JP2014122267A - Moisture proof insulation coating, encapsulation and insulation treatment method by using moisture proof insulation coating and encapsulation and insulation treated electronic component obtained using moisture proof insulation coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable moisture proof insulation coating excellent in curability with low exposure dose, and having high long term insulation reliability.SOLUTION: There is provided a photocurable moisture proof insulation coating containing a (meth)acryloyl group-containing compound having no silicon atoms, and a photo-curing initiator having an oxime ester structure. Polyol poly(meth)acrylate, epoxy(meth)acrylate, urethane(meth)acrylate and a (meth)acryl monomer are preferable as the (meth)acryloyl group-containing compound and a compound represented by the formula (I), where Ris a hydrocarbon group, Ris a hydrocarbon group having 1 to 10 carbon atoms, and Ris a hydrocarbon group having 1 to 6 carbon atoms, is preferable as the photo-curing initiator.

Description

  The present invention relates to a moisture-proof insulating paint, a sealing / insulating method using the moisture-proof insulating paint, and an electronic component sealed and insulated with the moisture-proof insulating paint.

  Electrical devices tend to be smaller and lighter and more multifunctional year after year, and the mounting circuit boards mounted on the various electrical devices that control them are insulated for the purpose of protecting them from moisture, dust, and gas. . In this insulation treatment method, a protective coating treatment with a paint such as an acrylic resin or a urethane resin is widely adopted. In addition, many resin compositions that can be cured by irradiation with ultraviolet rays or electron beams have been developed, and various photo-curable coatings have already been put into practical use and used for insulation treatment of mounted circuit boards. As such a resin composition, a modified acrylate resin composition derived from a polyester polyol compound or a polyolefin polyol compound is known.

  On the other hand, there is an increasing demand for ultraviolet irradiation devices using LED lamps as UV lamps. An ultraviolet irradiation device using an LED lamp has low power consumption and generates less ozone. Therefore, there is an advantage that the running cost and the influence on the natural environment can be reduced. However, unlike other UV lamps, LED lamps have a single wavelength, so that a resin composition that is cured requires high sensitivity to ultraviolet rays. Further, for further cost reduction, it is also required to cure the ends of the laminated electronic components at a time with a smaller exposure amount. Since the laminated ends are sealed at one time, if the resin film thickness is large and the exposure dose is reduced, poor curing at the resin / electronic component substrate interface where ultraviolet rays are difficult to reach easily occurs. Also in this respect, high ultraviolet sensitivity is required. However, many photocuring initiators having high ultraviolet sensitivity deteriorate the electrical insulation, and there is a problem that they are not suitable for a resin composition used for insulation treatment.

  In response to the technical demands from the market as described above, Patent Document 1 discloses that a polyolefin polyol compound, an ethylenically unsaturated compound having a hydroxyl group, and a compound having two or more isocyanate groups in one molecule are reacted. A urethane compound having an ethylenically unsaturated double bond, a photopolymerizable monomer having 5 to 10 ethylenically unsaturated double bonds in the molecule, and a photopolymerization initiator. A photocurable resin composition is disclosed. However, although the compositions described in Examples of Patent Document 1 are cured with a small exposure amount, there is a problem that curing failure tends to occur at the resin / electronic component base material interface as the film thickness increases.

  Patent Documents 2 and 3 disclose a composition containing a binder polymer, a polymerizable compound, and a photocuring initiator having an oxime ester structural unit, but these are premised on printing / development for use as a solder resist. The technical field is different. Further, there is no description of a moisture-proof insulating coating containing a photocuring initiator having an oxime ester structural unit.

JP 2008-280414 A JP 2008-233421 A JP 2012-220794 A

The present invention has been made in view of the above-mentioned problems of the prior art, and is a photocurable moisture-proof material that has a low environmental burden, is excellent in deep curability at a low dose, and is hydrophobic and has high long-term insulation reliability. An object is to provide an insulating paint.
Another object of the present invention is to provide a sealing treatment or insulation treatment method by curing a photocurable moisture-proof insulating paint for a mounting circuit board with an LED lamp.
Another object of the present invention is to provide a highly reliable electronic component that is sealed or insulated with the photocurable moisture-proof insulating coating for the mounting circuit board.

  As a result of repeated studies to solve the above problems, the inventors of the present invention have provided a photocurable moisture-proof insulation containing both a (meth) acryloyl group-containing compound not containing a silicon atom and a photocuring initiator having an oxime ester structural unit. The present invention has been completed by finding that the paint has a low environmental impact, is excellent in deep part curability at a low irradiation dose, is hydrophobic and has high long-term insulation reliability.

That is, the present invention (I)
The present invention relates to a moisture-proof insulating paint comprising (1) a (meth) acryloyl group-containing compound not containing a silicon atom, and (2) a photocuring initiator having an oxime ester structural unit.
The present invention (II) relates to a sealing treatment or insulation treatment method characterized in that the moisture-proof insulating paint of the present invention (I) is applied, and an LED lamp is irradiated to the application portion and cured.
The present invention (III) relates to an electronic component that is sealed or insulated with the moisture-proof insulating paint of the present invention (I).

Furthermore, the present invention relates to the following [1] to [12].
[1] A moisture-proof insulating paint comprising (1) a (meth) acryloyl group-containing compound not containing a silicon atom, and (2) a photocuring initiator having an oxime ester structural unit.
[2] A photocuring initiator (2) having an oxime ester structural unit is represented by the formula (1)

(In the formula, R ¹ is a hydrocarbon group which may contain a hetero atom, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and R ³ is a hydrocarbon group having 1 to 6 carbon atoms. .)
The moisture-proof insulating paint according to claim 1, which is a compound represented by the formula:
[3] R ¹ is the formula (2)

Or formula (3)

The moisture-proof according to claim 2, wherein R ² is a hydrocarbon group having 8 to 10 carbon atoms including a cycloalkyl group, and R ³ is a methyl group or a phenyl group. Insulating paint.
[4] The (meth) acryloyl group-containing compound (1) containing no silicon atom is selected from the group consisting of polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. The moisture-proof insulating paint according to any one of [1] to [3], including at least one kind.
[5] The (meth) acryloyl group-containing compound (1) containing no silicon atom is selected from the group consisting of urethane (meth) acrylate, and polyol poly (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylic monomer. The moisture-proof insulating paint according to [4], comprising at least one selected from the above.
[6] The urethane (meth) acrylate includes a structure derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol [4] ] Or the moisture-proof insulating paint according to [5].
[7] The moisture-proof insulating paint according to any one of [1] to [6], further comprising (4) a silane coupling agent.
[8] The moisture-proof insulating paint according to any one of [1] to [7], further comprising (5) a tackifier.
[9] The moisture-proof insulating paint according to [8], wherein the tackifier (5) contains a petroleum resin-based tackifier.
[10] The moisture-proof insulating paint according to any one of [1] to [9], wherein a viscosity at 25 ° C. is 2000 mPa · s or less.
[11] Sealing treatment or insulation treatment characterized in that the moisture-proof insulating paint according to any one of [1] to [10] is applied, and an LED lamp that emits ultraviolet rays is applied to the application portion and cured. Method.
[12] An electronic component sealed or insulated with the moisture-proof insulating paint according to any one of [1] to [10].

