JP2004190010A - Gel composition, coating agent and sealing method - Google Patents

Abstract

〔ｎ≧１、ｍ＝１の時、Ｍ¹はモノオール又はポリオールから水酸基を除いた残基、ｍ≧２の時、Ｍ¹はポリオールから水酸基を除いた残基、Ｒ¹はアルキレン基又は側鎖がエーテル基で置換されたアルキレン基、Ｘは水素原子又はグリシジル基を表す。〕
【化２】

〔ｍ＝１の時、Ｍ²はモノオール又は２価以上のアルコールから水酸基を除いた残基、ｍ≧２の時、Ｍ²は２価以上のアルコールから水酸基を除いた残基、Ｘは水素原子又はグリシジル基を表す。〕
【選択図】 なし
【Task】
Provided are a gel composition, a coating agent, and a sealing method having excellent adhesion without requiring complicated processing and expensive compositions, and without causing electrical contact failure.
[Solution]
(A) a crosslinkable silyl group-containing organic polymer; (B) at least one organic compound of a liquid organic compound represented by the following general formula (1) and a liquid organic compound represented by the following general formula (2); C) A curing catalyst for (A) was included.
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[When n ≧ 1, m = 1, M ¹ is a residue obtained by removing a hydroxyl group from a monool or polyol; when m ≧ 2, M ¹ is a residue obtained by removing a hydroxyl group from a polyol; R ¹ is an alkylene group or An alkylene group having a side chain substituted with an ether group, X represents a hydrogen atom or a glycidyl group. ]
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[When m = 1, M ² is a residue obtained by removing a hydroxyl group from a monool or a divalent or higher alcohol, when m ≧ 2, M ² is a residue obtained by removing a hydroxyl group from a divalent or higher alcohol, and X is Represents a hydrogen atom or a glycidyl group. ]
[Selection diagram] None

Description

  The present invention relates to a gel composition, a coating agent, and a sealing method, and more particularly, to a gel composition, a coating agent, and a coating composition that have good adhesion to electronic components and the like and do not cause electrical contact failure. The present invention relates to a method of coating, potting, dipping, or molding an electronic component by using (hereinafter, referred to as coating or sealing in the present invention).

  BACKGROUND ART Conventionally, silicone gel compositions and urethane gel compositions have been used as coating agents and potting agents in the fields of electricity and electronics, optics and optoelectronics, sensors, and the like. In particular, the silicone gel composition is used for potting and sealing parts in the electric and electronic fields, particularly for covering control circuit elements such as power transistors, ICs and capacitors, and for protecting them from thermal and mechanical obstacles. Used as a coating material. In these applications, in order to protect the electronic components from moisture and the like, adhesion to the electronic components and the like is required. However, the silicone gel composition has a disadvantage that adhesion to a substrate is poor due to low adhesiveness, and when used as a potting agent for an electronic component, peeling between the component and the cured gel product occurs. In some cases, moisture, moisture, and the like invade therefrom, causing corrosion, poor insulation, and the like.

  Further, the silicone gel composition generally contains a low-molecular-weight cyclic siloxane, and there is a problem in that the low-molecular-weight siloxane causes electrical contact failure. As a countermeasure against low-molecular-weight siloxane, methods for removing low-molecular-weight siloxane, methods for reducing the content, and the like have been studied, but all have problems such as requiring complicated treatment and expensive compositions (for example, And Patent Documents 1 to 4.).

In order to solve the above-mentioned problem, switching to a material other than the silicone gel composition has been studied, but a material having the same characteristics as the silicone gel composition and low cost has not been found.
JP-A-6-329803 JP 2001-26648 A JP-A-6-136270 JP-A-6-321966 JP-A-52-73998 JP-A-55-9669 JP-A-59-122541 JP-A-60-6747 JP-A-61-233043 JP-A-63-112642 JP-A-3-79627 JP-A-4-283259 JP-A-5-70531 JP-A-5-287186 JP-A-11-80571 JP-A-11-116763 JP-A-11-130931 JP-A-11-100427 JP-A-2000-143775 JP 2000-169544 A JP 2002-212415 A Japanese Patent No. 3030020 Japanese Patent No. 3295566 Japanese Patent No. 3313360 Japanese Patent No. 3317353 Japanese Patent No. 3350011 JP-A-59-78223 JP-A-60-228516

  The present invention has been made in view of the above-described problems, and does not require complicated processing or an expensive composition, does not cause electrical contact failure, and has a gel composition having excellent adhesion, a coating agent, and the like. It is intended to provide a coating method.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have succeeded in forming a modified silicone into a gel composition. In the present invention, the gel composition means a composition that becomes a gel after curing.

