly preferably an integer of 0 or greater than or equal to 2. When c is an integer of 2 or greater, each R 4 are preferably the same.

[0081] Furthermore, a+b+c is an integer of 3 or greater. When a+b+c is an integer of 3 or greater, the main skeleton becomes a cyclic organosiloxane. From the viewpoint of ease of synthesis, a+b+c is preferably an integer of 3 to 8, and particularly preferably an integer of 4 to 6.

[0082] Component (C) is preferably one or more compounds selected from the group consisting of Compounds 1 to 9 in the Examples.

[0083] Component (C) may be one kind of component or a combination of two or more kinds of components.

[0084] <Method for producing component (C)> Component (C) can be obtained by reacting a salt of benzimidazolidinone or a salt of 5-amino-2-benzimidazolidinone with a silane compound. Specifically, component (C) can be obtained by reacting a siloxane having a halogenated alkyl group with benzimidazolidinone or a salt of 5-amino-2-benzimidazolidinone.

[0085] The ratio of the amount of the benzimidazolidinone salt or the 5-amino-2-benzimidazolidinone salt to the amount of the siloxane having a halogenated alkyl group can be set as appropriate, but the amount of the benzimidazolidinone salt or the 5-amino-2-benzimidazolidinone salt relative to the amount of the siloxane having a halogenated alkyl group is preferably 0.5 to 1.5 mol, and particularly preferably 0.8 to 1.2 mol.

[0086] In the method for producing component (C), a solvent may be used as needed. The solvent is not particularly limited as long as it is non-reactive with the raw material compounds. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and cyclohexane; ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; halogenated solvents such as chloroform and dichloromethane; amide solvents such as formamide, dimethylformamide, and N-methylpyrrolidone; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0087] In the method for producing component (C), the reaction temperature and reaction time can be set appropriately. When a solvent is used, the reaction temperature can be in the range of room temperature (23°C) to the boiling point of the solvent. The reaction time is preferably 1 to 12 hours and can be set appropriately depending on the reaction temperature.

[0088] [Additional Ingredients] The composition may contain additional components within the scope of the present invention. These additional components include (D) a crosslinking agent, (E) an adhesion promoter, (F) a polyorganosiloxane that does not have a silicon-bonded hydrolyzable group, and a component (G) other than components (D) to (F). Components (D) to (F) exclude components that fall under components (A) to (C).

[0089] <(D) Crosslinking Agent> Component (D) is a crosslinking agent. Examples of component (D) include an organosilicon compound having at least two silicon-bonded hydrolyzable groups or a partial hydrolysis condensate thereof. Here, the organosilicon compound is preferably a compound having one silicon atom per molecule. Component (D) is a compound that undergoes a crosslinking reaction (condensation reaction) with component (A), specifically, with the silicon-bonded hydrolyzable groups of component (A). Component (D) does not contain any reactive functional groups other than the hydrolyzable groups. Here, examples of the reactive functional groups include primary amino groups, epoxy groups, (meth)acryloyl groups, (meth)acryloxy groups, mercapto groups, and isocyanato groups.

[0090] Component (D) is R 10 u Si(OR 11 ) 4-u (In the formula, R 10 is independently in each occurrence an unsubstituted or substituted monovalent hydrocarbon group; R 11 is preferably an organosilicon compound represented by the formula (I) or a partial hydrolysis condensate thereof, wherein each occurrence of is independently an unsubstituted or substituted monovalent hydrocarbon group, and u is 0, 1, or 2.

[0091] R 10 is preferably an unsubstituted or halogen-substituted alkyl, cycloalkyl, aryl, aralkyl or alkenyl group.

[0092] R 11is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably CH3- or C2H5-.

[0093] Preferably, u is 1 or 2.

[0094] Component (D) is particularly preferably an alkoxy group-containing compound selected from the group consisting of tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and 3-chloropropyltrimethoxysilane; a partial hydrolysis condensate of the alkoxy group-containing compound; or a combination thereof.

[0095] Component (D) may be one kind of component or a combination of two or more kinds of components.