The moisture-proof insulating paint of the present invention has a low environmental impact, is excellent in deep part curability at a low dose, and is hydrophobic and has a long-term insulation reliability.By applying and curing this moisture-proof insulating paint, It has the effect that a highly reliable electronic component can be manufactured.
In addition, by applying the moisture-proof insulating paint of the present invention, irradiating the application part with an LED lamp and curing, a highly reliable electronic component can be manufactured at low cost and with a small environmental load.

Hereinafter, the present invention will be specifically described.
In the present specification, “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group. As used herein, “(meth) acrylate” means acrylate and / or methacrylate.

First, the present invention (I) will be described.
The present invention (I)
(1) A moisture-proof insulating paint comprising a (meth) acryloyl group-containing compound not containing a silicon atom, and (2) a photocuring initiator having an oxime ester structural unit.

First, the (meth) acryloyl group-containing compound (1) containing no silicon atom will be described.
If this component is a (meth) acryloyl group containing compound which does not contain a silicon atom, there will be no restriction | limiting in particular.
Examples of the (meth) acryloyl group-containing compound (1) not containing a silicon atom include polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and a (meth) acrylic monomer not containing a silicon atom. It is done.

Generally, polyol poly (meth) acrylate is an ester compound of polyol and acrylic acid or methacrylic acid. There is no restriction | limiting in particular in the polyol chosen in this case. Specifically, for example, hydrogenated dimer diol (chain-like), 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol Chain aliphatic polyols other than dimer diols such as 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, etc., hydrogenated dimer diols (having an alicyclic structure) ), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclo [5.2.1.0 ^{2, 6]} Dekanjimetano Polyol having an alicyclic structure other than dimer diol such as 2-methylcyclohexane-1,1-dimethanol, trimer triol, p-xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct, biphenolethylene Polyols having aromatic rings such as oxide adducts, polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate and polycaprolactone, α, ω-poly (1,6-hexylene carbonate) diol, α, ω-poly (3-methyl-1,5-pentylene carbonate) diol, α, ω-poly [(1,6-hexylene : 3-methyl-pentamethylene) carbonate] diol, α, ω-poly [(1,9-nonylene: 2-methyl-1,8-octylene) carbonate] diol, and the like (poly) carbonate diol, hydrogenated dimer acid Polyester polyol having a structural unit derived from hydrogenated dimer diol and a structural unit derived from hydrogenated dimer diol, and commercially available products include trade names PLACEL, CD-205, 205PL, 205HL, 210, manufactured by Daicel Chemical Industries, Ltd. 210PL, 210HL, 220, 220PL, 220HL, trade names Kuraray Polyol C-590, C-1065N, C-1015N, C-2015N, and the like manufactured by Kuraray Co., Ltd. can be mentioned. These may be used alone or in combination of two or more.

Generally, epoxy (meth) acrylate is a compound obtained by adding acrylic acid or methacrylic acid to a terminal epoxy group of an epoxy resin. There is no restriction | limiting in particular in the epoxy resin selected in this case. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.
Examples of commercially available products of epoxy (meth) acrylate include epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL600 (manufactured by Daicel-Cytec Co., Ltd.), EBECRYL6040 (manufactured by Daicel-Cytech Co., Ltd.), and the like.

  In general, urethane (meth) acrylate is a compound obtained by reacting polyol and polyisocyanate with hydroxyl group-containing (meth) acrylate, or polyol and isocyanate group-containing (meth) acrylate. There are no particular restrictions on the polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, and isocyanate group-containing (meth) acrylate selected at this time. The polyol is the same as the polyol used in the polyol poly (meth) acrylate. Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. And the like. These may be used alone or in combination of two or more. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate. 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl Methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3- (o-phenylphenoxy) pro Methacrylate, and the like. These may be used alone or in combination of two or more. Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. These may be used alone or in combination of two or more.

Examples of (meth) acrylic monomers not containing a silicon atom include (meth) acryloyl-containing compounds having a cyclic ether group such as glycidyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, and isobornyl. Acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclo Pentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, disic Monofunctional (meth) acryloyl group-containing compound having a cyclic aliphatic group such as pentanylethyl methacrylate, 4-tert-butylcyclohexyl methacrylate, lauryl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, Monofunctional (meth) acryloyl group containing chain aliphatic groups such as isooctyl acrylate, isoamyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, isoamyl methacrylate Compounds, benzyl acrylate, phenoxyethyl acrylate, benzyl methacrylate, phenoxy Monofunctional (meth) acryloyl group-containing compounds having aromatic rings such as xylethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tri Mention may be made of polyfunctional (meth) acryloyl group-containing compounds such as cyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like. .
In the present specification, the (meth) acrylic monomer not containing a silicon atom includes the above-mentioned polyol poly (meth) acrylate, the epoxy (meth) acrylate and the urethane (from the (meth) acryloyl group-containing compound not containing a silicon atom). It is a compound excluding (meth) acrylate.

  The amount of the (meth) acrylic monomer not containing silicon atoms in the moisture-proof insulating coating of the present invention (I) is preferably 30 to 80% by mass, more preferably 40%, based on the total polymerizable components. It is -70 mass%, Most preferably, it is 45-70 mass%. If the amount of the (meth) acrylic monomer containing no silicon atom is more than 80% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating may be lowered, which is not preferable. On the other hand, when the amount of the (meth) acrylic monomer containing no silicon atom is less than 30% by mass relative to the total polymerizable component, the viscosity of the moisture-proof insulating coating becomes too high, which is not preferable for handling.

  Further, a silicon atom having a chain aliphatic hydrocarbon group having 9 or more carbon atoms such as lauryl acrylate, isononyl acrylate, lauryl methacrylate, and isononyl methacrylate with respect to the total amount of (meth) acrylic monomer not containing silicon atom (Meth) acrylic monomer not containing benzene, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, isobol Nyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate, 4-tert Having a number of 9 or more cyclic aliphatic hydrocarbon group having a carbon such as butyl cyclohexyl methacrylate, do not contain silicon atoms (meth) the total amount of the acrylic monomers is preferably at least 50 wt%.

Next, the photocuring initiator (2) having an oxime ester structural unit will be described.
The photocuring initiator (2) having an oxime ester structural unit is a compound represented by the following formula (1).

In the formula, R ¹ is a hydrocarbon group which may contain a hetero atom, and preferably a group represented by the formula (2) or the formula (3).

R ² is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 8 to 10 carbon atoms including a cycloalkyl group, and most preferably a cyclopentylethyl group.
R ³ is a hydrocarbon group having 1 to 6 carbon atoms, preferably a methyl group or a phenyl group.