  The gel composition of the present invention comprises (A) a crosslinkable silyl group-containing organic polymer, (B) a liquid organic compound represented by the following general formula (1) and a liquid organic compound represented by the following general formula (2). It is characterized by containing one kind of organic compound and a curing catalyst for (C) and (A).

[In the above formula (1), n and m are each an integer of 1 or more; when m = 1, M ¹ is a residue obtained by removing a hydroxyl group from a monool or polyol; when m ≧ 2, M ¹ is A residue obtained by removing a hydroxyl group from a polyol, R ¹ represents an alkylene group or an alkylene group having a side chain substituted with an ether group, and X represents a hydrogen atom or a glycidyl group. ]

[In the above formula (2), m is an integer of 1 or more; when m = 1, M ² is a residue obtained by removing a hydroxyl group from a monool or a divalent or higher alcohol; when m ≧ 2, M ² Is a residue obtained by removing a hydroxyl group from a divalent or higher alcohol, and X represents a hydrogen atom or a glycidyl group. ]

  It is preferable that the component (B) is at least one organic compound of an epoxy resin and a polyol.

  The component (A) is preferably at least one polymer of a crosslinkable silyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer.

  It is preferable to further add the component (D) to the gel composition of the present invention.

  More preferably, the component (D) is a styrene (co) polymer.

  The coating agent of the present invention is characterized by containing the above gel composition of the present invention.

  The sealing method of the present invention is characterized in that electronic parts and the like are sealed using the coating agent of the present invention.

  ADVANTAGE OF THE INVENTION According to the gel composition of this invention and the coating agent of this invention, a gel composition and coating agent which do not generate an electrical contact failure and do not require a complicated process and an expensive composition, and have excellent adhesiveness. With the sealing method of the present invention, the electronic component is sealed so that it does not require complicated processing and expensive compositions, does not cause electrical contact failure, and has excellent adhesion. Can be stopped.

  Hereinafter, embodiments of the present invention will be described. However, these embodiments are illustratively shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

The gel composition of the present invention is characterized by containing the following components (A), (B) and (C).
(A) a crosslinkable silyl group-containing organic polymer (B) at least one organic compound (C) of the liquid organic compound represented by the general formula (1) and the liquid organic compound represented by the general formula (2) Curing catalyst for A)

  As the crosslinkable silyl group-containing organic polymer used as the component (A), conventionally known ones can be widely used, and a siloxane bond is formed in the molecule to form a crosslinked rubbery cured product. There is no particular limitation as long as it is an organic polymer containing one or more silyl groups. Examples of such a crosslinkable silyl group-containing organic polymer (A) include those disclosed in Patent Documents 5 to 26. Specific examples of the crosslinkable silyl group-containing organic polymer (A) include a polyoxy group containing one or more crosslinkable silyl groups in the molecule, and a main chain each of which may contain an organosiloxane. Examples thereof include an alkylene polymer, a vinyl-modified polyoxyalkylene polymer, a vinyl polymer, a polyester polymer, an acrylate polymer, a methacrylate polymer, and copolymers and mixtures thereof. It is preferable that 1 to 5 crosslinkable silyl groups are included in the molecule from the viewpoint of the curability of the composition and the physical properties after curing. Further, the crosslinkable silyl group is preferably a compound represented by the following general formula (3) which is easily crosslinked and easily produced.

(Wherein R ² is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group shown is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group. In the case of Y, Y may be the same or different groups, wherein Y is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, and 1 Is most preferred.)