[0096] <(E) Adhesion promoter> Component (E) is an adhesion promoter. Component (E) is a component that improves the adhesion of a cured product of the composition to substrates such as metals, glass, and plastics. Examples of component (E) include compounds having a silicon-bonded hydrolyzable group and a reactive organic functional group, and / or partial hydrolysis condensates of the above compounds (excluding those corresponding to components (A) to (C)). Examples of the reactive organic functional group include a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group, and an isocyanato group.

[0097] Specific examples of component (E) include alkoxysilyl group-containing isocyanurate compounds, alkoxysilyl group-containing carbasilatrane compounds, alkoxysilyl group-containing fumaric acid ester compounds, and alkoxysilyl group-containing amine compounds.

[0098] Examples of the alkoxysilyl group-containing isocyanurate compound include tris[(3-trialkoxysilyl)propyl]isocyanurates such as tris[(3-trimethoxysilyl)propyl]isocyanurate and tris[(3-triethoxysilyl)propyl]isocyanurate.

[0099] Examples of alkoxysilyl group-containing fumaric acid ester compounds include bis(3-trimethoxysilylpropyl)fumarate, bis(3-triethoxysilylpropyl)fumarate, etc. Examples of alkoxysilyl group-containing amine compounds include bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, etc.

[0100] Examples of alkoxysilyl group-containing epoxy compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3,4-epoxycyclohexylethyltrimethoxysilane.

[0101] Component (E) may be one kind of component or a combination of two or more kinds of components.

[0102] <(F) Polyorganosiloxane having no hydrolyzable groups bonded to silicon atoms> Component (F) is a polyorganosiloxane that does not have a silicon-bonded hydrolyzable group. When the composition contains component (F), the hardness of the cured product of the composition and / or the viscosity of the composition tend to be controlled. Furthermore, when the composition contains component (F), the handleability of the composition and the required physical properties can be widely accommodated.

[0103] Examples of component (F) include siloxane resins such as polydimethylsiloxane that do not have a curable functional group. Examples of the siloxane resin of component (F) include resins obtained by combining the M unit, D unit, T unit, and / or Q unit and that do not have a hydrolyzable group.

[0104] Component (F) is a compound represented by the following general formula (7): R 6 3Si-O-(SiR 6 2O) v -SiR 6 3(7) (In the formula, R 6 is as defined in general formula (6), v is the number that gives a viscosity of 1 mPa·s to 10,000 mPa·s at 23°C. Preferably, the siloxane resin is represented by the formula:

[0105] The viscosity of component (F) is preferably 1 mPa·s to 10,000 mPa·s, and particularly preferably 1 mPa·s to 1,000 mPa·s, at 23° C. When the viscosity of component (F) is within this range, viscosity adjustment can be carried out more efficiently.

[0106] Component (F) may be one kind of component or a combination of two or more kinds of components.

[0107] <Ingredients (G) other than ingredients (D) to (F)> Examples of the component (G) include inorganic fillers, flame retardants, heat resistance imparting agents, organic solvents, inorganic pigments, and organic pigments. Component (G) may be one kind of component or a combination of two or more kinds of components.

[0108] The composition preferably further comprises one or more members selected from the group consisting of (D) a crosslinking agent, (E) an adhesion promoter, and (F) a polyorganosiloxane that does not have a hydrolyzable group bonded to a silicon atom.

[0109] <Content of each ingredient> In the composition, the content of each component is preferably as follows.

[0110] The content of component (A) is not particularly limited as long as it is an amount that allows the curable polyorganosiloxane composition to have a handleable viscosity range. The content of component (A) is preferably 50.0 to 99.9 parts by mass, more preferably 70.0 to 98.0 parts by mass, and particularly preferably 80.0 to 95.0 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C).

[0111] The content of component (B) is a catalytic amount relative to the total amount of the curable polyorganosiloxane composition. From the viewpoint of curability, the content of component (B) is preferably 0.01 to 10.0 parts by mass, particularly preferably 0.03 to 5.0 parts by mass, relative to 100 parts by mass of component (A).

[0112] From the viewpoint of corrosion prevention, the content of component (C) is preferably 0.1 to 30.0 parts by mass, more preferably 0.2 to 20.0 parts by mass, and particularly preferably 0.3 to 10.0 parts by mass, per 100 parts by mass of component (A).