Examples of the photocuring initiator having an oxime ester structural unit include Irgacure OXE 01, Irgacure OXE 02 (both manufactured by BASF), TR-PBG-304 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), TR-PBG-305 (Changzhou Power Electronics New Materials Co., Ltd., 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime)) and the like. Alternatively, two or more kinds may be used in appropriate combination.
The use amount of the photocuring initiator having an oxime ester structural unit is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the total photopolymerizable component. Part range. The photocuring initiators having these oxime ester structural units may be used alone or in combination of two or more. When the amount of the photocuring initiator having an oxime ester structural unit is less than 0.1 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, it is not preferable because deep curability is hardly expressed. . Moreover, when the usage-amount of the photocuring initiator which has an oxime ester structural unit becomes more than 10 mass parts with respect to 100 mass parts of all the photopolymerizable components, it may have a bad influence on the physical property of hardened | cured material, and is preferable. Not that.

  The urethane (meth) acrylate is as described above, and among them, in particular, it is derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. Urethane (meth) acrylate is preferred.

  In general, “dimer acid” means a fatty acid having 14 to 22 carbon atoms having 2 to 4 ethylenic double bonds (hereinafter referred to as unsaturated fatty acid A), preferably 14 carbon atoms having two ethylenic double bonds. 14 to 22 fatty acids having 1 to 4 fatty acids and 1 to 4 ethylenic double bonds (hereinafter referred to as unsaturated fatty acids B), preferably 14 to 1 carbon atoms having 1 or 2 ethylenic double bonds The dimer acid obtained by reacting 22 fatty acids with a double bond part shall be said. As the unsaturated fatty acid A, tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (linolenic acid, etc.), eicosatetraenoic acid ( Arachidonic acid and the like), and linoleic acid is most preferable. Moreover, as unsaturated fatty acid B, in addition to the above-mentioned examples, tetradecenoic acid (tuzuic acid, spermic acid, myristoleic acid) as a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond , Hexadecenoic acid (such as palmitoleic acid), octadecenoic acid (such as oleic acid, elaidic acid, vaccenic acid), eicosenoic acid (such as gadoleic acid), docosenoic acid (such as erucic acid, cetreic acid, brassic acid), etc. Acid or linoleic acid is most preferred.

  In the dimerization reaction, the use ratio (molar ratio) of the unsaturated fatty acid A and the unsaturated fatty acid B is preferably about 1: 1.2 to 1.2: 1, and most preferably 1: 1. The dimerization reaction can be performed according to a known method, for example, a method described in JP-A-9-136861. That is, for example, an unsaturated fatty acid A and an unsaturated fatty acid B are mixed with a Lewis acid or Bronsted acid type liquid or solid catalyst, preferably montmorillonite activated clay, and the total amount of unsaturated fatty acid A and unsaturated fatty acid B is 100 parts by mass. It can be carried out by adding 1 to 20 parts by mass, preferably 2 to 8 parts by mass, and heating to 200 to 270 ° C, preferably 220 to 250 ° C. The pressure during the reaction is usually a slightly pressurized state, but may be normal pressure. The reaction time varies depending on the amount of catalyst and the reaction temperature, but is usually 5 to 7 hours. After completion of the reaction, the catalyst can be filtered off and then distilled under reduced pressure to distill off unreacted raw materials and isomerized fatty acids, and then dimer acid fraction can be distilled off. The dimerization reaction is thought to proceed through double bond transfer (isomerization) and Diels-Alder reaction, but the present invention is not limited thereto.

  The obtained dimer acid is usually a mixture of dimer acids having different structures depending on the bonding site or isomerization of the double bond, and may be used separately, but can be used as it is. Further, the obtained dimer acid contains a small amount of monomeric acid (for example, 6% by mass or less, particularly 4% by mass or less), trimer acid or higher polymer acid (for example, 6% by mass or less, particularly 4% by mass or less). May be.

The “hydrogenated dimer acid” described in the present specification refers to a saturated dicarboxylic acid obtained by hydrogenating the carbon-carbon double bond of the dimer acid.
When the dimer acid having 36 carbon atoms produced from, for example, linoleic acid and linoleic acid or oleic acid is used as the raw material, the structure of the main component of the hydrogenated dimer acid is represented by the following formula (4 ) And formula (5).

(In the formula, each of R ⁴ and R ⁵ is an alkyl group, and the total number of carbon atoms contained in R ⁴ and R ⁵ , a and b is 28 (that is, the number of carbon atoms contained in R ⁴ + R ⁵ The number of carbons included + a + b = 28).)

(In the formula, R ⁶ and R ⁷ are both alkyl groups, and the number of carbon atoms contained in R ⁶ and R ⁷ , and the sum of c and d is 32 (that is, the number of carbon atoms contained in R ⁶ + R ⁷ The number of carbons included + c + d = 32).)

  Examples of the commercially available hydrogenated dimer acid include PRIPOL (registered trademark) 1009 (manufactured by Croda), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF).

The “hydrogenated dimer diol” described in the present specification means a reduction of at least one of the dimer acid, the hydrogenated dimer acid and the lower alcohol ester thereof in the presence of a catalyst, When the carboxylate moiety is alcohol and the raw material has a carbon-carbon double bond, the main component is a diol obtained by hydrogenating the double bond.
For example, when a hydrogenated dimer diol is produced by reducing a hydrogenated dimer acid containing a compound having a structure represented by formula (4) or formula (5) as a main component, the main component of the hydrogenated dimer diol is reduced. The structure is a structure represented by the following formulas (6) and (7).

(In the formula, R ⁸ and R ⁹ are both alkyl groups, and the total number of carbon atoms contained in R ⁸ and R ⁹ , e and f is 30 (that is, the number of carbon atoms contained in R ⁸ + R ⁹ The number of carbons included + e + f = 30).)

(In the formula, R ¹⁰ and R ¹¹ are both alkyl groups, and the total number of carbon atoms contained in R ¹⁰ and R ¹¹ , g and h is 34 (that is, the number of carbon atoms contained in R ¹⁰ + R ¹¹ The number of carbons included + g + h = 34).)

  Examples of the commercially available hydrogenated dimer diol include PRIPOL (registered trademark) 2033 and the like (manufactured by Croda) and Sovermol (registered trademark) 908 (manufactured by BASF).

A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol, an acid component containing the hydrogenated dimer acid as an essential component and the hydrogenated dimer diol as essential The polyol component as a component can be produced by performing a condensation reaction in the presence of an esterification catalyst.
Since the esterification reaction removes water, the reaction is generally performed at a reaction temperature of about 150 to 250 ° C. In general, the reaction is performed under normal pressure or reduced pressure.

A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol includes a lower alkyl ester of an acid containing a hydrogenated dimer acid as an essential component, and the hydrogenated dimer described above. A polyol component containing diol as an essential component can also be produced by performing a transesterification reaction in the presence of a transesterification catalyst.
Since the transesterification reaction removes alcohol, the reaction is generally performed at a reaction temperature of about 120 to 230 ° C. In general, the reaction is performed under normal pressure or reduced pressure.