  The main chain of the crosslinkable silyl group-containing organic polymer (A) may contain an organosiloxane from the viewpoint of physical properties such as tensile adhesion and modulus after curing. Preferred are oxyalkylene polymers, copolymers and mixtures thereof. In particular, as component (A), a polyoxyalkylene polymer or an acryl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule and having a main chain each containing an organosiloxane. Preferred are methacryl-modified polyoxyalkylene polymers, copolymers and mixtures thereof, and the main chains may each contain an organosiloxane, polyoxypropylene polymer, acryl-modified polyoxypropylene polymer, methacryl-modified Those which are polyoxypropylene polymers, copolymers or mixtures thereof are more preferred.

  The above-mentioned molecule containing one or more crosslinkable silyl groups in the molecule, the vinyl-modified polyoxyalkylene polymer which may contain an organosiloxane contains one or more crosslinkable silyl groups in the molecule, In the presence of a polyoxyalkylene polymer which may contain an organosiloxane, one or two or more vinyl monomers are produced by a usual radical polymerization method such as addition of a radical polymerization initiator or irradiation with ultraviolet light. It can be obtained by polymerization or the like (Patent Documents 27 and 28 and the like are cited as reference, but are not limited thereto).

  The vinyl monomer is a compound having one or more polymerizable unsaturated bonds in the molecule, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid , Vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate , Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacryl Amide, n-methylol acrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxy Bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, triacrylate Methylol propane triacrylate Ethoxylated isocyanuric acid triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, polyurethane diacrylate , Ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, polyester polyacrylate, 1,6-hexanediol diacrylate, 2- (2-ethoxy) Ethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofur Lyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, zinc diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, pentaacrylate ester, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , Lauryl methacrylate , Polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc dimethacrylate, trimethylolpropane trimethacrylate, and compounds represented by the following chemical formulas (4) to (27) But are not limited to these.

  The vinyl monomer is used in an amount of 0.1 to 1000 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer which may contain an organosiloxane. preferable. The vinyl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing the organosiloxane may contain one or more crosslinkable silyl groups in the molecule. A cross-linkable silyl obtained by introducing a cross-linkable silyl group into a polyoxyalkylene polymer which may contain an organosiloxane and a polymer obtained by polymerizing at least one of the vinyl monomers. What blended with the group-containing vinyl polymer can also be used.

  In the present invention, the crosslinkable silyl group-containing organic polymer (A) having a number average molecular weight of 1,000 or more, particularly 6,000 to 30,000, and having a narrow molecular weight distribution is easy to handle because the viscosity before curing is low, and the strength after curing. Physical properties such as elongation, modulus and the like are suitable. The above component (A) may be used alone or in combination of two or more.

  As the component (B), at least one kind of a liquid organic compound represented by the following general formula (1) and a liquid organic compound represented by the following general formula (2) can be used.

In the above general formula (1), m is an integer of 1 or more, and when m = 1, M ¹ represents a residue obtained by removing a hydroxyl group from a monool or a residue obtained by removing a hydroxyl group from a polyol; In the formula, M ¹ represents a residue obtained by removing a hydroxyl group from a polyol. In M ^1, as the monol, for example, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 3-methyl-propanol, 2-methyl-2-propanol, 1-pen Tertanol, 2-pentanol, 3-pentanol, 2-methylbutanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethylpropanol, 1-hexanol, 2-hexanol, 3- Methylpentanol, heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 2-ethyl-3-hexanol, 2,5-dimethyl-2-hexanol, 3-ethyl-1-heptanol, 2-methyl-2 -Ethyl-hexanol, 1-decanol, 2-decanol, 1- Decanol, 2-dodecanol, 1-tetradecanol, 2-tetradecanol, 1-hexadecanol, 2-hexadecanol, 1-octadecanol, 2-octadecanol, cyclohexanol, cyclohexanemethanol, hydroxymethyl Monohydric alcohols such as benzene; and monohydric phenols such as phenol, cresol, xylenol, thymol, naphthol, and t-butylphenol. In M ^1, as the polyol, such as ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol (2, 2-dimethyl-1,3-propanediol), isoprene glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Diol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexane Diol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-te Ladecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, 1,12-octadecanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4 , 7-diol, dihydric alcohols such as bis (hydroxymethyl) benzene; glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3 4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4- Trihydric alcohols such as propyl-3,4,5-heptanetriol and pentamethylglycerin (2,4-dimethyl-2,3,4-pentanetriol); pentaerythritol, 1,2,3,4-pentanetetrol , 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, Tetrahydric alcohols such as N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine; adonitol, arabitol, xy Pentahydric alcohols such as toll and triglycerin; hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, daritol, talose, allose; octahydric alcohols such as sucrose; polyvinyl alcohol, polyglycerin, phenoxy resin (bisphenol Polyhydric alcohols such as A and epichlorohydrin); dihydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, brominated bisphenol A, bisphenol F and bisphenol S; tris (4-hydroxyphenyl) methane, tris ( Trihydric phenols such as 4-hydroxyphenyl) ethane and 1,1,3-tris (3-t-butyl-4-hydroxy-6-methylphenyl) butane; reaction of phenols with divinylbenzene Examples include polyphenols such as products, formaldehyde condensates of phenols, and hydroxystyrene polymers.