[0113] The total content of components (A) to (C) relative to the total amount of the composition is preferably 50 to 100 parts by mass, more preferably 75 to 100 parts by mass, and particularly preferably 80 to 100 parts by mass.

[0114] From the viewpoints of storage stability and curability, the content of component (D) is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.5 to 15 parts by mass, per 100 parts by mass of component (A).

[0115] Component (D) can contain, for example, 1 to 30 moles, and specifically 2 to 20 moles, of hydrolyzable groups of component (D) per mole of hydrolyzable groups bonded to silicon atoms of component (A).

[0116] From the viewpoint of exhibiting higher adhesion to the substrate, the content of component (E) is preferably 0 to 20 parts by mass, more preferably 0.05 to 20 parts by mass, even more preferably 0.1 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A).

[0117] From the viewpoint of coating performance, the content of component (F) is preferably 0 to 50 parts by mass, more preferably 0.1 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of component (A).

[0118] The content of component (G) is not particularly limited as long as it does not impair the intended use of the curable polyorganosiloxane composition.

[0119] [Method for producing curable polyorganosiloxane composition] The curable polyorganosiloxane composition can be produced by uniformly kneading components (A) to (C) and optional components (D) to (F) using a mixing means such as a universal mixer or kneader.

[0120] [Uses of the curable polyorganosiloxane composition] The curable polyorganosiloxane composition can be used as a metal surface treatment agent. Examples of metals include aluminum, copper, nickel, iron, brass, and stainless steel. The curable polyorganosiloxane composition can also be used as a coating agent for electronic components.

[0121] [Cured product of curable polyorganosiloxane composition] A cured product obtained by curing the curable polyorganosiloxane composition can be obtained by curing the curable polyorganosiloxane composition. For a thickness of about 0.1 mm, curing can be accelerated by heating at room temperature (20 to 30°C) for 2 to 4 hours, optionally at 30 to 60°C. Preferred curing conditions are room temperature (20 to 30°C) and a relative humidity of 40 to 60%RH.

[0122] The cured product obtained by curing the curable polyorganosiloxane composition can be used as a surface coating for metals. The cured product obtained by curing the curable polyorganosiloxane composition can also be used as a coating for electronic components such as electronic devices and integrated circuit elements. Therefore, electronic components containing the curable polyorganosiloxane composition are also within the scope of the present invention.

[0123] [Article containing a cured product of the curable polyorganosiloxane composition] The article comprising the cured product of the curable polyorganosiloxane composition is preferably an article comprising a substrate and a cured product of the composition. Examples of articles comprising a substrate and a cured product of the composition include electronic devices, integrated circuit elements, and other electronic components.

[0124] The method for producing the article is not particularly limited, and preferably includes the steps of preparing a component including a substrate and a composition, applying the composition to a surface of the substrate, and curing the composition to form a cured product of the composition on the substrate.

[0125] In addition to metals, examples of the substrate include epoxy resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate (PBT) resins, engineering plastics such as polycarbonate resins, acrylic resins, polyimide resins, phenolic resins, polyamide resins, polyphenylene sulfide (PPS) resins, and modified polyphenylene ether (PPE) resins; and glass. If necessary, the wall surfaces of the gaps may be treated with a primer in accordance with conventional methods. The shape and thickness of the substrate are not particularly limited.

[0126] Examples of methods for applying the curable polyorganosiloxane composition include dripping, pouring, casting, extrusion from a container, coating such as bar coating or roll coating, screen printing, dipping, brushing, spraying, and dispensing. The composition may be applied uniformly over the entire surface of the part, or unevenly or partially, such as in lines, stripes, or dots. The applied thickness of the composition is preferably 0.01 to 3 mm, and particularly preferably 0.05 to 2 mm.

[0127] The curing conditions for the composition are as described above for the cured product of the composition.

[0128] [(C) A compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule] Another aspect of the present invention is a compound (C) (hereinafter sometimes referred to as "compound (C)") containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule. Compound (C), including preferred embodiments, is as described above for component (C). Therefore, compound (C) is preferably a compound containing one or two benzimidazolidinone moieties, a siloxane chain, and a hydrolyzable group bonded to a silicon atom in one molecule. Furthermore, compound (C) is particularly preferably a compound represented by general formula (1), (2), or (3).