  In the production method of urethane (meth) acrylate, polyol and polyisocyanate and hydroxyl group-containing (meth) acrylate, or polyol and isocyanate in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate. Although the synthesis can be performed by reacting the group-containing (meth) acrylate, the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time. However, if too much is used, there is a possibility that the physical properties at the time of actual use as a cured film will be adversely affected, so the amount used is polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, or polyol. It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amounts of isocyanate group containing (meth) acrylate.

  Moreover, the said urethanization catalyst catalyzes the hydrolysis reaction of an alkoxy silyl group, when the alkoxy silyl group is contained in the moisture-proof insulating coating material of this invention (I). In such a case, it is necessary to consider the balance between the stability over time of the moisture-proof insulating paint of the present invention (I) and the adhesion to the substrate, and the amounts used in that case include polyol, polyisocyanate and hydroxyl group-containing ( It is preferably 0.003 to 0.2 parts by mass, more preferably 0.005 to 0.15 parts by mass with respect to 100 parts by mass of the total amount of (meth) acrylate or polyol and isocyanate group-containing (meth) acrylate. Part. When the amount is less than 0.001 part by mass, the effect of adding a catalyst is hardly exhibited, and when it is used more than 1 part by mass, the physical property value at the time of actual use as a cured film is adversely affected as described above. There is.

  There are no particular restrictions on the order in which the raw materials are charged. Usually, in the case of a reaction of a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, the polyisocyanate and, if necessary, a urethanization catalyst are charged into the reactor. Stirring is performed, and then the polyol is charged at a temperature in the reactor of 50 ° C. to 140 ° C., preferably 60 ° C. to 120 ° C., and then the temperature in the reactor is 50 ° C. to 160 ° C., preferably 60 ° C. These are reacted at ~ 140 ° C. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., a polymerization inhibitor and, if necessary, a urethanization catalyst are added, and a hydroxyl group-containing (meth) acrylate is added dropwise. During the dropping, the temperature in the reactor is preferably maintained at 30 to 120 ° C, desirably 50 to 100 ° C. After completion of the dropping, the temperature in the reactor is maintained at 30 to 120 ° C., preferably 50 to 100 ° C., to complete the reaction. In the case of a polyol and an isocyanate group-containing (meth) acrylate, an isocyanate group-containing (meth) acrylate, a polymerization inhibitor and, if necessary, a urethanization catalyst are charged into the reactor, followed by stirring, and then the temperature in the reactor The polyol is charged at 50 ° C. to 140 ° C., preferably 60 ° C. to 120 ° C., and then these are reacted at a temperature in the reactor of 50 ° C. to 160 ° C., preferably 60 ° C. to 140 ° C. Thereafter, the temperature in the reactor is maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C., to complete the reaction.

In the case of a reaction of a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, the raw material charge molar ratio (that is, (number of hydroxyl groups in the polyol) / (number of isocyanate groups in the polyisocyanate) / (hydroxyl group-containing (meta)) ) The number of hydroxyl groups in the acrylate)) is adjusted according to the molecular weight of the target polyurethane. However, it is necessary to increase the number of isocyanate groups in the polyisocyanate than the number of hydroxyl groups in the polyol.
When the ratio between the total number of hydroxyl groups in the polyol and the number of isocyanate groups in the polyisocyanate is close to 1.0, the molecular weight increases. When the ratio deviates from 1.0, the molecular weight decreases.
The feed molar ratio of the raw materials is not particularly limited, but the ratio of the number of isocyanate groups in the polyisocyanate and the total number of hydroxyl groups in the polyol is preferably in the range of 4: 1 to 1.5: 1.
If this ratio is larger than 4: 1, the abundance of structural units derived from polyol may be reduced, which may be undesirable in terms of moisture resistance of the moisture-proof insulating coating. Moreover, when it is smaller than 1.4: 1, the molecular weight becomes too large, and when used in the moisture-proof insulating paint of the present invention (I), the viscosity may become too high.

  The amount of urethane (meth) acrylate used in the moisture-proof insulating paint of the present invention (I) is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, based on the total polymerizable components. It is particularly preferably 24 to 55% by mass. If the amount of urethane (meth) acrylate used is less than 20% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating may be lowered, which is not preferable. Moreover, when the usage-amount of urethane (meth) acrylate becomes more than 70 mass% with respect to all the polymeric components, the viscosity of a moisture-proof insulating coating will become high too much and it cannot be said that it is preferable on handling.

In the moisture-proof insulating paint of the present invention (I), a polymerization inhibitor may be added and is preferable in order to increase storage stability.
The polymerization inhibitor is not particularly limited. For example, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, 2,5-di-tert-butyl-3-methylphenol, pt-butylcatechol, 2,5-di-t- Butyl hydroquinone, p-tert-butyl catechol, mono-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, di-t-butyl paracresol hydroquinone monomethyl ether, alpha naphthol, acetamidine acetate, acetamidine sulfate , Phenylhydrazine hydrochloride, hydride Gin hydrochloride, trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyltrimethylammonium chloride, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium malate, trimethylbenzylammonium tartrate, Trimethylbenzylammonium glycolate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, pyrogallol, tannic acid, resorcin, triethylamine hydrochloride, dimethyl Aniline hydrochloride and dibutyla Down the hydrochloride salt, and the like.
These may be used alone or in combination of two or more.

Among these, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy- p-benzoquinone, p-t-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t -Butyl paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.
Usually, it is preferable to add 0.01-10 mass parts of this polymerization inhibitor with respect to 100 mass parts of all the polymerizable components.

  The “polymerizable component” described in the present specification means a compound that can be polymerized by radical polymerization, and the “total polymerizable component” means the total amount of the polymerizable component. The (meth) acryloyl group-containing compound (1) and urethane (meth) acrylate that do not contain a silicon atom are both included in the polymerizable component. P-styryltrimethoxysilane, p-styryltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxy in the silane coupling agent (4) described later Radicals of silane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane It means that a silane coupling agent having a polymerizable unsaturated group is also included in the polymerizable component.

The moisture-proof insulating paint of the present invention (I) can further contain (4) a silane coupling agent for the purpose of imparting adhesion to glass, metal or metal oxide.
(4) A silane coupling agent is an organosilicon compound having a functional group reactively bonded to an organic material and a functional group reactively bonded to an inorganic material in the molecule, and generally has a structure represented by the following formula (8). Shown in

Here, Y is a functional group reactively bonded to an organic material, and representative examples thereof include a vinyl group, an epoxy group, an amino group, a substituted amino group, a (meth) acryloyl group, a mercapto group and the like. X is a functional group that reacts with an inorganic material and is hydrolyzed by water or moisture to produce silanol. This silanol reacts with the inorganic material. Representative examples of X include an alkoxy group, an acetoxy group, a chloro atom, and the like. R ¹² is a divalent organic group, and R ¹³ represents an alkyl group. i represents an integer of 1 to 3, and j represents an integer of 0 to 2. However, i + j = 3.