In the above general formula (1), R ¹ is represented by an alkylene group or an alkylene group in which a side chain is substituted with an ether group, and a part of (R ¹ O) _n is ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran ( 1,4-butylene oxide), alkylene oxides such as long-chain α-olefin oxides and styrene oxides; obtained by addition polymerization of monoglycidyl ethers such as methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether and phenyl glycidyl ether. be able to. When the (R ¹ O) _n portion is formed by addition polymerization of an alkylene oxide, a monoglycidyl ether, or the like, R ¹ O is determined by the alkylene oxide, the monoglycidyl ether, or the like to be added.

The polymerization form of the added alkylene oxide, monoglycidyl ether, etc. is not limited, and homopolymerization of one kind of alkylene oxide or glycidyl ether, random copolymerization of two or more kinds of alkylene oxides, monoglycidyl ether, etc., block copolymerization Or random / block copolymerization may be used. R ¹ is an alkylene group when an alkylene oxide is used, and an alkylene group whose side chain is substituted with an ether group when a monoglycidyl ether is used. R ¹ is preferably an alkylene group having 2 to 4 carbon atoms, and most preferably an ethylene group. When R ¹ is two or more groups, at least one of them is preferably an ethylene group. The polymerization degree n is 1 or more, preferably 1 to 300, more preferably 1 to 200, and most preferably 5 to 100. Incidentally, in the general formula (1), groups represented by (R ¹ O) _n is m number exists, the number of groups and n represented by each of (R ¹ O) _n is optionally substituted by one or more identical You may.

  In the above general formula (1), X represents a hydrogen atom or a glycidyl group represented by the following formula (28). In the general formula (1), there are m groups represented by X, but each X may be the same or different.

  Examples of the liquid organic compound represented by the general formula (1) include compounds represented by the following chemical formulas (29) to (34).

  In the above formula (31), n is 6 or 7, in the above formula (32), n is 11 or 12, and in the above formula (34), n is an arbitrary integer.

In the general formula (2), m is an integer of 1 or more, and when m = 1, M ² represents a residue obtained by removing a hydroxyl group from a monool or a residue obtained by removing a hydroxyl group from a divalent or higher alcohol. When m ≧ 2, M ² represents a residue obtained by removing a hydroxyl group from a divalent or higher valent alcohol. In M ² , examples of the monool and the dihydric or higher alcohol include the monool and the dihydric or higher alcohol as described above in M ¹ .

  In the above general formula (2), X represents a hydrogen atom or a glycidyl group represented by the above formula (28), similarly to X described in the above general formula (1). In the general formula (2), there are m groups represented by X, but each X may be the same or different.

  Examples of the liquid organic compound represented by the general formula (2) include compounds represented by the following chemical formulas (35) to (44).

In the above chemical formula (35), R ³ represents a hydrocarbon group having 12 or 13 carbon atoms.