[0129] Compound (C) can impart excellent corrosion resistance and uniformity to the curable silicone composition. Therefore, compound (C) can be used as an agent for improving corrosion resistance and uniformity for the second curable polyorganosiloxane composition. Here, the second curable polyorganosiloxane composition contains component (A) and component (B), and optionally contains one or more components selected from the group consisting of component (D), component (E), component (F), and component (G). The components and their contents, including preferred embodiments, are as described above for the curable polyorganosiloxane composition. [Example]

[0130] The present invention will be described in more detail below with reference to examples and comparative examples. In these examples, parts are by mass and viscosity is measured at 23° C. The present invention is not limited to these examples.

[0131] <Ingredients used> Component (A): α,ω-bis(trimethoxysiloxy)polydimethylsiloxane (viscosity 300 mPa·s) Component (B): Diisopropoxybis(ethylacetoacetate) titanium Component (C): Compound 1 to Compound 9 Component (D): Methyltrimethoxysilane Component (E): Tris[(3-trimethoxysilyl)propyl]isocyanurate Component (F): Polydimethylsiloxane (viscosity 1 mPa·s)

[0132] Comparative component (C'): 2-Hydroxybenzimidazole 1-Isopropenyl-2-benzimidazolidinone 1-(3-chloropropyl)-1,3-dihydro-2H-benzimidazol-2-one 1,2,3-benzotriazole

[0133] (Production of Component (C) (Compounds 1 to 9))

[0134] <Compound 1> A 2,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 800 g of xylene, 94 g (0.7 mol) of 2-hydroxybenzimidazole, and 8.5 g of a basic catalyst, followed by 131 g (0.66 mol) of 3-chloropropyltrimethoxysilane, and stirred under a nitrogen stream at 120° C. for 8 hours. After cooling, the mixture was filtered, and the xylene and excess materials were distilled off at 135° C. to obtain 171 g of compound 1. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0135] NH:10.8ppm, C6H4:6.9ppm~7.2ppm, -Si(OCH3):3.5ppm, N-CH:4.6ppm, Si-CH2-:0.5-0.7ppm, Si-CH2-C H 2-: 1.6~1.8ppm, Si-CH2-CH2-C H 2-: 2.3 to 2.6 ppm

[0136] [ka]

[0137] <Compound 2> A 1,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 600 g of tetrahydrofuran, 89 g (0.51 mol) of 1-isopropenyl-2-benzimidazolidinone, 110.3 g (0.56 mol) of 3-mercaptopropyltrimethoxysilane, and 0.5 g of AIBN (azobisisobutyronitrile), and the mixture was heated and stirred at 60°C for 7 hours. Tetrahydrofuran and excess materials were removed by heating at 130°C under reduced pressure, yielding 248 g of compound 2. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0138] NH:10.8ppm, C6H4:6.9ppm~7.2ppm, -Si(OCH3):3.5ppm, N-CH:4.6ppm, N-CH(C H 3): 1.4 ppm, N-CH(CH3)-C H 2:2.9~3.2ppm, S-CH2-:2.4ppm, S-CH2-C H 2-: 1.6 ppm, S-CH2-CH2-C H 2-:0.6 ppm,

[0139] [ka]

[0140] <Compound 3> A 2,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 800 g of xylene, 169 g (0.8 mol) of 1-(3-chloropropyl)-1,3-dihydro-2H-benzimidazol-2-one, and 9.0 g of an amine catalyst, followed by 158 g (0.88 mol) of 3-aminopropyltrimethoxysilane. The mixture was stirred at 80° C. for 6 hours under a nitrogen stream. Distillation was performed to remove excess unreacted material, yielding 206 g of compound 3. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0141] NH:10.8ppm, C6H4:6.9ppm~7.2ppm, -Si(OCH3):3.5ppm, N-CH:4.6ppm, Si-CH2-:0.5~0.7ppm, Si-CH2-C H 2-: 1.6~1.8ppm, Si-CH2-CH2-C H 2-: 2.3 to 2.6 ppm

[0142] [ka]

