TW201446900A - Electronic component which is sealed/insulated using light-shielding moisture-proof insulating coating material - Google Patents

Abstract

Provided is a photocurable moisture-proof insulating coating material which has little impact on the environment, can exhibit excellent deep part curability upon the irradiation of a small quantity of light, is hydrophobic, has high long-term insulation reliability, and also has a light-shielding property against visible light in a broad wavelength range. A moisture-proof insulating coating material comprising (1) a compound containing a (meth)acryloyl group, (2) a photopolymerization initiator and (3) at least two types of dyes, said coating material being characterized in that: a 500 [mu]m-thick cured film produced by curing the coating material has a total light transmittance of less than 10%, wherein the sum total of wavelength regions which fall within the wavelength range from 400 to 700 nm and in which the transmittance becomes 10% or more is 50 nm or less; and a cured film produced by irradiating the coating material applied in a thickness of 1 mm or more with ultraviolet ray under such conditions that the illuminance at a wavelength of 365 nm is 400 mW/cm2 and the light exposure quantity is 300 mJ/cm2 has a thickness of 500 [mu]m or more.

Description

Light-shielding moisture-proof insulating coating, sealed with a light-shielding moisture-proof insulating coating. Insulation treatment method, and sealed by a light-shielding moisture-proof insulating coating. Insulated electronic parts

The present invention relates to a light-shielding moisture-proof insulating paint, a seal using a light-shielding moisture-proof insulating paint, an insulation treatment method, and an electronic component which is sealed and insulated by a light-shielding moisture-proof insulating paint.

Electrical equipment has a tendency to be small, lightweight, and multi-functional, and the mounted circuit boards mounted on various electrical machines that control them are implemented for the purpose of protection from moisture, dust, gas, etc. Insulation treatment. In this insulating treatment method, a protective coating treatment by a coating material such as an acrylonitrile-based resin or an urethane-based resin is widely used. Further, various resin compositions which can be cured by irradiation with ultraviolet rays or electron beams have been developed, and various photocurable coating materials have been put into practical use and provided for use in the insulation treatment of mounted circuit boards. As such a resin composition, a denatured acrylate resin composition derived from a polyester polyol compound or a polyolefin polyol compound or the like is known.

On the other hand, UV lamps use UV rays from LED-UV lamps. The need for an illumination device is also increasing. The ultraviolet ray irradiation device using the LED-UV lamp has low power consumption and generates less ozone. Therefore, it has the advantage of reducing the running cost and the impact on the natural environment. However, unlike other UV lamps, LED-UV lamps require a high sensitivity to ultraviolet rays to the resin composition to be hardened because of its single wavelength. Moreover, in order to further reduce the cost, it is also required to harden the end of the laminated electronic component at a small exposure amount at a time. Since the laminated end is sealed at one time, if the film thickness of the resin is large and the amount of exposure is small, the curing failure at the interface of the resin/electronic component substrate which is difficult to reach by ultraviolet rays is likely to occur. High UV sensitivity is also required at this point. However, since the photopolymerization initiator having a high ultraviolet sensitivity is often deteriorated in electrical insulation properties, it is unsuitable for use in a resin composition for insulation treatment. In recent years, due to the popularity of liquid crystal screens, in order to prevent light leakage from LED backlights, it is also strongly required to impart a light-shielding property to visible light for protective coating, but materials that absorb or scatter visible light also cause absorption or scattering of ultraviolet rays, and thus It becomes easy to cause a problem of poor hardening at the interface.

A photocurable resin composition containing a polyolefin polyalcohol compound, an ethylenically unsaturated compound having a hydroxyl group, and a photo-curable resin composition is disclosed in Japanese Laid-Open Patent Publication No. 2008-280414. a urethane compound having an ethylenically unsaturated double bond obtained by reacting a compound having two or more isocyanato groups in one molecule, and an ethylenically unsaturated double having 5 or more and 10 or less in the molecule The photopolymerizable monomer of the bond and the photopolymerization initiator are used. However, in the embodiment of Japanese Laid-Open Patent Publication No. 2008-280414, Although the composition to be loaded is hardened at a small exposure amount, when the film thickness is increased, there is a problem that the hardening at the interface of the resin/electronic component substrate is liable to occur. Further, there is no description about the light blocking property against visible light.

Further, Japanese Laid-Open Patent Publication No. 2006-045340 discloses a composition comprising an A-B-A type styrene block copolymer rubber of a thermoplastic elastomer and an azo compound chromate mis-salt of a dye. However, azo dyes have the disadvantage of affecting the environment and the human body. Further, even if a dye is added in an amount of up to 25 parts by mass based on 100 parts by mass of the thermoplastic elastomer, the transmittances of 10% and 25% are respectively displayed in the wavelength fields of 650 nm and 700 nm, which is difficult to say. It is sufficient to have a light-shielding property, and a large amount of a dye is added to reduce the proportion of the resin responsible for electrical insulation, resulting in a decrease in electrical insulation. Further, this composition contains a solvent, and is subjected to moisture-proof insulating coating by volatilizing a solvent, and has a disadvantage of a larger environmental load than a moisture-proof insulating coating which is hardened by ultraviolet rays.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-280414

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-045340

The present invention is based on the problems of the prior art described above. For the purpose of providing a photocurable moisture-proof insulating coating which is excellent in the deep-hardening property under the low-intensity, and which is excellent in the long-term insulation reliability and has long-term insulation reliability, and which has a light-shielding property in a wide wavelength range. .

Further, the present invention has an object of providing a sealing treatment or an insulation treatment method for curing a photocurable moisture-proof insulating coating material for a board-mounted circuit board using an LED-UV lamp.

Moreover, the present invention has an object of providing an electronic component which is highly reliable in sealing treatment or insulation treatment and which can suppress light leakage by the photocurable moisture-proof insulating coating material for mounting the above-mentioned circuit board.

In order to solve the above problems, the inventors of the present invention have found that a photocurable moisture-proof insulating coating material containing a (meth)acryl-based fluorenyl compound, a photopolymerization initiator, and two or more types of dyes is obtained. The present invention has been completed in that the environmental load is small, the deep curing property at a low irradiation amount is excellent, and it is hydrophobic and has high long-term insulation reliability, and has light-shielding properties for visible light in a wide wavelength range.

That is, the present invention (I) relates to a moisture-proof insulating coating characterized by containing (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) 2 or more types of dyes. The total light transmittance of the cured film having a thickness of 500 μm obtained by hardening the coating is less than 10%, and the total wavelength range of the transmittance of 10% or more in the wavelength range of 400 to 700 nm is 50 nm or less. The illuminance at a wavelength of 365 nm was 400 mW/cm ² and the exposure amount was 300 mJ/cm ² , and the thickness of the cured film obtained by applying ultraviolet rays to the coating material having a thickness of 1 mm or more was 500 μm or more.

The invention (II) relates to a moisture-proof insulating coating characterized by comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) 2 or more kinds of dyes; (3) At least two of them are obtained by adjusting the transmittance at the maximum wavelength of absorption to a concentration of 10% when the UV-visible light transmittance is measured under conditions of a butyl acetate solution and an optical path length of 10 mm. The solution has a dye having a transmittance of 50% or more at a wavelength of 365 nm.

The invention (III) relates to a sealing treatment or an insulation treatment method for an electronic component, comprising applying a moisture-proof insulating coating material according to the invention (I) to an electronic component, and irradiating the coating portion with an LED-UV lamp; The step of hardening it.

The present invention (IV) relates to an electronic component which is subjected to a sealing treatment or an insulation treatment by the moisture-proof insulating coating material of the invention (I).

Furthermore, the present invention relates to the following [1] to [15].

[1] A moisture-proof insulating coating comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) 2 or more types of dyes; The total light transmittance of the cured film having a thickness of 500 μm is less than 10%, and the total wavelength range of the transmittance of 10% or more in the wavelength range of 400 to 700 nm is 50 nm or less, and the illuminance at a wavelength of 365 nm is The thickness of the cured film obtained by irradiating the coating material to a thickness of 1 mm or more under conditions of 400 mW/cm ² and an exposure amount of 300 mJ/cm ² was 500 μm or more.

[2] The moisture-proof insulating coating according to [1], wherein the cured film having a thickness of 500 μm obtained by hardening the coating has a total light transmittance of less than 10% and a transmittance in a wavelength range of 400 to 700 nm. Less than 10%.