  In the above component (B), the liquid organic compound means an organic compound that is liquid at ordinary temperature, and has a vapor pressure of 1 mmHg / 100 ° C or more, more preferably 10 mmHg / 100 ° C or more, and has a fluidity. Organic compounds having a minimum temperature of 0 ° C or lower, more preferably -20 ° C or lower, are preferred.

  The liquid organic compound represented by the general formula (1) and the liquid organic compound represented by the general formula (2) are not particularly limited, but at least one organic compound of an epoxy resin and a polyol is preferably used. The epoxy resin and the polyol can be used as a mixture. Particularly, an epoxy resin is preferable because of its high compatibility. Further, the liquid organic compound represented by the general formula (1) and a modified product of the liquid organic compound represented by the general formula (2), for example, a urethane modified product or an ester modified product, also include the component (B) of the present invention. Can be used as Specifically, for example, a urethane-modified epoxy resin obtained by reacting a polypropylene glycol with an epoxy resin using a urethane bond, such as Adeka Resin EPU-16A (manufactured by Asahi Denka Kogyo KK), is preferably used.

  The above component (B) may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not particularly limited. For example, the liquid organic compound represented by the above general formula (1) and the liquid organic compound represented by the above general formula (2) may be used in combination. The compounding ratio of the component (B) is preferably from 10 to 2,000 parts by weight, more preferably from 25 to 1500 parts by weight, based on 100 parts by weight of the component (A). If the blending ratio of the component (B) is less than 10 parts by weight, the gel becomes too hard (exceeding 30 in Asker C hardness), and if it exceeds 2000 parts by weight, the liquid material bleeds or the curability is poor. There are cases.

  The component (C) is not particularly limited as long as it exhibits a function of a curing catalyst with respect to the component (A). Examples thereof include organometallic compounds and amines. Is preferred. Examples of the silanol condensation catalyst include, for example, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate Organic tin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; organic acid bismuth compounds such as bismuth trioctylate and bismuth versatate; reaction products of dibutyltin oxide and phthalic acid ester Titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diiso Organoaluminum compounds such as ropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; and other acidic and basic catalysts known as silanol condensation catalysts. No. Of these, dibutyltin diacetylacetonate is particularly preferred because it is a liquid having a high crosslinking rate, toxicity and relatively low spontaneity. The mixing ratio of the component (C) is from 0.1 to 30 parts by weight, especially from 0.1 to 30 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer (A) in view of the crosslinking rate, the physical properties of the cured product, and the like. It is preferable to use 5 to 20 parts by weight. These curing catalysts may be used alone or in combination of two or more.

  It is preferable to further add a component (D) to the gel composition of the present invention. In the present invention, it is necessary to use, as the component (B), a component that is compatible with the component (A) and does not cause bleeding or opacity on the surface during the curing process. By adding the compound, a stable gel composition that does not cause bleeding or opacity of the component (B) is obtained even in a high temperature range from an extremely cold temperature of 0 ° C. or less to about 100 ° C. to 120 ° C. outside the room temperature range. It becomes possible. When a highly compatible compound such as an epoxy resin is used as the component (B), the compatibility is further increased by further adding the component (D), which is preferable. Further, by using a styrene (co) polymer as the component (D), it is possible to obtain a colorless transparent gel which is less likely to be discolored with time.

  As the component (D), conventionally known compatibilizers can be widely used and are not particularly limited. Examples thereof include a styrene-based (co) polymer; a coumarone-indene resin, a naphthenic resin, a coumarone resin, and a phenol resin. Resin such as a mixture of rosin and rosin; pt-butylphenol-acetylene resin; phenol formaldehyde resin having a low degree of polymerization and a low softening point (about 60 to 100 ° C.); xylene-phenol resin; xylene resin; Phenolic and terpene resins such as terpene-phenol resins and terpene resins that also improve the adhesiveness, adhesiveness and heat resistance; synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and aliphatic cyclic hydrocarbon resins Petroleum hydrocarbon resins, such as hydrogenated and hydrogenated hydrocarbon resins; Ester, glycerol ester of rosin, hydrogenated rosin, highly hydrogenated wood resin, methyl ester of hydrogenated rosin, triethylene glycol ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, polymerized rosin And rosin derivatives such as glycerol ester of polymerized rosin, zinc resinate, and cured rosin; low molecular weight polystyrene; and other specially prepared products. Of these, styrene (co) polymers are particularly preferred. These compatibilizers may be used alone or in combination of two or more.