  Examples of the silane coupling agent include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethyl Xysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-minoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-a Nopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Examples include triethoxysilane and allyltrimethoxysilane.

  Among these, Y is preferably a (meth) acryloyl group-containing compound (1) containing no silicon atom and a compound having reactivity with urethane (meth) acrylate, and among them, p-styryltrimethoxy. Silane, p-styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxy Silane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxy Lan, 3-acryloyloxypropylmethyldiethoxysilane, and 3-methacryloyloxypropylmethyldiethoxysilane are preferred, and more preferably 3-acryloyloxypropyltrimethoxysilane that is easily incorporated into the cured product during the photocuring reaction. 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxy Propylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, considering the reactivity of the alkoxysilyl group, - acryloyloxypropyltrimethoxysilane, 3-methacryloyloxy propyl trimethoxy silane, 3-acryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane is preferable.

  The silane coupling agent (4) is preferably in the range of 0.01 to 8 parts by weight, more preferably 100 parts by weight of the total polymerizable component in the moisture-proof insulating paint of the present invention (I). , 0.1 parts by mass to 5 parts by mass. In the case of less than 0.01 part by mass with respect to 100 parts by mass of all polymerizable components in the moisture-proof insulating paint of the present invention (I), adhesion to glass, metal or metal oxide may not be sufficiently exhibited. It is not preferable. Moreover, when it is more than 8 mass% with respect to 100 mass parts of all the polymeric components in the moisture-proof insulating coating material of this invention (I), depending on the kind of silane coupling agent to be used, the surface tack of hardened | cured material increases. Tend.

The moisture-proof insulating paint of the present invention (I) can further contain a tackifier (5) for the purpose of imparting adhesion to the substrate.
The tackifier used in the moisture-proof insulating paint of the present invention (I) is a substance for providing an adhesive function by blending with a polymer compound represented by urethane (meth) acrylate or elastomer having rubber elasticity. In general, it is a compound in an oligomer region having a molecular weight of several hundred to several thousand, and has a property of not exhibiting rubber elasticity by itself in a glass state at room temperature.
In general, petroleum resin tackifiers, terpene resin tackifiers, rosin resin tackifiers, coumarone indene resin tackifiers, styrene resin tackifiers, and the like can be used as tackifiers.

  Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product. The synthetic petroleum resin may be C5 or C9.

  Examples of the terpene resin tackifier include β-pinene resin, α-pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. Many of these terpene resins are resins having no polar group.

  Rosin resin tackifiers include rosins such as gum rosin, tall oil rosin, wood rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as maleated rosin; rosin glycerin ester, hydrogenated rosin ester, water Examples thereof include rosin esters such as rosin glycerol ester. These rosin resins have polar groups.

These tackifiers can be used alone or in combination of two or more.
Among these tackifiers, it preferably contains at least one petroleum resin tackifier and a terpene resin tackifier, and more preferably at least one petroleum resin tackifier. It contains the agent.

  It is desirable that the total amount of tackifier is 0.1 to 35 parts by mass with respect to 100 parts by mass of all polymerizable components. When the total amount of the tackifier is less than 0.1 parts by mass with respect to 100 parts by mass of the total polymerizable component, it is not preferable that the effect of adding the tackifier is hardly expressed. Further, when the total amount of the tackifier is more than 35 parts by mass with respect to 100 parts by mass of all polymerizable components, the moisture-proof insulating paint of the present invention (I) may become cloudy or the viscosity may become too high. This is not preferable.

The moisture-proof insulating paint of the present invention (I) can and preferably contains a photopolymerization initiator other than the photocuring initiator (2) having an oxime ester structural unit.
The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane. -1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2- Methyl-1- (4-dodecylphenyl) propanone and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 4-methoxy Nzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4 , 4'-bis (dialkylamino) benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (dihydroxyethylamino) benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4- Dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2 -(Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin) Isopropyl ether, Zoin isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2, 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

  Moreover, a metallocene compound can also be used as a photopolymerization initiator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.

These photopolymerization initiators can be used alone or in combination of two or more with the photocuring initiator (2) having an oxime ester structural unit.
A preferable photopolymerization initiator to be combined with the photocuring initiator (2) having an oxime ester structural unit is a compound represented by the following formula (9).

(In the formula, R ¹⁴ represents H or CH _3. )
The compound represented by formula (9) is, for example, when R ¹⁴ is H, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and R ¹⁴ is methyl. In the case of a group, it is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.

  The amount of photopolymerization initiator other than the photocuring initiator having an oxime ester structural unit is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of the total photopolymerizable component. It is the range of 0.5-6 mass parts. Photopolymerization initiators other than the photocuring initiators having these oxime ester structural units may be used alone or in combination of two or more. When the amount of the photopolymerization initiator other than the photocuring initiator having the oxime ester structural unit is less than 0.1 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, the photopolymerization initiation performance is exhibited. It is not preferable because it is difficult to be done. Moreover, when the usage-amount of photoinitiators other than the photocuring initiator which has an oxime ester structural unit exceeds 10 mass parts with respect to 100 mass parts of all photopolymerizable components, it will have a bad influence on the physical property of hardened | cured material. It is possible and not preferred.

Moreover, a radical chain transfer agent can be used for the moisture-proof insulating paint of this invention (I) as needed.
As the radical chain transfer agent, a compound that has a function of reactivating a polymerization active species trapped by an inert radical scavenger such as oxygen and contributes to an improvement in surface curability can be used without limitation. Examples of the compound serving as a chain transfer agent include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N. -Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl -4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di ( 2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, , N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5 -Di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, trimethylamine, Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanol Amine, N-lauryl diethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine tri Among them, 2-ethylhexyl-4-dimethylaminobenzoate is a particularly suitable amine.

  In the moisture-proof insulating paint of the present invention (I), when using a radical chain transfer agent, the amount used is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable component. High sensitivity and improved surface curability in air. More preferably, the surface curability is further improved within the range of 0.5 to 5 parts by mass. These radical chain transfer agents may be used alone or in combination of two or more.

  The moisture-proof insulating paint of the present invention (I) preferably has a viscosity at 25 ° C. of 2000 mPa · s or less. More preferably, the viscosity at 25 ° C. is 1600 mPa · s or less. When the viscosity at 25 ° C. is higher than 2000 mPa · s, when the curable composition is applied by a drawing application method using a dispenser, the spread after application is suppressed, and as a result, the thickness after curing is more than necessary. May be higher.

  In the moisture-proof insulating paint of the present invention (I), a filler, a modifier, an antifoaming agent, a colorant, and the like can be added as necessary within a range that does not adversely affect fluidity and photocurability. .

  Examples of the filler include fine powder silicon oxide, magnesium oxide, aluminum hydroxide, calcium carbonate and the like.