[3] The moisture-proof insulating coating according to [1] or [2], wherein at least two of the dyes (3) are respectively subjected to UV-visible light penetration under conditions of forming a butyl acetate solution and having an optical path length of 10 mm. In the measurement of the rate, the dye having a transmittance at a maximum wavelength of 10% is adjusted to have a transmittance of 50% or more at a wavelength of 365 nm.

[4] The moisture-proof insulating coating according to any one of [1] to [3], wherein at least one of the dyes (3) has a maximum absorption wavelength of less than 450 nm when the butyl acetate solution is formed. In the range of 550 nm, and at least one of the other types of absorption in the butyl acetate solution, the absorption maximum wavelength is in the range of 550 nm or more and 700 nm or less.

[5] A moisture-proof insulating coating comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) Two or more types of dyes; at least two of the dyes (3) are respectively absorbed at a maximum wavelength when UV-visible light transmittance is measured under conditions of a butyl acetate solution having an optical path length of 10 mm. The transmittance of the solution having a concentration of 10% is a dye having a transmittance of 50% or more at a wavelength of 365 nm.

[6] The moisture-proof insulating coating according to [5], wherein at least one of the dyes (3) has a maximum absorption wavelength in a range of 450 nm or more and less than 550 nm when the butyl acetate solution is formed, and at least one of the other The type of the absorption maximum when the butyl acetate solution is formed is in the range of 550 nm or more and 700 nm or less.

[7] The moisture-proof insulating coating according to any one of [1] to [6] wherein at least two of the dyes (3) are an anthraquinone dye.

[8] The moisture-proof insulating coating according to any one of [1] to [7] wherein the photopolymerization initiator (2) is a compound represented by the formula (1) or a benzyldimethylketal; (wherein R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are a hydrocarbon group).

[9] The moisture-proof insulating coating according to any one of [1] to [8], wherein The acryl-based fluorenyl compound (1) is selected from the group consisting of polyalcohol poly(meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates, and (meth) propylene. At least one of the group of thiol monomers.

[10] The moisture-proof insulating coating according to any one of [1] to [9] wherein the (meth)acryl fluorenyl compound (1) is selected from the group consisting of poly (poly) poly (meth) acrylate, epoxy At least one of a group of a (meth) acrylate and a (meth) acryl fluorenyl monomer, and a urethane (meth) acrylate.

[11] The moisture-proof insulating coating according to [9] or [10] wherein the urethane (meth) acrylate is a structure derived from a polyester polyol having a hydrogenation a structural unit derived from a polyacid and a structural unit derived from a hydrogenated dimer diol.

[12] The moisture-proof insulating coating according to any one of [1] to [11] which further comprises (4) a decane coupling agent.

[13] The moisture-proof insulating coating according to any one of [1] to [12], which further comprises (5) an adhesion-imparting agent.

[14] A method for sealing or insulating an electronic component, comprising applying the moisture-proof insulating coating according to any one of [1] to [13] to an electronic component, and irradiating the coating portion with LED-UV The step of hardening the lamp.

[15] An electronic component which is subjected to a sealing treatment or an insulation treatment by a moisture-proof insulating coating according to any one of [1] to [13].

The moisture-proof insulating coating of the present invention has low environmental load, is excellent in deep hardenability at low irradiation, is hydrophobic, has high long-term insulation reliability, and has light-shielding properties for visible light in a wide wavelength range, by coating this When the moisture-proof insulating coating is hardened, it is possible to manufacture an electronic component that is highly reliable and can suppress light leakage.

In addition, by applying the moisture-proof insulating coating material of the present invention, the coated portion is irradiated with an LED-UV lamp to be cured, that is, an electronic component capable of suppressing light leakage can be manufactured at low cost and under environmental load.

Hereinafter, the present invention will be specifically described.

Further, the "(meth)acryloyl group" in the present specification is an alkyl acrylate group and/or a methacryl fluorenyl group.

First, the invention (I) will be explained.

The present invention (I) is a moisture-proof insulating coating characterized by comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) 2 or more kinds of dyes; The total light transmittance of the cured film having a thickness of 500 μm obtained by hardening the paint is less than 10%, and the total wavelength range of the transmittance of 10% or more in the wavelength range of 400 to 700 nm is 50 nm or less at a wavelength of 365 nm. The illuminance was 400 mW/cm ² and the exposure amount was 300 mJ/cm ² , and the thickness of the cured film obtained by irradiating the coating material to a thickness of 1 mm or more was 500 μm or more.

First, the (meth)acryl-containing fluorenyl compound (1) will be described.

This component is not particularly limited as long as it contains a (meth) acrylonitrile compound. However, the (meth)acrylonitrile-based compound (1) is one which has a (meth) acrylonitrile group in the decane coupling agent (4) which will be described later. That is, the moisture-proof insulating coating of the present invention contains a (meth) acrylonitrile-based decane when the decane coupling agent (4) contains a (meth) acryl oxime group in the decane coupling agent (4). The coupling agent is considered to be included in the decane coupling agent (4), and is not included in the (meth) acrylonitrile-containing compound (1).

Examples of the (meth)acrylonitrile-containing compound (1) include polyalcohol poly(meth)acrylate, epoxy (meth)acrylate, and urethane (meth)acrylate. (Meth) propylene fluorenyl monomer and the like.

In general, polyalcohol poly(meth)acrylate refers to a polyalcohol, an ester compound with acrylic acid or methacrylic acid. The polyol to be used at this time is not particularly limited. Specific examples thereof include hydrogenated dimer diol (chain-like), 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, and 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, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin a chain aliphatic alcohol other than a dimer diol such as a polyhydric alcohol or a hydrogenated polyolefin polyalcohol, a hydrogenated dimer diol (having an alicyclic structure), 1,4-cyclohexane dimethanol, 1, 3-cyclohexanedimethanol, tricyclo[5.2.1.02,6]decane dimethanol, 2-methylcyclohexane-1,1-dimethanol, etc. Polyol having a alicyclic structure other than the polymer diol, trimer triol, p-nonanediol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol a polyether polyol such as an aromatic ring-containing polyalcohol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like, an ethylene oxide adduct or the like, polyhexamethylene adipate, and poly 6 Polyester polyols such as methylene succinate or polyhexadiester, α,ω-poly(1,6-carbonic acid) diol, α,ω-poly(3-methyl-1, 5-mercaptoacetate)diol, α,ω-poly[(1,6-extensionyl:3-methyl-pentamethylene)carbonate]diol, α,ω-poly[(1,9) - (poly)carbonate diol, such as 2-methyl-1,8-exenyl)carbonate], having a structural unit derived from a hydrogenated dimer acid and a hydrogenated dimer A polyester polyol which is a structural unit derived from a diol; a commercial product such as PLACCEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL manufactured by Dell Chemical Co., Ltd. Kuraray Polyol C-590, C-1065N, C-1015N, C-2015N, etc., manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more. Further, from the viewpoint of adhesion to the substrate, a polyalcohol having an aromatic ring, a polyether polyol, a (poly)carbonate diol, or a polyester polyol is preferred. More preferred are polyester polyols having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol.

The amount of the polyhydric poly(meth) acrylate used in the moisture-proof insulating coating of the invention (I) is preferably from 20 to 70% by mass, more preferably from 24 to 60, based on the total polymerizable component. The mass% is particularly preferably 24 to 55 mass%. When the amount of the polyhydric poly(meth) acrylate is less than 20% by mass based on the total polymerizable component, the moisture-proof insulating coating is moisture-proof. It is difficult to say that the performance is degraded. When the amount of the poly(poly)poly(meth)acrylate used is more than 70% by mass based on the total polymerizable component, the viscosity of the moisture-proof insulating coating material becomes too high, which is difficult to handle.

In general, an epoxy (meth) acrylate refers to a compound obtained by adding an epoxy group to a terminal epoxy group of an epoxy resin to obtain acrylic acid or methacrylic acid. The epoxy resin selected at this time is not particularly limited. Specific examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a glycidyl ester type epoxy resin, and a biphenyl type epoxy resin. These may be used alone or in combination of two or more.

Examples of the commercially available product of the epoxy group (meth) acrylate include Epoxyester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL 600 (manufactured by Daicel-Cytec Co., Ltd.), and EBECRYL 6040 (limited by Daicel-Cytec Co., Ltd.). Company system) and so on.