  As the styrene-based (co) polymer, conventionally known ones can be widely used and are not particularly limited. Examples thereof include styrene-based polymers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, and salts thereof. (Co) polymers obtained by (co) polymerizing one or more monomers are exemplified. As the styrene-based polymer, specifically, trade names: FTR-8100 and FTR-8120 manufactured by Mitsui Chemicals, Inc. can be used. Further, as the styrene copolymer, a copolymer obtained by copolymerizing at least one styrene monomer with at least one other monomer copolymerizable therewith may be used. It is possible. Examples of the copolymerizable monomer include, but are not particularly limited to, α-olefins having 2 to 12 carbon atoms such as 1-heptene, ethyl-1-butene, and methyl-1-nonene; -Unsaturated compounds such as non-conjugated dienes such as pentadiene and dicyclopentadiene. As the styrene-based copolymer, specifically, trade names: FTR-6100, FTR-6125, FTR-7125, etc., manufactured by Mitsui Chemicals, Inc. can be used. The styrene (co) polymers may be used alone or in combination of two or more.

  The component (D) is preferably used in an amount of 2 to 400 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the component (A). If the compounding ratio of the component (D) is less than 2 parts by weight, bleeding of the liquid material tends to occur, and if it exceeds 400 parts by weight, the viscosity of the composition may increase, resulting in poor workability.

  Further, it is preferable that a silane coupling agent is further added to the gel composition of the present invention. The silane coupling agent is not particularly limited and known ones can be used. For example, N-β (γ-aminoethyl) γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and γ- (methacryloxypropyl) trisilane can be used. Methoxysilane and the like can be mentioned. Preferable examples include an aminosilane compound and a compound which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule. One or more of these silane coupling agents can be used simultaneously.

  In the gel composition of the present invention, as long as the performance as a gel composition is not impaired, in addition to the above-mentioned components, a filler and a pigment, a plasticizer, an adhesion promoter, a stabilizer, a wax, an antioxidant Known additives such as an ultraviolet absorber, a light stabilizer, a thixotropic agent, and a coloring agent can be blended. For example, it is preferable to use a colorant or a pigment, since the component coated with the gel composition of the present invention can be intentionally made invisible from the outside.

  The gel composition of the present invention is suitably used as a coating agent. The coating agent of the present invention containing the gel of the present invention has good adhesion to electronic / electric parts (referred to as electronic parts in the present invention) and the like, and does not cause electric contact failure. It is particularly suitably used as a coating agent for coating, potting, dipping, or molding.

  Hereinafter, the present invention will be described more specifically with reference to Examples. However, it is needless to say that the Examples are illustrative and should not be construed as limiting.

(Example 1)
As shown in Table 1, 100 parts by weight of Cyril MA430 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) as the component (A) and 200 parts by weight of Exenol 3020 (manufactured by Asahi Glass Co., Ltd.) were blended as the component (B). Heat to 100 ° C. with stirring. While maintaining this temperature, the mixture is stirred under reduced pressure for 1 hour to remove water in the system, and then cooled to room temperature. After cooling, 1 part by weight of a silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 6 parts by weight of U-700ES (manufactured by Nitto Kasei Co., Ltd.) are added as the component (C), and further under reduced pressure. Stirring was performed for 10 minutes to obtain the target composition.