[0143] <Compound 4> A 2,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 1,200 g of xylene, 113 g (0.84 mol) of 2-hydroxybenzimidazole, and 110 g (0.4 mol) of 1-(1-chloromethyl)-3-(2-trimethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, and the mixture was heated and stirred at 80° C. for 4 hours. After cooling, the mixture was filtered, and the xylene and excess materials were distilled off at 135° C. to obtain 140 g of compound 4. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0144] NH:10.8ppm, C6H4:7.1ppm~7.8ppm, -Si(OCH3):3.5ppm, Si-CH2-CH2-Si:0.5~1ppm, Si-CH2-N:0.6~0.8ppm, CH3-Si-CH3:-0.2ppm~0.2ppm

[0145] [ka]

[0146] <Compound 5> A 2,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 800 g of xylene, 120 g (0.8 mol) of 5-amino-1,3-dimethyl-1,3-dihydro-2H-benzimidazol-2-one, and 149 g (0.75 mol) of trimethoxysilylpropyl chloride, and the mixture was heated under a nitrogen stream at 80°C for 8 hours and at 120°C for 2 hours. After filtration, the xylene and excess trimethoxysilylpropyl chloride were removed by thermal stripping under reduced pressure, yielding 196 g of compound 5. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0147] NH:10.8ppm, C6H4:6.8ppm~7.2ppm, -Si(OCH3):3.3ppm, C6H3-NH:3.5~3.7ppm, N-CH:4.4ppm, N-CH2- CH 2-CH2: 3.5 to 3.8 ppm, N-CH2-CH2- CH 2: 2.8-3.1 ppm

[0148] [ka]

[0149] <Compound 6> A 1,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 500 g of xylene, 76 g (1.0 mol) of allyl chloride, and 186.5 g (0.95 mol) of 3-mercaptopropyltrimethoxysilane, and 0.5 g of AIBN was added under a nitrogen stream, followed by heating and stirring at 60°C for 7 hours. Excess materials were removed, yielding 248 g of intermediate compound 1.

[0150] A 2000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 800 g of xylene and 120 g (0.8 mol) of 5-amino-1,3-dimethyl-1,3-dihydro-2H-benzimidazol-2-one, followed by the addition of 204 g of the intermediate compound described above. The mixture was heated under a nitrogen stream at 80°C for 8 hours and at 120°C for 2 hours. After filtration, the xylene, unreacted material, and excess material were removed by thermal stripping under reduced pressure, yielding 262 g of compound 6. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0151] NH:10.8ppm, C6H4:6.8ppm~7.2ppm, -Si(OCH3):3.3ppm, C6H3-NH:3.5~3.7ppm, N-CH:4.4ppm, N-CH2- CH 2-CH2: 3.5 to 3.8 ppm, N-CH2-CH2- CH 2:2.8~3.1ppm, S-CH2:2.3ppm, S-CH2- CH 2: 1.4 ppm, S-CH2-CH2- CH 2:0.6 ppm

[0152] [ka]

[0153] <Compound 7> A 2,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 1,200 g of xylene, 113 g (0.84 mol) of 2-hydroxybenzimidazole, and 296 g (0.4 mol) of α,ω-bis(1-chloromethyldimethoxysilyl)-1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, and the mixture was heated and stirred at 80°C for 4 hours. The mixture was then treated with activated carbon and filtered. The xylene was then distilled off, yielding 368 g of compound 7. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0154] NH:10.8ppm, C6H4:6.8ppm~7.2ppm, -Si(OCH3):3.3ppm, N- CH 2:3.8~4.4ppm, CH3-Si-CH3:-0.2ppm~0.2ppm, Si-CH2-:0.6~0.8ppm

[0155] [ka]

[0156] <Compound 8> A 1,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 100 g of α,ω-dihydroxydodecamethylhexasiloxane, 196.3 g (1.0 mol) of 3-mercaptopropyltrimethoxysilane, and 0.5 g of a condensation catalyst, and the mixture was heated and stirred at 80°C for 4 hours to yield 139 g of an intermediate compound, a siloxane oligomer containing terminal mercaptopropyl groups.