The amount of the epoxy group (meth) acrylate used in the moisture-proof insulating coating material of the invention (I) is preferably from 20 to 70% by mass, more preferably from 24 to 60, based on the total polymerizable component. The mass% is particularly preferably 24 to 55 mass%. When the amount of the epoxy group (meth) acrylate used is less than 20% by mass based on the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating material may be lowered, which is not preferable. In addition, when the amount of the epoxy group (meth) acrylate is more than 70% by mass based on the total polymerizable component, the viscosity of the moisture-proof insulating coating material is too high, which is difficult to handle.

In general, urethane (meth) acrylate means a polyalcohol with a polyisocyanate and a hydroxyl group-containing (meth) acrylate, or a polyalcohol and an isocyanate-containing (meth) acrylate. The compound obtained by the reaction. The polyalcohol, polyisocyanate, hydroxyl group-containing (meth) acrylate, and isocyanate group-containing (meth) acrylate selected at this time are not particularly limited. The polyalcohol is the same as the polyalcohol used in the poly (poly) poly (meth) acrylate. Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl group). Cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, diphenylmethane-4 , 4 '- diisocyanate, 1,3-extending crop-yl diisocyanate, 1,4-crop yl diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, norbornane diisocyanate, 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, and 4- Hydroxybutyl acrylate, 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)propyl methacrylate, and the like. These may be used alone or in combination of two or more. Examples of the isocyanato group-containing (meth) acrylate include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. These may be used alone or in combination of two or more.

The method for producing urethane (meth) acrylate is in the presence or absence of a known urethane catalyst such as dibutyltin dilaurate or dioctyltin dilaurate. Synthesizable by reacting a polyalcohol with a polyisocyanate with a hydroxyl group-containing (meth) acrylate or a polyalcohol with an isocyanato group-containing (meth) acrylate, in the presence of a catalyst The reaction is preferred because it can shorten the reaction time. However, when it is used too much, there is a possibility that the physical property value at the time of actual use as a cured film may be adversely affected, so the amount used is relative to the polyhydric alcohol and the polyisocyanate and the hydroxyl group-containing (meth) acrylate. It is preferably 0.001 to 1 part by mass based on 100 parts by mass of the total amount of the polyhydric alcohol and the isocyanato group-containing (meth) acrylate.

Further, when the urethane-based catalyst contains an alkoxyfluorenyl group in the moisture-proof insulating coating material of the invention (I), the hydrolysis reaction of the alkoxy fluorenyl group is catalyzed. In this case, it is necessary to consider the balance between the stability of the moisture-proof insulating coating of the present invention (I) and the adhesion to the substrate, and the amount used in this case is relative to the polyhydric alcohol and the polyisocyanate. The hydroxyl group (meth) acrylate, or 100 parts by mass of the total amount of the polyhydric alcohol and the isocyanato group-containing (meth) acrylate, is preferably 0.003 to 0.2 parts by mass, more preferably 0.005 to 0.15 parts by mass. When the amount is less than 0.001 part by mass, it is difficult to find the effect of adding the catalyst. When more than 1 part by mass is used, there is a case where the physical property value at the time of actual use as the cured film is adversely affected as described above.

There is no particular limitation on the order in which the raw materials are added, usually When the polyol reacts with the polyisocyanate and the hydroxyl group-containing (meth) acrylate, the polyisocyanate and the necessary urethane catalyst are put into the reactor for stirring, and then the temperature in the reactor is 50. The alcohol is fed at a temperature of from ° C to 140 ° C, preferably from 60 ° C to 120 ° C, and thereafter the reaction is carried out at a temperature of from 50 ° C to 160 ° C, preferably from 60 ° C to 140 ° C. Thereafter, the temperature in the reactor is set to 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, a polymerization inhibitor and a necessary urethane catalyst are added, and the hydroxyl group is added dropwise. (meth) acrylate. In the dropping, the temperature in the reactor is preferably maintained at 30 ° C to 120 ° C, and preferably maintained at 50 ° C to 100 ° C. After the completion of the dropwise addition, the temperature in the reactor is maintained at 30 ° C to 120 ° C, and preferably maintained at 50 ° C to 100 ° C to complete the reaction. In the case of a polyalcohol and an isocyanato group-containing (meth) acrylate, an isocyanato group-containing (meth) acrylate, a polymerization inhibiting agent, and a necessary urethane catalyst are put into reaction. Stirring, and then the temperature in the reactor is charged at 50 ° C ~ 140 ° C, preferably 60 ° C ~ 120 ° C, and then the temperature in the reactor is 50 ° C ~ 160 ° C, preferably These reactions were carried out at 60 ° C to 140 ° C. Thereafter, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably at 50 ° C to 100 ° C to complete the reaction.

When the polyol is reacted with a polyisocyanate and a hydroxyl group-containing (meth) acrylate, the molar ratio of the raw material is added (ie, (the number of hydroxyl groups in the polyalcohol) / (the number of isocyanato groups in the polyisocyanate) / / (the number of hydroxyl groups in the hydroxyl group-containing (meth) acrylate)) can be adjusted depending on the molecular weight of the intended polyurethane. Polyisocyanate The number of isocyanato groups in the ester is set to be greater than the number of hydroxyl groups in the polyalcohol.

When the ratio of the total number of hydroxyl groups in the polyhydric alcohol to the number of isocyanato groups in the polyisocyanate becomes 1.0, the molecular weight becomes large, and when it starts from 1.0, the molecular weight becomes small.

The molar ratio of the raw material to the addition is not particularly limited, but the ratio of the number of isocyanato groups in the polyisocyanate to the total number of hydroxyl groups in the polyalcohol is preferably in the range of 4:1 to 1.5:1.

When the ratio becomes larger than 4:1, the existence ratio of the structural unit derived from the polyhydric alcohol becomes small, and there is a case where the moisture-proof property of the moisture-proof insulating coating is unfavorable. Moreover, when it is less than 1.4:1, the molecular weight becomes too large, and when it is used for the moisture-proof insulating coating material of the invention (I), the viscosity may become too high.

The amount of the urethane (meth) acrylate in the moisture-proof insulating coating of the present invention (I) is preferably from 20 to 70% by mass, more preferably from 24 to 70% by mass based on the total polymerizable component. ~60% by mass, particularly preferably 24 to 55% by mass. When the amount of the urethane (meth) acrylate is less than 20% by mass based on the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating is lowered, which is difficult. In addition, when the amount of the urethane (meth) acrylate is more than 70% by mass based on the total polymerizable component, the viscosity of the moisture-proof insulating coating material becomes too high, which is difficult to operate. good.

Among the urethane (meth) acrylates, in particular, structural units derived from hydrogenated dimer acids and hydrogenated dimers The urethane (meth) acrylate derived from the polyester polyol of the structural unit derived from the alcohol is preferred.

In general, "dimer acid" means a fatty acid having 14 to 22 carbon atoms (hereinafter referred to as unsaturated fatty acid A) having 2 to 4 ethylenic double bonds, preferably having 2 ethylenic double bonds. a fatty acid having 14 to 22 carbon atoms and a fatty acid having 14 to 22 carbon atoms (hereinafter referred to as unsaturated fatty acid B) having 1 to 4 ethylenic double bonds, preferably having 1 or 2 ethylenic double bonds A fatty acid having a carbon number of 14 to 22 obtained by reacting a double bond at a double bond. Examples of the unsaturated fatty acid A include, for example, tetradecadienoic acid, hexadecadienic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, and twenty-two carbon two. The oleic acid, octadecatrienoic acid (linolenic acid, etc.), arachidonic acid (arachidonic acid, etc.), etc., are preferably linoleic acid. Further, as the unsaturated fatty acid B, in addition to the above-mentioned examples, there may be mentioned tetradecenoic acid (tsuzuic acid, scented) which is a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond. Acid, nutmeg oleic acid), hexadecenoic acid (palmitoleic acid, etc.), oleic acid (oleic acid, oleic acid, isooleic acid, etc.), eicosenoic acid (oleic acid, etc.), twenty Oleic acid (sinapic acid, whaleic acid, glucosinolate, etc.) is preferably oleic acid or linoleic acid.