The compounding ratio of each compounding substance in Table 1 is shown by part by weight, and * 1 to * 16 are as follows.
* 1: Crosslinkable silyl group-containing organic polymer (Kanebuchi Chemical Industry Co., Ltd., trade name: Cyril MA430)
* 2: Crosslinkable silyl group-containing organic polymer (Kanebuchi Chemical Industry Co., Ltd., trade name: Cyril SAT200)
* 3: Crosslinkable silyl group-containing organic polymer (Kanebuchi Chemical Industry Co., Ltd., trade name: Cyril SAT350)
* 4: Bisphenol alkylene oxide-added epoxy resin (Adeka Resin EP-4000, manufactured by Asahi Denka Kogyo KK)
* 5: Urethane-modified epoxy resin (Adeka Resin EPU-16A manufactured by Asahi Denka Kogyo Co., Ltd.)
* 6: Dihydric alcohol-modified epoxy resin (Adeka Resin ED-503, manufactured by Asahi Denka Kogyo Co., Ltd.)
* 7: Trihydric alcohol-modified epoxy resin (Adeka Resin ED-505, manufactured by Asahi Denka Kogyo KK)
* 8: Polypropylene glycol-modified epoxy resin (Adeka Resin ED-506, manufactured by Asahi Denka Kogyo KK)
* 9: Polypropylene glycol (manufactured by Asahi Glass Co., Ltd., trade name: Exenol 3020)
* 10: Polypropylene glycol (manufactured by Asahi Glass Co., Ltd., trade name: Exenol 420)
* 11: Tin-based curing catalyst (Nitto Kasei Co., Ltd., trade name: U-700ES)
* 12: Styrene-based copolymer (trade name: FTR-6100, manufactured by Mitsui Chemicals, Inc.)
* 13: Styrene-based (co) polymer (trade name: FTR-8080, manufactured by Mitsui Chemicals, Inc.)
* 14: N-β (aminoethyl) γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM603)
* 15: Ketimine structure-containing aminosilane compound (Shin-Etsu Chemical Co., Ltd., trade name: X-12-817)
* 16: Bisphenol A type epoxy resin (trade name: EP-4100, manufactured by Asahi Denka Kogyo Co., Ltd.)

1. Analysis of low molecular siloxane The composition obtained in Example 1 was cured for 7 days in an atmosphere of 23 ° C. and 50% RH (relative humidity) to obtain a cured product. 10 mL of chloroform was added to 1 g of the cured product, and a soluble material was extracted for 24 hours. This solution was subjected to gas chromatography analysis, and it was confirmed that low molecular siloxanes (D13 to D11) were not detected (detection limit: 10 ppm).

2. Test Method of Composition The composition obtained in Example 1 was tested for transparency, hardness, bleed, and adhesiveness as follows. The results are shown in Table 2- (1).

(transparency)
The composition is poured into a paper cup having a diameter of about 5 cm (marked with a circle in advance by magic) to a depth of about 5 mm, cured at 23 ° C. and 50% RH for 4 days, and further cured at 50 ° C. for 3 days. . After curing, it was evaluated whether or not the circle mark at the bottom could be confirmed.

(hardness)
The cured product produced in the above-mentioned transparency test is taken out, and the hardness is measured with an Asker hardness meter (type C).

(Bleed)
When the cured product prepared in the above-described transparency test is touched with a finger, it is confirmed that the liquid material does not adhere to the finger.

(Adhesive adhesion)
The composition obtained in Example 1 was applied to an aluminum plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm to a thickness of 50 μm in an atmosphere of 23 ° C. and 50% RH. A film (thickness: 50 μm) is stuck and three times reciprocating with a hand roller. This was cured in an atmosphere of 23 ° C. and 50% RH for 11 days and further at 50 ° C. for 3 days to obtain a test piece. The 180 ° C. peel strength of the PET film is measured (pulling speed 200 mm / min). The adhesiveness on the electronic substrate was examined by evaluating the adhesiveness of the aluminum plate.

The evaluation method in Table 2 is as follows.
Hardness: ：: measured value of 30 or less, x: when measured value exceeds 30,-: unmeasurable.
Transparency: ：: O mark can be confirmed, ×: O mark could not be confirmed.
Adhesive property; ：: measured value 0.15 KM / m (400 gf / 25 mm) or more
Δ: About 0.13KM / m (350gf / 25mm)
X: The side constant value is 0.09 KM / m (250 gf / 25 mm) or less.
Bleed; ○: no adhesion, ×: adhesion.