[0157] A 1,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 300 g of tetrahydrofuran, 41 g (0.52 mol) of 1-isopropenyl-2-benzimidazolidinone, 85 g of the intermediate compound (mercaptopropyl-terminated siloxane oligomer) and 0.5 g of AIBN, and the mixture was heated and stirred at 60°C for 7 hours. Tetrahydrofuran and other components were removed by heating at 130°C under reduced pressure, yielding 119 g of compound 8. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0158] NH:10.8ppm, C6H4:6.8ppm~7.2ppm, -Si(OCH3):3.3ppm, N-CH:4.4ppm, N-CH( CH 3): 1.4 ppm, N-CH(CH3) -CH 2:2.8~3.1ppm, S-CH2:2.3ppm, S-CH2 -CH 2: 1.4 ppm, S-CH2-CH2- CH 2:0.6ppm, CH3-Si-CH3:-0.2ppm~0.2ppm

[0159] [ka]

[0160] <Compound 9> A 1,000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 400 g of toluene, 108 g (0.7 mol) of 1,1,3,5,7-pentamethylcyclotetrasiloxane, and 1.54 g of alumina-supported platinum catalyst, followed by the dropwise addition of 54 g (0.7 mol) of allyl chloride over approximately 1 hour. The temperature was raised to 120°C under a nitrogen stream. The reaction was then continued at 105°C for 4 hours, yielding Reaction Solution 1.

[0161] The resulting reaction solution 1 was cooled to room temperature, and 118 g (0.8 mol) of vinyltrimethoxysilane was added dropwise over approximately 1 hour. The temperature was raised to 120°C under a nitrogen stream. The reaction was then continued at 105°C for 4 hours to obtain reaction solution 2. The resulting reaction solution 2 was cooled to room temperature, and then 108 g (0.8 mol) of 2-hydroxybenzimidazole was added, followed by heating and stirring at 80°C for 4 hours. After cooling, the solution was filtered, and toluene and excess materials were removed by distillation under reduced pressure, resulting in concentration and yielding 303 g of compound 9. 1 Analysis by H-NMR revealed the following results, confirming that this was the target compound.

[0162] C6H4:6.8ppm~7.2ppm, -Si(OCH3):3.3ppm, N-CH2-CH2- CH 2:2.8~3.1ppm, -Si-CH2-CH2-Si(OCH3)3:0.5~1ppm, Si-CH3:0.1ppm~0.2ppm, Si-CH2-:0.5-0.7ppm, Si-CH2-CH2-:1.6~1.8ppm, Si-CH2-CH2-CH2-:2.3~2.6ppm

[0163] [ka]

[0164] (Preparation of Curable Silicone Composition) Curable polyorganosiloxane compositions were prepared by mixing the components according to the compositions shown in Tables 1 to 3.

[0165] (Evaluation method) <Appearance> The appearance (uniformity and coloration) of the polyorganosiloxane compositions was evaluated after preparation, storage at room temperature (23°C) for 7 days, or storage at 5°C for 3 days. The appearance was evaluated by visually inspecting the composition. The uniformity of the composition was evaluated on the following four-point scale. The higher the value, the higher the evaluation of the uniformity of the composition. The coloration of the composition was also evaluated on the following two-point scale. The lower the value, the less the evaluation of the composition. Uniformity assessment 4: Transparent 3: Transparent ~ Translucent 2: Translucent 1: Not dissolved or precipitated Coloring evaluation 2:Pale yellow 1: Pale yellow

[0166] <Viscosity> The viscosity of the polyorganosiloxane composition was measured at 23°C using a VISCOMETER TVB-10M manufactured by Toki Sangyo Co., Ltd. The rotor used was TM2, and the viscosity was measured under conditions of 60 pm and 1 minute value.

[0167] <Tuck-free time> The polyorganosiloxane composition was applied to a thickness of 100 μm on the surface of a 5 cm diameter aluminum petri dish whose surface had been cleaned with an organic solvent. The time (minutes) until the composition was confirmed to be dry was measured by touching the surface with a finger under an environment of 23°C and 50% relative humidity (RH).