In the above dimerization reaction, the use ratio (molar ratio) of the unsaturated fatty acid A and the unsaturated fatty acid B is preferably from 1:1.2 to 1.2:1, and most preferably from 1:1. The dimerization reaction can be carried out according to a known method, for example, the method described in JP-A-9-136861. That is, for example, relative to unsaturated fatty acids A and unsaturated fatty acids a total of 100 parts by mass of B, and a Lewis or Brine acid type liquid or solid catalyst is added to the unsaturated fatty acid A and the unsaturated fatty acid B, preferably 1 to 20 parts by mass of the activated montmorillonite activated clay. It is preferred to add 2 to 8 parts by mass, and it can be carried out by heating to 200 to 270 ° C, preferably to 220 to 250 ° C. The pressure at the time of the reaction is usually in a state of being slightly pressurized, or may be a normal pressure. The reaction time varies depending on the amount of the catalyst and the reaction temperature, but it is usually 5 to 7 hours. After completion of the reaction, the catalyst is separated by filtration, and then the unreacted raw material or the isomerized fatty acid is distilled off under reduced pressure, and then the dimer acid fraction is distilled off to obtain. The above dimerization reaction is considered to be carried out by the movement (isomerization) of the double bond and the Diels-Alder Reaction, but the present invention is not limited thereto.

The obtained dimer acid is usually a mixture of dimeric acids which are different in structure due to the binding site or isomerization of the double bond, and can be used after separation or directly. Further, the obtained dimer acid may contain a small amount of a monomeric acid (for example, 6 mass% or less, particularly 4 mass% or less) or a polymer acid or the like of a trimer acid or the like (for example, 6 mass% or less, particularly 4 mass%). the following).

The "hydrogenated dimer acid" described in the present specification means a saturated dicarboxylic acid obtained by hydrogenating a carbon-carbon double bond of the above dimer acid.

When the dimer acid is used as a raw material, for example, a dimer acid having a carbon number of 36 produced from linoleic acid and linoleic acid or oleic acid, the main component of the hydrogenated dimer acid has a structure of the following formula (4). And the structure represented by the formula (5).

(wherein R ⁴ and R ⁵ are alkyl groups, and the total number of carbon atoms, a and b contained in R ⁴ and R ⁵ is 28 (that is, the carbon number contained in R ⁴ + the carbon contained in R ⁵ Number +a+b=28).)

(wherein R ⁶ and R ⁷ are alkyl groups, and the total number of carbons, c and d contained in R ⁶ and R ⁷ is 32 (i.e., the carbon number contained in R ⁶ + the carbon contained in R ⁷⁾ Number +c+d=32).)

For example, PRIPOL (registered trademark) 1009 (manufactured by Croda Co., Ltd.), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF Corporation) can be cited.

The "hydrogenated dimer diol" described in the present specification means that at least one of the above-mentioned dimer acid, the above-mentioned hydrogenated dimer acid, and a lower alcohol ester thereof is reduced in the presence of a catalyst to form a carboxylic acid of a dimer acid. Acid or carboxylate The fraction is an alcohol, and when the carbon-carbon double bond is contained in the raw material, the diol obtained by hydrogenating the double bond is used as a main component.

For example, when a hydrogenated dimer acid is produced by reducing a hydrogenated dimer acid having a compound represented by the formula (4) and the formula (5) as a main component, the main component of the hydrogenated dimer diol is constructed. It is a structure represented by the following formula (6) and formula (7).

(wherein R ⁸ and R ⁹ are alkyl groups, and the total number of carbons, e and f contained in R ⁸ and R ⁹ is 30 (i.e., the carbon number contained in R ⁸ + the carbon contained in R ⁹⁾ Number +e+f=30).)

(wherein R ¹⁰ and R ¹¹ are an alkyl group, and the total number of carbon atoms, g and h contained in R ¹⁰ and R ¹¹ is 34 (that is, the carbon number contained in R ¹⁰ + the carbon contained in R ¹¹ Number +g+h=34).)

The commercially available product of the hydrogenated dimer diol is, for example, PRIPOL (registered trademark) 2033 (manufactured by Croda Corporation) or Sovermol (registered trademark) 908 (manufactured by BASF Corporation).

A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol can be obtained by using an acid component which has a hydrogenated dimer acid as an essential component as described above The polyalcohol component which contains a hydrogenated dimer diol as an essential component is produced by carrying out a condensation reaction in the presence of an esterification catalyst.

Since the above esterification reaction removes water, it is generally carried out at a reaction temperature of about 150 to 250 °C. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

Further, the polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol can also be a lower alkane of an acid which has a hydrogenated dimer acid as an essential component. The base ester is produced by performing a transesterification reaction with a polyhydric alcohol component containing the hydrogenated dimer diol as an essential component in the presence of a transesterification catalyst.

Since the above transesterification reaction removes alcohol, the reaction is generally carried out at a reaction temperature of about 120 to 230 °C. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

The (meth) acrylonitrile-based single system in the present specification excludes the above-mentioned polyol poly(meth) acrylate, the above epoxy (meth) acrylate, and the like from the above-mentioned (meth) acrylonitrile-containing compound. A compound of the aforementioned urethane (meth) acrylate.

Examples of the (meth)acrylonitrile-based monomer include epoxypropyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate. (meth)acryloyl group-containing compound, cyclohexyl acrylate, isodecyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate , dicyclopentanyl acrylate, dicyclopentylethyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, isodecyl methacrylate, dicyclopentan Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentylethyl methacrylate, 4 Monofunctional (meth)acryl-containing fluorenyl compound having a cyclic aliphatic group such as -tert-butylcyclohexyl methacrylate, lauryl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate , isobutyl acrylate, te Rt-butyl acrylate, isooctyl acrylate, isoamyl acrylate, lauryl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, Monofunctional (meth)acryloyl-containing compound having a chain aliphatic group such as tert-butyl methacrylate, isooctyl methacrylate or isoamyl methacrylate, benzyl acrylate, phenoxy a monofunctional group having an aromatic ring such as etheth acrylate, benzyl methacrylate, phenoxyethyl methacrylate or 2-hydroxy-3-phenoxypropyl methacrylate a propylene fluorenyl compound, polyethylene glycol diacrylate, decanediol diacrylate, decanediol diacrylate, Hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. The functional group contains a (meth) acrylonitrile compound.

The amount of the (meth) acrylonitrile-based monomer used in the moisture-proof insulating coating material of the invention (I) is preferably from 30 to 80% by mass, preferably from 40 to 70, based on the total polymerizable component. The mass% is more preferably 45 to 70% by mass. When the amount of the (meth) acrylonitrile-based monomer is more than 80% by mass based on the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating material may be lowered, which is preferable. In addition, when the amount of the (meth) acrylonitrile-based monomer is less than 30% by mass based on the total polymerizable component, the viscosity of the moisture-proof insulating coating material becomes too high, which is difficult to handle. .

In addition, the "polymerizable component" described in the present specification means a compound which can be polymerized by radical polymerization, and the "all-polymerizable component" means the total amount of a polymerizable component. The (meth)acrylonitrile-based compound (1) and the urethane (meth)acrylate are all included in the polymerizable component. P-styryltrimethoxydecane, p-styryltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropene oxime in the decane coupling agent (4) described later. Oxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenylmethoxypropylmethyldi Methoxydecane, 3-methacryloxypropylmethyldimethoxydecane, 3-propenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl Diethoxylate The decane coupling agent having a radical polymerizable unsaturated group of decane is also meant to be included in the polymerizable component.

Further, the lauryl acrylate, isodecyl acrylate, lauryl methacrylate, isodecyl methacrylate or the like has a carbon number of 9 or more with respect to the total amount of the (meth) acrylonitrile-based monomer. a (meth) acrylonitrile-based monomer of a chain aliphatic hydrocarbon group, and an isodecyl acrylate, a dicyclopentenyl acrylate, a dicyclopentenyloxyethyl acrylate, a dicyclopentyl acrylate, Dicyclopentylethyl acrylate, 4-tert-butylcyclohexyl acrylate, isodecyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate a cyclic aliphatic hydrocarbon group having a carbon number of 9 or more, such as ester, dicyclopentyl methacrylate, dicyclopentylethyl methacrylate, 4-tert-butylcyclohexyl methacrylate The total amount of the acryl-based monomer is preferably 50% by mass or more.

Next, the photopolymerization initiator (2) will be explained.

The photopolymerization initiator is not particularly limited as long as it can generate a radical which imparts a radical which initiates radical polymerization by irradiation with light such as near-infrared rays, visible rays, or ultraviolet rays.

Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and 1-hydroxycyclohexylphenyl. Ketone, 1,2-hydroxy-2-methyl-1-phenylpropan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, 2-hydroxyl -2-methyl-1-(4-isopropylphenyl)acetone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)acetone, and 2-hydroxy-2-methyl 1-[(2-hydroxyethoxy)phenyl]acetone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonyldiphenyl Ketone, 4-benzylindolyl-4 ' -methyldiphenyl sulfide, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4 ' -bis(dialkylamino)benzol Ketones (eg 4,4 ' -bis(dimethylamino)benzophenone, 4,4 ' -bis(dicyclohexylamino)benzophenone, 4,4 ' -bis(diethyl) amino) benzophenone, 4,4 '- bis (dihydroxy diethylamino) benzophenone), 4-methoxy-4' - dimethylamino benzophenone 4,4 '- dimethoxy benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino acetophenone, benzil, anthraquinone, 2-t -butyl hydrazine, 2-methyl hydrazine, phenanthrenequinone, anthrone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2 -(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol Polymer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether) , benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridine Ketone, 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide, 2,6-dimethoxybenzylidene diphenylphosphine oxide, 2,6-dichlorobenzylhydrazine diphenyl Phosphine oxide, 2,4,6-trimethylbenzylidene methoxyphenylphosphine oxide, 2,4,6-trimethylbenzylideneethoxyphenylphosphine oxide, 2,3 ,5,6-tetramethylbenzylhydrazine Diphenylphosphine oxide, benzamidine bis-(2,6-dimethylphenyl)phosphonate, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2 -(O-benzylindenyl), 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]ethanone-1-(O-ethenyl)肟), 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylacetone-1-(O-ethylindenyl) , 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzylindenyl) and the like. Examples of the bis-fluorenylphosphine oxides include bis-(2,6-dichlorobenzylidene)phenylphosphine oxide and bis-(2,6-dichlorobenzylidene)-2,5-. Dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-1-naphthalene Phosphine oxide, bis-(2,6-dimethoxybenzylidene)phenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethyl Pentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzylhydrazine Phenylphosphine oxide, (2,5,6-trimethylbenzylidene)-2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-iso Propyl thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

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

These photopolymerization initiators may be used singly or in combination of two or more.

The photopolymerization initiator used in the present invention is preferably a compound represented by the following formula (1) or a benzyldimethylketal.

In the formula, the structures of R ¹ , R ² and R ^{3 are} not particularly limited, and R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are a hydrocarbon group. Preferably, R ¹ is a structure containing a hetero atom, and R ² and R ³ are a structure including an alkyl group, and/or a phenyl group, and/or a cycloalkyl group. More preferably represented by the formula R & lt system ¹ (2) or (3) by, R ² is a 1 to 10 carbons which may contain hydrocarbon group of the cycloalkyl, R ³ is methyl or phenyl. More preferably, R ² is an alkyl group having 1 to 6 carbon atoms.

Examples of the compound represented by the formula (1) include Irgacure OXE 01, Irgacure OXE 02 (all manufactured by BASF Corporation), TR-PBG-304, and TR-PBG-305 (all of which are Changzhou Power Electronic New Materials Co., Ltd.). The company (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), etc. Further, as the benzyl dimethyl ketal, Irgacure 651 (manufactured by BASF Corporation) may be mentioned. These may be used alone or in combination of two. The above is suitably used in combination, and benzyl dimethyl ketal is preferred from the viewpoint of preservation stability when incorporated in a moisture-proof insulating coating.

The amount of the compound represented by the formula (1) or the benzyl dimethyl ketal is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass based on 100 parts by mass of the all-photopolymerizable component. The scope of the share. When the amount of the compound represented by the formula (1) or the benzyldimethylketal is less than 0.1 part by mass based on 100 parts by mass of the all-photopolymerizable component, it is difficult to exhibit deep hardenability, which is not preferable. . In addition, when the amount of the compound represented by the formula (1) or the benzyl dimethyl ketal is more than 10 parts by mass based on 100 parts by mass of the all-photopolymerizable component, the physical properties of the cured product may be generated. Bad influence, so it is not good.

The photopolymerization initiator which is combined with the photohardening initiator or the benzyldimethylketal represented by the formula (1) is preferably 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl)-1-butanone or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-? Polinyl)phenyl]-1-butanone. Examples of the 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone include Irgacure 369 (manufactured by BASF Corporation). Further, as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, For example, Irgacure 379EG (manufactured by BASF Corporation) or the like is mentioned.

The amount of the photopolymerization initiator other than the compound represented by the formula (1) or the benzyl dimethyl ketal is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total photopolymerizable component. More preferably, it is in the range of 0.5 to 6 parts by mass. The photopolymerization initiator other than the compound represented by the formula (1) or the benzyl dimethyl ketal may be used singly or in combination of two or more kinds. When the amount of the compound represented by the formula (1) or the benzyl dimethyl ketal is less than 0.1 part by mass based on 100 parts by mass of the all-photopolymerizable component, the photopolymerization initiation property becomes difficult to exhibit, so good. In addition, when the amount of the photopolymerization initiator other than the compound represented by the formula (1) or the benzyl dimethyl ketal is more than 10 parts by mass based on 100 parts by mass of the all-photopolymerizable component, there is a possibility that It has a bad influence on the physical properties of the hardened material, so it is not good.

Next, two or more types of dyes (3) will be described.

The dye (3) is used in combination of two or more types in order to impart light-shielding properties to visible light in a wide wavelength range.

Examples of the dye used as the component of the moisture-proof insulating coating of the present invention (I) include direct dyes, acid dyes, basic dyes, mord dyes, acid mord dyes, vat dyes, disperse dyes, and the like. For the reactive dye, the fluorescent whitening dye, the plastic dye, and the like, two or more kinds of dyes selected from the above are used.

In addition, the term "dye" as used in the present specification means "a substance which is soluble in a solvent or has compatibility with a resin and has a property of coloring a substance which has been dissolved and dissolved."

Moreover, the "direct dye" described in the present specification means a dye which is water-soluble and which is used as an auxiliary agent in a neutral or weakly alkaline bath for fibers.

The "acid dye" described in the present specification means a dye which is water-soluble and which is dyed with an acid bath such as sulfuric acid, formic acid or acetic acid.

The "basic dye" described in the present specification means a dye which is water-soluble and which is dyed in a neutral or weakly alkaline bath for fibers in which an acidic substance such as tannic acid is adhered in advance.

The "mord dye" described in the present specification means a dye which is dyed in a bath of a mord dye solution for a fiber in which a metal hydroxide or oxide of chromium, aluminum, iron, tin or the like is fixed in advance.

The "acid mord dye" described in the present specification means water-soluble, and the fiber may be dyed in an acid bath such as sulfuric acid, formic acid or acetic acid, or may be a metal to which chromium, aluminum, iron, tin or the like is previously fixed. A dye of a hydroxide or oxide fiber dyed in a mordant dye solution bath.

“Shilin dyes” as used in this specification means insoluble in water or A dye which is poorly soluble, which is dissolved in an alkaline bath by reducing a carbonyl group in a chemical structure, and is dyed by air oxidizing the fibers immersed therein.

The "dispersion dye" described in the present specification means a dye which is insoluble or poorly soluble in water and which is dyed by dipping a liquid in which a surfactant is dispersed in water.

The "reactive dye" described in the present specification means a dye having a chemical structure capable of forming a covalent bond with cellulose, wool, nylon or the like, and dyeing by reacting with the fibers.

The "fluorescent whitening dye" described in the present specification means a dye which absorbs ultraviolet rays and emits a blue-violet light having a wavelength longer than the above.

The term "plastic dye" as used in the present specification means a dye which is oil-soluble and has high compatibility with a resin, and is not a dyed fiber but is a dyed resin.

Among these, a plastic dye is preferable, and examples thereof include a azo dye (Colour Index Constitution Number 11000 to 19999), a azo dye (Colour Index Constitution Number 20000-29999), and a triaryl system. Dye (Colour Index Constitution Number 42000~44999), Quoline Index Dye (Colour Index Constitution Number 47000~47999), Carbonation Index Number 48000~48999, and azine dye (Colour Index) Constitution Number 50000~50999), amino acid ketone dye (Colour Index Constitution Number 56000~56999), lanthanide dye (Colour Index Constitution Number 58000~72699) ), an indigoid dye (Colour Index Constitution Number 72000-72999), or the like, containing at least one dye selected from the above dyes, and when two or more types of dyes are used at the same time, because of the wide visible light wavelength It is preferable to impart light shielding properties within the range.