  Examples of the modifier include a leveling agent for improving leveling properties. As the leveling agent, for example, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, etc. can be used. . These may be used alone or in combination of two or more. 0.01-10 mass parts can be added with respect to 100 mass parts of all the polymerizable components. When the amount is less than 0.01 part by mass, the effect of adding the leveling agent may not be exhibited. On the other hand, when the amount is more than 10 parts by mass, depending on the type of leveling agent used, there is a possibility of surface tack or deterioration of electrical insulation characteristics.

The antifoaming agent is not particularly limited as long as it literally has an action of eliminating or suppressing bubbles generated or remaining when the moisture-proof insulating coating of the present invention (I) is applied.
Examples of the antifoaming agent used in the moisture-proof insulating coating of the present invention (I) include known antifoaming agents such as silicone oils, fluorine-containing compounds, polycarboxylic acid compounds, polybutadiene compounds, and acetylenic diol compounds. . Specific examples thereof include, for example, BYK-077 (manufactured by Big Chemie Japan Co., Ltd.), SN deformer 470 (manufactured by San Nopco Co., Ltd.), TSA750S (manufactured by Momentive Performance Materials LLC), silicone oil SH-203 (Toray Industries, Inc.) -Silicone defoaming agents such as Dow Corning Co., Ltd., Dappo SN-348 (San Nopco Co., Ltd.), Dappo SN-354 (San Nopco Co., Ltd.), Dappo SN-368 (San Nopco Co., Ltd.), Disparon 230HF Acetylene diol system such as acrylic polymer antifoaming agents (made by Enomoto Kasei Co., Ltd.), Surfynol DF-110D (made by Nissin Chemical Industry Co., Ltd.), Surfynol DF-37 (made by Nissin Chemical Industry Co., Ltd.) Defoaming agent, fluorine-containing silico such as FA-630 Emissions-based anti-foaming agents, and the like can be mentioned. These may be used alone or in combination of two or more. Usually, 0.001-5 mass parts can be added with respect to 100 mass parts of all the polymerizable components. If the amount is less than 0.01 parts by mass, the effect of adding the antifoaming agent may not be exhibited. On the other hand, when the amount is more than 5 parts by mass, depending on the type of antifoaming agent to be used, surface tack may occur or electrical insulation characteristics may be deteriorated.

  Examples of the colorant include known inorganic pigments, organic pigments, organic dyes, and the like, and each is blended according to a desired color tone. These may be used alone or in combination of two or more.

Next, the sealing treatment or insulation treatment method of the present invention (II) will be described.
In the sealing treatment or insulation treatment method of the present invention (II), the moisture-proof insulating paint of the present invention (I) is applied to an electronic component, and then the LED lamp that emits ultraviolet rays is applied to the moisture-proof insulating paint coating portion to be cured. That's it. The method for applying the moisture-proof insulating coating is not particularly limited, but examples include dipping, brushing, spraying, and drawing. The method of irradiating the moisture-proof insulating paint application part with the ultraviolet light emitted from the LED lamp is not particularly limited, but the method of irradiating the electronic component coated with the moisture-proof insulating paint by holding or operating the flexible light guide tube by hand or machine Another example is a method in which an electronic component coated with a moisture-proof insulating coating is placed on a conveyor and irradiated through an area irradiated with ultraviolet rays from an LED lamp.

Next, the electronic component of the present invention (III) will be described.
The present invention (III) is an electronic component that has been sealed or insulated with the moisture-proof insulating paint of the present invention (I). Examples of the electronic component include a microcomputer, a transistor, a capacitor, a resistor, a relay, a transformer, and a mounting circuit board on which these are mounted, and also includes a lead wire, a harness, a film substrate, and the like that are joined to these electronic components. be able to.
Moreover, the signal input part of flat panel display panels, such as a liquid crystal display panel, a plasma display panel, an organic electroluminescent panel, a field emission display panel, the touch sensor of a touch panel, its wiring, etc. are mentioned as an electronic component.

  The electronic component of the present invention (III) can be produced by applying the moisture-proof insulating paint of the present invention (I) to the electronic component and then curing the applied moisture-proof insulating paint. As a specific manufacturing method of the electronic component of the present invention (III), first, the above-mentioned moisture-proof insulating paint is applied to the electronic component by a generally known method such as a dipping method, a brush coating method, a spray method, or a drawing method. Apply to. Next, an electronic component is obtained by irradiating ultraviolet rays using a high pressure mercury lamp, a metal halide lamp, an LED or the like as a light source and curing the coating film of the electronic circuit reinforcing agent applied to the electronic component.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited only to a following example.

(Execution synthesis example 1)
In a reaction vessel equipped with a stirrer and a water separator, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, hydrogenated dimer diol purity 97.5 wt%) 22.00 g, EMPOL (registered trademark) 1008 (hydrogenated dimer manufactured by BASF) Acid, hydrogenated dimer acid purity 92.0%) 23.00 g, Neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) 0.01 g, while starting condensed water at about 240 ° C. under normal pressure A dehydration esterification reaction was performed while reducing the pressure, and a mixture of a polyester polyol and a hydrogenated dimer diol having a hydroxyl value of 59 mg KOH / g and a number average molecular weight of 2000 and containing 15% by mass of a hydrogenated dimer diol (hereinafter referred to as polyester polyol A). )

(Execution synthesis example 2)
16. In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 45.00 g of polyester polyol A, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5 wt%) 94 g, Nonion (registered trademark) L-2 (polyethylene glycol monolaurate manufactured by NOF Corporation) 0.82 g, Irganox (registered trademark) 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl manufactured by BASF) -4-hydroxyphenyl)] propionate) 0.12 g, Neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.), and VESTANAT (registered trademark) H12MDI (methylenebis (4-cyclohexyl) manufactured by Evonik Degussa Cyanate)) 32.62g was charged, with stirring, the temperature was raised to 75-80 ° C. using an oil bath. Thereafter, the reaction was continued with stirring for 2.5 hours. Thereafter, 20.69 g of 4-HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was charged into the reaction vessel, and the temperature in the reaction vessel was kept within the range of 80 ° C. ± 5 ° C. while continuing stirring. The reaction was continued for 10 hours. Thereafter, an infrared absorption spectrum was measured to confirm that the absorption of the isocyanate group had disappeared, and the reaction was terminated to obtain urethane acrylate (hereinafter referred to as urethane acrylate B).