[0168] <Heat resistance> The heat resistance of copper foil coated with the polyorganosiloxane composition was evaluated by placing it in a 150°C atmosphere for 30 minutes or in an 85°C, 85% RH atmosphere for 24 hours. The evaluation was performed by visually judging the change in color tone of the coating film, and was rated on the following 5-point scale. The higher the value, the higher the heat resistance. 5: Almost no change 4: Slight discoloration 3: Yellowing 2: Orange 1: Dark brown

[0169] <Heat cycle test (reliability)> The copper foil coated with the polyorganosiloxane composition was placed in an atmosphere where the temperature changed from -40 to 125°C over the course of one hour, and this cycle was repeated 250 times. One cycle consisted of changing from -40°C to 125°C in 30 minutes, and then changing from 125°C to -40°C in 30 minutes. Evaluation was performed by visually determining whether cracks occurred in the coating film, and was rated on the following five-point scale. The higher the value, the better the evaluation of reliability. 5: No change 4: Some fine cracks 3: Fine cracks present 2: Cracked 1: Large crack

[0170] <Corrosion resistance> The polyorganosiloxane composition was applied to a copper plate (JIS.H.3100:C1100P) whose surface had been polished with 4,000 mesh abrasive paper to a thickness of 100 μm and then cleaned, and the plate was left in an atmosphere of 23 ° C and 50% RH for 3 days to obtain a sample. The obtained sample was used to test for corrosion resistance (saltwater resistance) and corrosion resistance (sulfur resistance).

[0171] <Corrosion prevention (sulfur resistance)> A 100 ml glass bottle was charged with 0.2 g of sulfur and 5 g of water to obtain a sulfur-containing aqueous solution. The obtained sample was immersed in the sulfur-containing aqueous solution and left at 80°C for 10 days. After drying at room temperature (23°C) for 7 days, the condition of the substrate (discolored location, color, and area ratio) was confirmed. The area ratio of the discolored portion was evaluated according to the following "Corrosion Prevention Evaluation Criteria." The higher the value, the higher the evaluation of corrosion prevention (sulfur resistance).

[0172] <Corrosion prevention (saltwater resistance)> The obtained samples were immersed in a 5 wt% aqueous solution of sodium chloride (saltwater), left at 50°C for 7 days, and then dried at room temperature (23°C) for a further 7 days, after which the condition of the substrate (percentage of discolored area) was checked. The percentage of the discolored area was evaluated according to the "Corrosion Prevention Evaluation Criteria" below. The higher the value, the higher the evaluation of corrosion prevention (saltwater resistance).

[0173] <Corrosion resistance evaluation criteria> 10:0-9% 9-10: More than 9% and less than 15% 9: More than 15% and less than 20% 8: More than 20% and less than 30% 7: More than 30% and less than 40% 6: More than 40% and less than 50% 5: More than 50% and less than 60% 4: More than 60% and less than 70% 3: More than 70% and less than 80% 2: More than 80% and less than 90% 1: More than 90% and less than 100%

[0174] The results are summarized in Tables 1 to 3.

[0175] [Table 1]

[0176] [Table 2]

[0177] [Table 3]

[0178] As can be seen from Tables 1 and 2, the compositions of the examples were excellent in corrosion prevention and uniformity. In particular, comparison of Examples 1 to 4 and 6 to 7 with Examples 5 and 8 to 13 showed that saltwater resistance was superior when component (C) was a compound containing a benzimidazolidinone moiety, a siloxane chain, and a hydrolyzable group bonded to a silicon atom in one molecule.

[0179] Comparative Example 1 does not contain a component corresponding to compound (C). Comparative Examples 2 to 7 contain benzotriazole, imidazole, or the like, which are used as conventional rust inhibitors, as a component corresponding to compound (C). Comparative Example 8 does not use a composition.

[0180] The compositions of Comparative Examples 2 to 5 were poor in uniformity and saltwater resistance. In particular, the compositions of Comparative Examples 2 and 4 to 5 exhibited precipitation of benzotriazole, imidazole, etc., and the uniformity of the composition was significantly poor. The composition of Comparative Example 3 exhibited precipitation of 1-isopropenyl-2-benzimidazolidinone after storage at 5°C, and the uniformity of the composition was significantly poor. Furthermore, the compositions of Comparative Examples 1 and 6 to 7 exhibited poor corrosion prevention properties. Furthermore, the result of the saltwater resistance of Comparative Example 8, which did not use a composition, showed significant corrosion.