More preferably, at least two of the dyes (3) are adjusted to have a transmittance at a maximum wavelength of absorption when the UV-visible light transmittance is measured under conditions of a butyl acetate solution and a light path length of 10 mm. a dye having a transmittance of 10% or more at a wavelength of 365 nm and a dye having a transmittance of 50% or more, and at least one of the at least two dyes (3) is most absorbed in a solution of butyl acetate. The wavelength is in the range of 450 nm or more and less than 550 nm, and at least one of the other types is a dye having a maximum absorption wavelength in the range of 550 nm or more and 700 nm or less when the butyl acetate solution is prepared. Preferably, at least two of the dyes are lanthanide dyes, and the dyes are all preferably lanthanide dyes. Here, the lanthanide dyes should be used in the Colour Index Constitution Number 58000~72699.

When the UV-visible light transmittance is measured under the conditions of a butyl acetate solution and a light path length of 10 mm, the solution having the concentration at the absorption maximum wavelength is adjusted to a concentration of 10% at a wavelength of 365 nm. The transmittance (hereinafter also referred to as "T ₃₆₅ ") is 50% or more, and the maximum absorption wavelength (hereinafter also referred to as "λ _max ") when the butyl acetate solution is formed is in the range of 450 nm or more and less than 550 nm. Examples of the oxime dyes include, for example, 1,4-diamino-2,3-diphenoxy-9,10-fluorene (T ₃₆₅ = 95%, λ _max = 516 nm), 1-amino group. -2-phenoxy-4-hydroxy-9,10-fluorene (T ₃₆₅ =83%, λ _max =516 nm), 1-(methylamino)phosphonium (T ₃₆₅ =90%, λ _max = 500nm) and so on. Further, when UV-visible light transmittance is measured under conditions of a butyl acetate solution having an optical path length of 10 mm, a solution having a concentration at which the absorption wavelength at the maximum wavelength is adjusted to 10% is at a wavelength of 365 nm. The fluorene dye having a transmittance of 50% or more and having a maximum absorption wavelength in the range of 550 nm or more and 700 nm or less may, for example, be 1,4-bis(2,4,6-trimethylphenylamino group). )-9,10-蒽醌 (T ₃₆₅ =67%, λ _max =630 nm), 1,4-bis(butylamino)-9,10-蒽醌 (T ₃₆₅ =70%, λ _max =645 nm) ), 1,4-bis(4-methylanilino)fluorene-9,10-dione (T ₃₆₅ =52%, λ _max =640 nm), 5,8-bis(p-butylanilino)- 1,4-Dihydroxyindole (T ₃₆₅ = 68%, λ _max = 683 nm) and the like.

In addition, the "Colour Index Constitution Number" described in the present specification refers to the pigments and pigments (pigments and dyes) and the related compound database which are recorded in "The Society of Dyers and Colourists and The American Association of Textile Chemists and Colorists". In Index International, the number is given based on the chemical structure.

The amount of the dye used in the moisture-proof insulating coating of the present invention (I) is not particularly limited. However, if the concentration in the moisture-proof insulating coating is too low, sufficient light-shielding property cannot be obtained, and when the concentration is too high, ultraviolet light penetration is observed. The rate is reduced and the possibility of hardening is caused. Therefore, the amount of the dye to be used is preferably in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the total polymerizable component. More preferably, it is 0.15 to 5 parts by mass.

Description of hardening the moisture-proof insulating coating of the invention (I) And the method of measuring the thickness of the cured film. The thickness of the cured film was measured using an outer side micro-device. At this time, in order to reduce the measurement error of each measurement and the measurement error of each measurer, it is preferable to use the side side micro-device having a constant pressure mechanism. Examples of the constant pressure mechanism include a Ratchet stop type and the like.

In order to increase the storage stability, the moisture-proof insulating coating of the invention (I) may be added with a polymerization inhibiting agent and preferably added.

Further, the polymerization inhibiting agent is not particularly limited, and examples thereof include hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthrenequinone, toluene, and 2,5-diethyloxene. Base-p-benzoquinone, 2,5-dihexyloxy-p-benzoquinone, 2,5-decyloxy-p-benzoquinone, 2,5-di-tert-butyl-3-methyl Phenol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t- Amyl hydroquinone, di-t-butyl ‧ p-cresol hydroquinone monomethyl ether, alpha naphthol, acetamidine acetate, acetamidine sulphate, phenyl hydrazine hydrochloride, hydrazine hydrochloride, chlorine Trimethylbenzylammonium chloride, lauryl acridine chloride, hexadecyltrimethylammonium chloride, phenyltrimethylammonium chloride, trimethylbenzylammonium oxalate, bis(trimethylbenzyl) Alkyl ammonium) oxalate, trimethylbenzyl ammonium malate, trimethylbenzyl ammonium tartrate, trimethylbenzyl ammonium glycolate, phenyl-β-naphthylamine, p-benzylamine Phenol, di-β-naphthyl p-phenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, benzenetriol, tannic acid, resorcinol, triethylamine salt Acid salt, dimethylaniline hydrochloride And dibutyl amine hydrochloride.

These may be used alone or in combination of two or more.

Among these, hydroquinone, p-methoxyphenol, p-benzene are also more suitable. Bismuth, naphthoquinone, phenanthrenequinone, toluene, 2,5-diethyloxy-p-benzoquinone, 2,5-dihexyloxy-p-benzoquinone, 2,5-decyloxy-p -benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di- T-amylhydroquinone, di-t-butyl ‧ p-cresol hydroquinone monomethyl ether and phenothiazine.

In general, the polymerization inhibiting agent is preferably added in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total polymerizable component.

The moisture-proof insulating coating material of the invention (I) may further contain a decane coupling agent (4) for the purpose of imparting adhesion to glass, metal or metal oxide.

The decane coupling agent (4) is an organic ruthenium compound having both a functional group reactively reacted with an organic material in the molecule and a functional group reactively bonded to the inorganic material, and generally has a structure of the following formula (8). Representation.

Here, Y is a functional group which is bonded to an organic material, and examples thereof include a vinyl group, an epoxy group, an amine group, a substituted amine group, a (meth)acryl fluorenyl group, a fluorenyl group and the like. X is a functional group reactive with an inorganic material, and is hydrolyzed by water or moisture to form a stanol. This stanol is reacted with an inorganic material. Representative examples of X include alkoxy groups, ethoxylated groups, chlorine atoms and the like. R ¹² is a divalent organic group, and R ¹³ represents an alkyl group. i is an integer from 1 to 3, and j is an integer from 0 to 2. However, i+j=3.

Examples of the decane coupling agent include 3-isocyanate propyl triethoxy decane, 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl methyl diethoxy decane, and 3-isocyanate propyl group. Dimethoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy Decane, vinyl ginseng (2-methoxyethoxy)decane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-propene oxime Propyltriethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropane Methyldimethoxydecane, 3-propenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropane Propyl triethyl Oxydecane, 3-glycidoxypropylmethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2 -aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amino Propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, allyl Trimethoxy decane and the like.

Among these, Y is preferably a compound reactive with a (meth)acryl-based fluorenyl compound (1) or a urethane (meth) acrylate, and also a p-styrene-based trimethyl group. Oxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, vinyl ginseng (2-methoxy ethoxylate) Base) decane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-methyl Propylene methoxypropyl triethoxy decane, 3-propenyl methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3-propene oxime Preferably, oxypropylmethyldiethoxydecane or 3-methylpropenyloxypropylmethyldiethoxydecane is preferably introduced into the hardened material during photohardening reaction. 3-Allyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-methylpropeneoxime Propyl three Ethoxy decane, 3-propenyl methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3- propylene methoxy propyl methyl two Ethoxy decane, 3-methacryloxypropylmethyldiethoxy decane, especially when considering the reactivity of alkoxy fluorenyl groups, especially 3-propenyloxypropyltrimethoxy Decane, 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane It is better.

The decane coupling agent (4) is at 0.01 in terms of 100 parts by mass of the total polymerizable component in the moisture-proof insulating coating of the invention (I) The range of parts by mass to 8 parts by mass is preferably from 0.1 part by mass to 5 parts by mass. When 100 parts by mass of the total polymerizable component in the moisture-proof insulating coating material of the invention (I) is less than 0.01 parts by mass, the adhesion to glass, metal or metal oxide may not be sufficiently exhibited. Not good. In addition, when 100 parts by mass of the total polymerizable component in the moisture-proof insulating coating material of the invention (I) is more than 8% by mass, the surface viscosity of the cured product increases depending on the type of the decane coupling agent to be used. tendency.

In the moisture-proof insulating coating material of the invention (I), the adhesion-imparting agent (5) may be further included for the purpose of imparting adhesion to the substrate.