(Execution synthesis example 3)
A 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with 34.0 g of Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5 wt%) and 100 mg of hydroquinone monomethyl ether. While stirring, the temperature was raised to 40 ° C. using an oil bath. Thereafter, methylenebis (4-cyclohexylisocyanate) (Evonik Degussa, trade name: VESTANAT (registered trademark) H12MDI) 32.60 g (124.2 mmol) and Neostan U-810 (Nitto Kasei Co., Ltd. dioctyltin dilaurate) 0.01 g The internal temperature was raised to 90 ° C. while stirring was continued. After raising the temperature to 90 ° C., the reaction was continued with stirring for 4 hours. Thereafter, 17.91 g (124.2 mmol) of 4-hydroxybutyl acrylate was charged into the reaction vessel, and the reaction was continued for 6 hours while maintaining the temperature in the reaction vessel in the range of 90 ° C. ± 5 ° C. while continuing stirring. Continued. Thereafter, an infrared absorption spectrum was measured to confirm that the absorption of the isocyanate group had disappeared, and the reaction was terminated to obtain urethane acrylate (hereinafter referred to as urethane acrylate C).

(Execution synthesis example 4)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, HEA (2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 53.00 g, GI-1000 ( Charge 600.00 g of hydrogenated polybutadiene diol manufactured by Nippon Soda Co., Ltd., number average molecular weight: about 1,500) and 0.50 g of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) to 70 ° C. using an oil bath. The temperature rose. Then, it heat-retained for 30 minutes at 70-75 degreeC, stirring, and 70.00 g of Coronate (trademark) T-65 (Nippon Polyurethane Industry Co., Ltd. tolylene diisocyanate) was uniformly dripped at this in 3 hours. After completion of the dropwise addition, the reaction was continued at 70 to 75 ° C. with stirring for about 5 hours. Thereafter, an infrared absorption spectrum was measured to confirm that the absorption of the isocyanate group had disappeared, and the reaction was terminated to obtain urethane acrylate (hereinafter referred to as urethane acrylate D).

(Execution synthesis example 4)
In a 1 liter four-necked flask equipped with a stirrer and a distillation apparatus, hydrogenated polybutadiene polyol (trade name: NISSO-PB GI-2000 hydroxyl value 47.3 mgKOH / g, manufactured by Nippon Soda Co., Ltd.) 540.0 g, acrylic acid n- 162.0 g of butyl, 0.81 g of dioctyltin dilaurate and 3.51 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by BASF) Then, the mixture of n-butanol and n-butyl acrylate produced by heating to 130 ° C. under an air stream was gradually distilled out of the reaction system over about 10 hours while refluxing. After n-butanol and n-butyl acrylate disappeared, the pressure in the reaction system was reduced to 10 kPa using a vacuum pump, and n-butanol and n-butyl acrylate were again distilled out of the system. After holding at 50 Pa for about 1.5 hours, the reactor was cooled to obtain hydrogenated polybutadiene diacrylate (hereinafter referred to as polyol polyacrylate E).

(Example formulation 1)
4.50 g of urethane acrylate B, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.20 g and 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent Mixing was performed using Taro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable paint B1.

(Example of formulation 2)
4.50 g of urethane acrylate B, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.10 g, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) manufactured by BASF) -Butanone-1) 0.10 g, DISPALON L-1982N as antifoaming agent 0.025 g (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint B2.

(Example formulation 3)
Urethane acrylate B2.50g, EBECRYL3700 (Epoxy acrylate manufactured by Daicel Cytec Co., Ltd.) 2.00g, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50g, Blemmer LA (Lauril acrylate manufactured by NOF Corporation) ) 0.80 g, A-DPH (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.20 g, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd. 1- [9- 0.10 g of ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)), Irgacure (registered trademark) 369 (BASF 2- Benzyl-2-dimethylamino-1- (4-methyl Horinophenyl) -butanone-1) 0.10 g, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) 0.025 g as an antifoaming agent Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer) ) And mixed. This blend was designated as a photocurable paint B3.

(Example formulation 4)
Urethane acrylate C4.50 g, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (Noryo lauryl acrylate) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.10 g, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) manufactured by BASF) -Butanone-1) 0.10 g, DISPALON L-1982N as antifoaming agent 0.025 g (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint C1.

(Example formulation 5)
4.50 g of urethane acrylate D, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Co., Ltd.), 0.80 g of Bremer LA (lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.10 g, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) manufactured by BASF) -Butanone-1) 0.10 g, DISPALON L-1982N as antifoaming agent 0.025 g (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint D1.

(Example formulation 6)
4.50 g of the polyol polyacrylate E, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.80 g of Blemmer LA (Lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) Company dipentaerythritol hexaacrylate) 0.20g, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole as photopolymerization initiator -3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.10 g, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl, manufactured by BASF) ) -Butanone-1) 0.10 g, DISPALON L-19 as antifoaming agent 82N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) (0.025 g) was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable paint E1.

(Example formulation 7)
10.00 g of the urethane acrylate B, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd. 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-) as a photopolymerization initiator Yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) 0.10 g, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone manufactured by BASF) -1) 0.10 g, 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent, using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer) Mixed. This blend was designated as a photocurable paint F1.

(Example of formulation 8)
4.50 g of urethane acrylate B, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate manufactured by Irgacure (registered trademark) OXE01 (manufactured by BASF, 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) )) 0.20 g, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) 0.025 g as an antifoaming agent was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). did. This blend was designated as a photocurable paint G1.

(Comparative Formulation Example 1)
4.50 g of urethane acrylate B, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) Dipentaerythritol hexaacrylate) 0.20 g, Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) 0.30 g as a photopolymerization initiator In addition, 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint B4.

(Comparative Formulation Example 2)
Urethane acrylate B 2.50 g, EBECRYL 3700 (epoxy acrylate manufactured by Daicel-Cytec Co., Ltd.) 2.00 g, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) ) 0.80 g, A-DPH (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.), Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1) as a photopolymerization initiator -(4-morpholinophenyl) -butanone-1) 0.20 g, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) 0.025 g as an antifoaming agent Awatori Rentaro ARE-310 (Sinky Corporation) Made and revolving Miki Sir). This blend was designated as a photocurable paint B5.

(Comparative Formulation Example 3)
Urethane acrylate C4.50 g, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (Noryo lauryl acrylate) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) Dipentaerythritol hexaacrylate) 0.20 g, Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) 0.30 g as a photopolymerization initiator Then, 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint C2.

(Comparative Formulation Example 4)
4.50 g of urethane acrylate D, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Co., Ltd.), 0.80 g of Bremer LA (lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) Dipentaerythritol hexaacrylate) 0.20 g, Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) 0.30 g as a photopolymerization initiator In addition, 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint D2.

(Comparative Formulation Example 5)
4.50 g of the polyol polyacrylate E, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.80 g of Blemmer LA (Lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g of dipentaerythritol hexaacrylate manufactured by company, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 manufactured by BASF) as a photopolymerization initiator 30 g and 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent were mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable coating E2.

(Comparative Formulation Example 6)
4.50 g of urethane acrylate B, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (lauryl acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g dipentaerythritol hexaacrylate), 0.30 g LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) as a photopolymerization initiator, DISPALON L-1982N (Enomoto Kasei Co., Ltd.) as an antifoaming agent Acrylic copolymer (0.025 g) was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable coating B6.