Claims

1. (A) a polyorganosiloxane having two or more hydrolyzable groups bonded to silicon atoms in one molecule and not having a benzimidazolidinone moiety; (B) a curing catalyst, and (C) A compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule. A curable polyorganosiloxane composition comprising: The component (C) is represented by the following general formula (1), (2), or (3): 【Chemical 26】 [During the ceremony, A 1 is a group represented by formula (4) or (5): 【Chemical 27】 (In formula (4), R 21 is a hydrogen atom or a hydrocarbon group.) 【Chemical 28】 (In formula (5), R 22 and R 23 each independently represent a hydrogen atom or a hydrocarbon group.) is a group represented by X 1 is an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 1 is each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 1 is a hydrolyzable group. 【Chemical 29】 [During the ceremony, A 2 and A 3 each independently represent a group represented by formula (4) or (5); X 2 and X 3 each independently represent an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 2 s each independently represent a hydrolyzable group or a hydrocarbon group, provided that at least one R 2 is a hydrolyzable group; R 3 is independently a hydrocarbon group; L 1 is 0 or a number from 1 to 1,000. 【Chemistry 30】 [During the ceremony, A 4 is a group represented by formula (4) or (5), X 4 and X 5 each independently represent an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear siloxane chain; R 4 is independently a hydrocarbon group; R 5 s each independently represent a hydrolyzable group or a hydrocarbon group, provided that at least one R 5 is a hydrolyzable group; a is an integer of 1 or more, and when a is an integer of 2 or more, each A 4 , X 4 and R 4 are the same or different; b is an integer of 1 or more, and when b is an integer of 2 or more, each of X 5 , R 4 and R 5 is the same or different; c is an integer of 0 or 1 or more, and when c is an integer of 2 or more, each R 4 is the same or different; a+b+c is an integer of 3 or greater.

2. 2. The curable polyorganosiloxane composition according to claim 1, further comprising one or more selected from the group consisting of (D) a crosslinking agent, (E) an adhesion promoter, and (F) a polyorganosiloxane having no hydrolyzable groups bonded to silicon atoms.

3. A coating agent for electronic parts, comprising the curable polyorganosiloxane composition according to claim 1 or 2.

4. A metal surface treatment agent using the curable polyorganosiloxane composition according to claim 1 or 2.

5. A cured product obtained by curing the curable polyorganosiloxane composition according to claim 1 or 2.

6. An electronic component comprising the curable polyorganosiloxane composition of claim 1 or 2.

7. (C) A compound containing a benzimidazolidinone moiety and a hydrolyzable group bonded to a silicon atom in one molecule, the compound being represented by the following general formula (1), (2), or (3): 【Chemical 31】 [During the ceremony, A 1 is a group represented by formula (4) or (5): 【Chemical 32】 (In formula (4), R 21 is a hydrogen atom or a hydrocarbon group.) 【Chemical 33】 (In formula (5), R 22 and R 23 each independently represent a hydrogen atom or a hydrocarbon group.) is a group represented by X 1 is an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 1 is each independently a hydrolyzable group or a hydrocarbon group, provided that at least one R 1 is a hydrolyzable group. 【Chemical 34】 [During the ceremony, A 2 and A 3 each independently represent a group represented by formula (4) or (5); X 2 and X 3 each independently represent an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear or cyclic siloxane chain; R 2 s each independently represent a hydrolyzable group or a hydrocarbon group, provided that at least one R 2 is a hydrolyzable group; R 3 is independently a hydrocarbon group; L 1 is 0 or a number from 1 to 1,000. 【Chemistry 35】 [During the ceremony, A 4 is a group represented by formula (4) or (5), X 4 and X 5 each independently represent an alkylene group which may be interrupted by —S—, an alkylene group which may be interrupted by —NH—, or an alkylene group which may be interrupted by a linear siloxane chain; R 4 is independently a hydrocarbon group; R 5 s each independently represent a hydrolyzable group or a hydrocarbon group, provided that at least one R 5 is a hydrolyzable group; a is an integer of 1 or more, and when a is an integer of 2 or more, each A 4 , X 4 and R 4 are the same or different; b is an integer of 1 or more, and when b is an integer of 2 or more, each of X 5 , R 4 and R 5 is the same or different; c is an integer of 0 or 1 or more, and when c is an integer of 2 or more, each R 4 is the same or different; a+b+c is an integer of 3 or more.