The adhesion-imparting agent used in the moisture-proof insulating coating material of the invention (I) means that it is adhered by a polymer compound represented by a urethane (meth) acrylate or a rubber-elastic elastomer. The substance for use is generally a compound in the field of oligomers having a molecular weight of several hundred to several thousand, which is in a glass state at room temperature and which itself has a property of not exhibiting rubber elasticity.

As the adhesion-imparting agent, a petroleum-based resin adhesion-imparting agent, a terpene-based resin adhesion-imparting agent, a rosin-based resin adhesion-imparting agent, a coumarone-indene resin adhesion-imparting agent, and a styrene-based resin adhesion can be used. Agents, etc.

Examples of the petroleum-based resin adhesion-imparting agent include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymerized petroleum resin, an alicyclic petroleum resin, a dicyclopentadiene resin, and the like. Denatures such as hydrides. The synthetic petroleum resin can be either the C5 series or the C9 series.

Examples of the terpene-based resin adhesion-imparting agent include β-pinene resin, α-pinene resin, terpene-phenol resin, aromatic-modified terpene resin, and hydrogenated terpene resin. Many of these terpene-based resins are resins which do not have a polar group.

Examples of the rosin-based resin adhesion-imparting agent include rosin such as rosin gum, tall oil rosin, and wood rosin; denatured rosin such as hydrogenated rosin, uneven rosin, polymerized rosin, and maleated rosin; rosin glyceride, A rosin ester such as hydrogenated rosin ester or hydrogenated rosin glyceride. These rosin-based resins are those having a polar group.

These adhesion-imparting agents may be used singly or in combination of two or more.

Among these adhesion-imparting agents, at least one or more kinds of petroleum-based resin adhesion-imparting agents and terpene-based resin adhesion-imparting agents are preferable, and more preferably at least one type of petroleum-based resin adhesion-imparting agent is contained.

The total amount of the adhesion-imparting agent is preferably 0.1 to 35 parts by mass in terms of 100 parts by mass of the total polymerizable component. When the total amount of the adhesion-imparting agent is less than 0.1 part by mass based on 100 parts by mass of the total polymerizable component, it is difficult to exhibit the effect of adding the adhesion-imparting agent, which is not preferable. In addition, when the total amount of the adhesion-imparting agent is more than 35 parts by mass based on 100 parts by mass of the total polymerizable component, the moisture-proof insulating coating of the invention (I) may have turbidity or may have an excessively high viscosity. Sex, it is difficult to say that it is better.

Further, in the moisture-proof insulating coating material of the invention (I), a radical chain transfer agent may be used as necessary.

As a radical chain transfer agent, it can be used without limitation The polymerization active species captured by the inactive free radical scavenger reactivates and imparts a compound having enhanced surface hardenability. Examples of the compound to be a chain transfer agent include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, and N. N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-di Methyl-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-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyl Ethyl)-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-dimethylamino benzoic acid ethyl ester, 4- N,N-dimethylamino benzoic acid methyl ester, N,N-dimethylamino benzoic acid n-butoxyethyl ester, 4-N,N-dimethylamino benzoic acid 2- (methacryloxy)ethyl ester, 4-N,N-dimethylaminobenzophenone, trimethylamine, triethyl Base amine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, etc. A suitable amine is 2-ethylhexyl-4-dimethylaminobenzoate.

The moisture-proof insulating coating of the invention (I) uses a radical chain When the amount of the transfer agent is from 0.01 to 10 parts by mass based on 100 parts by mass of the total polymerizable component, the amount of the agent is high and the surface hardenability in air is improved. More preferably, the surface hardenability is further improved in the range of 0.5 to 5 parts by mass. These radical chain transfer agents may be used singly or in combination of two or more kinds.

The moisture-proof insulating coating of the present invention (I) preferably has a viscosity at 25 ° C of 2000 mPa ‧ or less. More preferably, the viscosity at 25 ° C is 1600 mPa ‧ or less. When the viscosity at 25 ° C is higher than 2000 mPa ‧ s, when the curable composition is applied by a scribing method using a dispenser, the spread after coating is suppressed, and as a result, the thickness after hardening becomes Become the required situation.

The moisture-proof insulating coating material of the present invention (I) may be added with a filler, a modifier, an antifoaming agent, a coloring agent, etc., as long as it does not adversely affect fluidity or photocurability.

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

The modifier is, for example, a leveling agent for improving flatness. The leveling agent may be, for example, a polyether-denatured dimethylpolysiloxane copolymer, a polyester-denatured dimethylpolysiloxane copolymer, a polyether-denatured methylalkyl polyoxyalkylene copolymer, an aralkyl group. Denatured methyl alkyl polyoxyalkylene copolymer and the like. These may be used alone or in combination of two or more. 0.01 to 10 parts by mass can be added to 100 parts by mass of the total polymerizable component. When it is less than 0.01 part by mass, there is a possibility that the effect of adding a leveling agent cannot be exhibited. Moreover, when it is more than 10 parts by mass, it is used according to The type of leveling agent, and the possibility of surface stickiness, which deteriorates electrical insulation properties.

The antifoaming agent described above is not particularly limited as long as it is used to apply the moisture-proof insulating coating of the present invention (I), and has a function of eliminating bubbles or suppression of generation or remaining.

Examples of the antifoaming agent used in the moisture-proof insulating coating material of the present invention (I) include a polyfluorene-based oil, a fluorine-containing compound, a polycarboxylic acid-based compound, a polybutadiene-based compound, and an acetylene glycol-based compound. Such as known defoamers. Specific examples thereof include BYK-077 (manufactured by BicChemy Japan Co., Ltd.), SN Deformer 470 (manufactured by San Nopco Co., Ltd.), TSA750S (manufactured by Momentive Performance Materials Co., Ltd.), and polyoxygenated oil SH-203. Polyoxygenated defoamer, etc., manufactured by Toray Dow Corning Co., Ltd., Dappo SN-348 (manufactured by San Nopco Co., Ltd.), Dappo SN-354 (manufactured by San Nopco Co., Ltd.), Dappo SN-368 Acrylate-based polymer defoamer, such as (San Nopco Co., Ltd.), Disparlon 230HF (manufactured by Nanben Chemical Co., Ltd.), Surfinol DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.), Surfinol DF-37 An acetylene glycol-based antifoaming agent such as (manufactured by Nissin Chemical Industry Co., Ltd.) or a fluorine-containing polyfluorinated defoaming agent such as FA-630. These may be used alone or in combination of two or more. Usually, it is added in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the total polymerizable component. When it is less than 0.01 part by mass, there is a possibility that the effect of adding an antifoaming agent cannot be exhibited. Moreover, when it is more than 5 parts by mass, surface tackiness is generated depending on the kind of the antifoaming agent to be used, and electrical insulation is caused. The possibility of deterioration of characteristics.

The coloring agent may, for example, be a known inorganic pigment, an organic pigment, or an organic dye, and may be individually blended in accordance with the desired color tone. These may be used alone or in combination of two or more.

Next, a sealing treatment or an insulation treatment method according to the invention (III) will be described.

In the sealing treatment or the insulation treatment method of the invention (III), the moisture-proof insulating coating material of the invention (I) is coated with an electronic component, and the LED-UV lamp is irradiated to the moisture-proof insulating coating coating portion to be hardened. The coating method of the moisture-proof insulating coating material is not particularly limited, and examples thereof include a dipping method, a brush coating method, a spray method, and a scribing method. The method of irradiating the ultraviolet ray irradiated by the LED-UV lamp toward the moisture-proof insulating coating application portion is not particularly limited, and for example, the flexible light-guiding tube is held by hand or mechanically, and the moisture-proof tube is coated and protected from moisture. A method of irradiating an electronic component of an insulating coating, or carrying an electronic component coated with a moisture-proof insulating coating onto a conveyor, and irradiating it through an area that can be irradiated with ultraviolet light from an LED-UV lamp Method, etc.

Next, the electronic component relating to the invention (IV) will be explained.

The invention (IV) is an electronic component which is subjected to a sealing treatment or an insulation treatment by the moisture-proof insulating coating material of the invention (I). Examples of the electronic component include a microcomputer, a transistor, a capacitor, a resistor, a relay, a transformer, and the like, and a mounting board or the like mounted thereon, and may also include a wire, a heald, and the like, which are bonded to the electronic component. Film substrate, etc.

Further, a liquid crystal display panel, a plasma display panel, and an organic battery can also be cited. A signal input portion of a flat panel display panel such as a light-emitting panel or a field emission display panel, a touch sensor of the touch panel, and wiring thereof are used as electronic components.