(Comparative Formulation Example 7)
Urethane acrylate B2.50g, EBECRYL3700 (Epoxy acrylate manufactured by Daicel Cytec Co., Ltd.) 2.00g, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50g, Blemmer LA (Lauril acrylate manufactured by NOF Corporation) 0.80 g, A-DPH (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.20 g, LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) as a photopolymerization initiator 0. 30 g and 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent were mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint B7.

(Comparative Formulation Example 8)
Urethane acrylate C4.50 g, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (Noryo lauryl acrylate) 0.80 g, A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g dipentaerythritol hexaacrylate), 0.30 g LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) as a photopolymerization initiator, DISPALON L-1982N (Enomoto Kasei Co., Ltd.) as an antifoaming agent Acrylic copolymer (0.025 g) was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable paint C3.

(Comparative Formulation Example 9)
4.50 g of urethane acrylate D, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Co., Ltd.), 0.80 g of Bremer LA (lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) 0.20 g dipentaerythritol hexaacrylate), 0.30 g LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) as a photopolymerization initiator, DISPALON L-1982N (Enomoto Kasei Co., Ltd.) as an antifoaming agent Acrylic copolymer (0.025 g) was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable paint D3.

(Comparative Formulation Example 10)
4.50 g of the polyol polyacrylate E, 4.50 g of IBXA (Isosbornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.80 g of Blemmer LA (Lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura Chemical Co., Ltd.) Company dipentaerythritol hexaacrylate) 0.20g, photopolymerization initiator LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) 0.30g, defoaming agent DISPALON L-1982N (Enomoto Kasei) Acrylic copolymer (0.025 g) was mixed using Awatori Rentaro ARE-310 (Sinky Corporation's rotation / revolution mixer). This blend was designated as a photocurable coating E3.

(Comparative Formulation Example 11)
10.0 g of the urethane acrylate B, 0.30 g of Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 manufactured by BASF) as a photopolymerization initiator, 0.025 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as a foaming agent was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable paint F2.

(Comparative Formulation Example 12)
10.0 g of urethane acrylate B, 0.30 g of LUCIRIN TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide) as a photopolymerization initiator, DISPARON L-1982N (acrylic manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent (Copolymer) 0.025 g was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable paint F3.

  Tables 1 and 2 collectively show the formulation compositions of Examples Formulation Examples 1-8 and Comparative Formulation Examples 1-12.

<Evaluation of deep curability>
Deep part curability was evaluated by the following method.
The thickness after curing of the photocurable coatings B1 to B7, C1 to 3, D1 to 3 and E1 to 3, respectively on a polyimide film (trade name: Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) is 700 μm. And using an ultraviolet ray irradiation device (made by Eye Graphics Co., Ltd.) using an LED lamp (wavelength 365 nm) and irradiating with ultraviolet rays under the condition of an irradiation amount of 350 mJ / cm ² , The case where there was no residual liquid in the interface of a polyimide film was set as (circle), and the case where there was residual liquid was set as x. The results are shown in Table 3.

<Evaluation of long-term electrical insulation reliability using flexible substrates>
A substrate having a fine comb pattern shape described in JPCA-ET01, manufactured by etching a flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd., grade name: Esperflex, copper thickness: 8 μm, polyimide thickness: 38 μm) (Copper wiring width / copper wiring width = 15 μm / 15 μm) A flexible wiring board subjected to tin plating treatment is coated with photocurable paints B1 to B7, C1 to 3, D1 to 3, and E1 to 3, respectively. The film was applied to a thickness of 150 μm, and cured by irradiating with ultraviolet rays under the condition of an irradiation amount of 350 mJ / cm ² using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.) using an LED lamp (wavelength 365 nm).
Using this test piece, a bias voltage of 30 V was applied, and a temperature and humidity steady test under conditions of a temperature of 85 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV). Table 3 shows resistance values 1000 hours after the start of the temperature and humidity steady test. Incidentally, in Table 3, the upper part is an example and the lower part is a comparative example.

  From the results of Table 3, it can be seen that the photocurable paints B1 to B3, C1, D1, E1, F1, and G1 containing a photocuring initiator having an oxime ester structural unit have both high deep curability and long-term insulation reliability. . Photocurable paints B4-7, C2-3, D2-3, E2-3, F2-3, which do not contain a photocuring initiator having an oxime ester structural unit, are inferior in either deep curable or long-term insulation reliability. I understand that. That is, it was found that the moisture-proof insulating paint of the present invention (I) has both high deep-curing property and long-term insulation reliability as compared with the moisture-proof insulating paint containing no existing photocuring initiator having an oxime ester structural unit.

  The moisture-proof insulating paint of the present invention (I) has both high deep part curability and long-term insulation reliability. Further, the sealing treatment / insulation treatment using the moisture-proof insulating paint and LED lamp of the present invention (I) has a low environmental load and is low in cost. An electronic component sealed and insulated using the moisture-proof insulating paint of the present invention (I) has high reliability and is useful for a mounted circuit board on which a microcomputer and various components are mounted.

Claims (12)

(1) A moisture-proof insulating paint comprising a (meth) acryloyl group-containing compound containing no silicon atom, and (2) a photocuring initiator having an oxime ester structural unit. The photocuring initiator (2) having an oxime ester structural unit is represented by the formula (1)

(In the formula, R ¹ is a hydrocarbon group which may contain a hetero atom, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and R ³ is a hydrocarbon group having 1 to 6 carbon atoms. .)
The moisture-proof insulating paint according to claim 1, which is a compound represented by the formula: R ¹ is the formula (2)

Or formula (3)

The moisture-proof according to claim 2, wherein R ² is a hydrocarbon group having 8 to 10 carbon atoms including a cycloalkyl group, and R ³ is a methyl group or a phenyl group. Insulating paint.   The (meth) acryloyl group-containing compound (1) containing no silicon atom is at least one selected from the group consisting of polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. The moisture-proof insulating paint according to claim 1, comprising:   The (meth) acryloyl group-containing compound (1) containing no silicon atom is at least 1 selected from the group consisting of urethane (meth) acrylate, and polyol poly (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylic monomer. The moisture-proof insulating paint according to claim 4, comprising seeds.   The urethane (meth) acrylate includes a structure derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. Moisture-proof insulating paint described in 1.   Furthermore, the moisture-proof insulation coating material of any one of Claims 1-6 containing (4) silane coupling agents.   Furthermore, the moisture-proof insulation coating material of any one of Claims 1-7 containing (5) tackifier.   The moisture-proof insulating paint according to claim 8, wherein the tackifier (5) contains a petroleum resin-based tackifier.   The moisture-proof insulating paint according to any one of claims 1 to 9, wherein the viscosity at 25 ° C is 2000 mPa · s or less.   A sealing treatment or an insulation treatment method, wherein the moisture-proof insulating paint according to any one of claims 1 to 10 is applied, and an LED lamp that emits ultraviolet rays is applied to the application portion and cured.   The electronic component by which the sealing process or the insulation process was carried out with the moisture proof insulation coating material of any one of Claims 1-10.