(Examples 2 to 5 and Comparative Examples 1 to 4)
As shown in Table 1, an experiment was performed in the same manner as in Example 1 except that the compounding substances and the compounding ratio were changed, to obtain a target composition. As in Example 1, tests for transparency, hardness, bleed, and adhesiveness were performed. The results of Examples 2 to 5 are shown in Table 2- (1), and the results of Comparative Examples 1 to 4 are shown in Table 2- (2).

(Example 6)
As shown in Table 1, 100 parts by weight of Cyril MA430 (manufactured by Kaneka Chemical Industry Co., Ltd.) as the component (A), 200 parts by weight of Exenol 420 (manufactured by Asahi Glass Co., Ltd.) as the component (B), (D) 50 parts by weight of FTR6100 (manufactured by Mitsui Chemicals, Inc.) are blended as components, and heated and melted at 100 ° C. while stirring. After melting, the mixture is stirred under reduced pressure for 1 hour while maintaining this temperature to remove water in the system, and then cooled to room temperature. After cooling, 1 part by weight of a silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 6 parts by weight of U-700ES (manufactured by Nitto Kasei Co., Ltd.) are added as the component (C), and further under reduced pressure. Stirring was performed for 10 minutes to obtain the target composition.

  As in Example 1, tests for transparency, hardness, bleed, and adhesiveness were performed. The results are shown in Table 2- (1).

(Examples 7 to 13 and Comparative Example 5)
As shown in Table 1, an experiment was conducted in the same manner as in Example 6 except that the compounding substances and the compounding ratio were changed, to obtain a target composition. As in Example 1, tests for transparency, hardness, bleed, and adhesiveness were performed. Table 2- (1) shows the results of Examples 7 to 13, and Table 2- (2) shows the results of Comparative Example 5.

(Comparative Example 6)
As shown in Table 1, an experiment was conducted in the same manner as in Example 1 except that 300 parts by weight of the epoxy resin was used instead of 200 parts by weight of the component (B) to obtain a target composition. As in Example 1, tests for transparency, hardness, bleed, and adhesiveness were performed. The results are shown in Table 2- (2).

As shown in Table 2, each of the compositions obtained in Examples 1 to 13 showed good results with respect to hardness, transparency, adhesiveness and bleed. On the other hand, Comparative Examples 1 to 5 had a problem in hardness, and Comparative Examples 1 and 3 further had poor adhesiveness. Comparative Example 6 was not a uniform cured product but a semi-cured semi-liquid, non-uniform and opaque state, and could not be evaluated as a gel. The composition obtained in Examples 2 to 13 was analyzed for low-molecular-weight siloxane in the same manner as in Example 1. As a result, no low-molecular-weight siloxane was detected.

Claims (7)

(A) a crosslinkable silyl group-containing organic polymer,
(B) A liquid organic compound represented by the following general formula (1) and at least one organic compound represented by the following general formula (2), and (C) a curing catalyst for (A). A gel composition characterized by the following.

[In the formula (1), n and m are each an integer of 1 or more; when m = 1, M ¹ is a residue obtained by removing a hydroxyl group from a monool or a polyol; when m ≧ 2, M ¹ is a polyol And R ¹ represents an alkylene group or an alkylene group having a side chain substituted with an ether group, and X represents a hydrogen atom or a glycidyl group. ]

[In the formula (2), m is an integer of 1 or more; when m = 1, M ² is a residue obtained by removing a hydroxyl group from a monool or a divalent or higher alcohol; when m ≧ 2, M ² is X represents a residue obtained by removing a hydroxyl group from a divalent or higher alcohol, and X represents a hydrogen atom or a glycidyl group. ]   The gel composition according to claim 1, wherein the component (B) is at least one organic compound of an epoxy resin and a polyol.   The component (A) is at least one polymer of a crosslinkable silyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer. Or the gel composition according to 2.   The gel composition according to any one of claims 1 to 3, further comprising a component (D) a compatibilizer.   The gel composition according to claim 4, wherein the component (D) is a styrene (co) polymer.   A coating agent comprising the gel composition according to claim 1. A method for sealing an electronic component using the coating agent according to claim 6.