The electronic component of the invention (IV) can be produced by applying the moisture-proof insulating coating of the invention (I) to an electronic component, and secondarily by curing the coated moisture-proof insulating coating. As a specific manufacturing method of the electronic component of the invention (IV), first, the moisture-proof insulating coating material is applied to the above by a method such as a generally known dipping method, a brush coating method, a spray method, or a scribing method. Electronic parts. Next, high-pressure mercury, a metal halide lamp, an LED, or the like is used as a light source to irradiate ultraviolet rays, and the coating film of the moisture-proof insulating coating applied to the electronic component is cured to obtain an electronic component.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the following examples.

(Synthesis Example 1)

Sovermol (registered trademark) 908 (hydrogenated dimer diol of BASF, purity of hydrogenated dimer diol: 97.5 wt%) 22.00 g, EMPOL (registered trademark) 1008 was added to a reaction vessel equipped with a stirrer and a water separator. BASF hydrogenated dimer acid, hydrogenated dimer acid purity 92.0%) 23.00g, Neostann U-810 (Nitto Chemical Co., Ltd. dioctyltin dilaurate) 0.01g, starting at about 240 ° C, atmospheric pressure The condensed water was allowed to flow out while decomposing the dehydration esterification reaction under reduced pressure to obtain a hydroxyl group having a valence of 59 mgKOH/g, a number average molecular weight of 2,000, and containing a hydrogenated dimer 2 A mixture of a polyester polyol and a hydrogenated dimer diol having 15% by mass of an alcohol (hereinafter referred to as polyester polyol A).

(Synthesis Example 2)

Adding polyester polyol A 45.00g, Sovermol (registered trademark) 908 (hydrogenated dimer diol of BASF, hydrogenated dimer diol purity 97.5wt) to a 300 mL reaction vessel equipped with a stirring device, a thermometer and a condenser %) 17.94g, Nonion (registered trademark) L-2 (single lauric acid polyethylene glycol manufactured by Nippon Oil Co., Ltd.) 0.82g, Irganox (registered trademark) 1010 (valence pentaerythritol BA [3-(3,5-) Di-tert-butyl-4-hydroxyphenyl)]propionate) 0.12g, Neostann U-810 (dioctyltin dilaurate manufactured by Nitto Chemical Co., Ltd.) 0.01g and VESTANAT (registered trademark) 32.62 g of H12MDI (methylene bis(4-cyclohexyl isocyanate) manufactured by Evonik Degussa) was stirred and heated to 75 to 80 ° C using an oil bath. Thereafter, the mixture was stirred for 2.5 hours while continuing the reaction. Thereafter, 20.69 g of 4-HBA (4-hydroxybutyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to the reaction vessel, and stirring was continued while maintaining the temperature in the reaction vessel at 80 ° C ± 5 ° C. In the range of the range, the reaction was continued for 10 hours. Thereafter, the infrared absorption spectrum was measured, and it was found that the absorption of the isocyanate group disappeared, and the reaction was terminated to obtain a urethane acrylate (hereinafter referred to as urethane acrylate B).

(Synthesis Example 3)

Sovermol (registered trademark) 908 (hydrogenated dimer diol of BASF, purity of hydrogenated dimer diol: 97.5 wt%) 34.0 g, hydroquinone monomethyl was added to a 300 mL reaction vessel equipped with a stirring device, a thermometer, and a condenser. 100 mg of the ether was stirred and heated to 40 ° C using an oil bath. Thereafter, methylene bis(4-cyclohexyl isocyanate) (manufactured by Evonik Degussa, trade name: VESTANAT (registered trademark) H12MDI) 32.60 g (124.2 mmol) and Neostann U-810 (Nitto Chemical Co., Ltd. Base tin dilaurate) 0.01 g, stirring was continued while the internal temperature was raised to 90 °C. After the temperature was raised to 90 ° C, the mixture was stirred for 4 hours and the reaction was continued. Thereafter, 17.91 g (124.2 mmol) of 4-hydroxybutyl acrylate was added to the reaction vessel, and stirring was continued while maintaining the temperature in the reaction vessel at a temperature of 90 ° C ± 5 ° C to continue the reaction. hour. Thereafter, the infrared absorption spectrum was measured, and after the absorption of the isocyanate group was found to disappear, the reaction was terminated to obtain a urethane acrylate (hereinafter referred to as urethane acrylate C).

(Synthesis Example 4)

After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and an air gas introduction pipe, HEA (2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 53.00 g, GI-1000 (Japan Soda) The hydrogenated polybutadiene diol produced by the company, the number average molecular weight: about 1,500), 600.00 g, and 0.50 g of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were heated to 70 ° C using an oil bath. Thereafter, stirring is carried out while maintaining the temperature at 70 to 75 ° C for 30 minutes, which is 3 70.00 g of Coronate (registered trademark) T-65 (manufactured by Nippon Polyurethane Industrial Co., Ltd.) was uniformly dropped in an hour. After the completion of the dropwise addition, stirring was carried out and the temperature was maintained at 70 to 75 ° C for about 5 hours, and the reaction was continued. Thereafter, the infrared absorption spectrum was measured, and it was found that the absorption of the isocyanate group disappeared, and the reaction was terminated to obtain a urethane acrylate (hereinafter referred to as urethane acrylate D).

(Synthesis Example 5)

Hydrogenated polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO-PB GI-2000, hydroxyl value 47.3 mgKOH/g) 540.0 g was added to a 1 liter four-necked flask equipped with a stirrer and a distillation apparatus. , n. butyl acrylate 162.0g, dioctyltin dilaurate 0.81g and pentaerythritol 肆 [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Corporation System, trade name: IRGANOX1010) 3.51g, under a stream of air, the mixture of n-butanol and n-butyl acrylate formed by heating to 130 ° C is refluxed and simultaneously distilled to the reaction system for 10 hours. outer. After n-butanol and n-butyl acrylate were no longer present, the pressure in the reaction system was reduced to 10 kPa using a vacuum, and n-butanol and n-butyl acrylate were again distilled off to the outside of the system. After maintaining the temperature at 50 Pa for 1.5 hours, the reactor was cooled to obtain hydrogenated polybutadiene diacrylate (hereinafter referred to as polyol polyacrylate E).

(Example 1)

Use defoaming Rantaro ARE-310 (made by THINKY Co., Ltd. Rotating ‧ revolution mixer) Blending the aforementioned urethane acrylate B 4.50 g, IBXA (isodecyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4.50 g, Blemmer LA (Lauryl Acrylic Co., Ltd.) Ester) 0.80g, A-DPH (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.20g, 1-(methylamino) oxime 0.01g of dye, 1,4-double (4-A) TR-PBG-304 of anilinium-9,10-dione 0.01g, photopolymerization initiator (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) 1-[9 -ethyl-6-(2-methylbenzylindenyl)-9H-indazol-3-yl]-3-cyclopentylacetone-1-(O-acetamidoxime) 0.20g, antifoaming agent DISPALON L-1982N (acrylonitrile-based copolymer produced by Nanben Chemical Co., Ltd.) was 0.025 g, and this complex was used as the moisture-proof insulating coating B1.

(Examples 2 to 8 and Comparative Examples 1 to 3)

In the same manner as in Example 1, the components and amounts shown in Table 1 were blended to obtain moisture-proof insulating coatings B2 to B6, C1, D1, E1, and F1.

In Table 1, Irgacure (registered trademark) 651 is a benzyl dimethyl ketal prepared by BASF, and Irgacure (registered trademark) 369 is 2-benzyl-2-dimethylamino-1-(4-morpholine) manufactured by BASF. Phenylphenyl)-butanone-1.

Further, the dyes used in the examples and comparative examples were as follows.

1-(methylamino)phosphonium (T ₃₆₅ = 90%, λ _max = 500 nm)

1-amino-2-phenoxy-4-hydroxy-9,10-fluorene (T ₃₆₅ =83%, λ _max =516 nm)

1,4-Bis(4-methylanilino)indole-9,10-dione (T ₃₆₅ =52%, λ _max =640 nm)

5,8-bis(p-butylanilino)-1,4-dihydroxyindole (T ₃₆₅ =68%, λ _max =683 nm)

1,4-Bis(2,4,6-trimethylphenylamino)-9,10-fluorene (T ₃₆₅ =67%, λ _max =630 nm)

2,3-Dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1h-acridine (T ₃₆₅ =42%, λ _max =595nm)

<Evaluation of deep hardenability>

The deep hardening system was evaluated according to the following method.

The moisture-proof insulating coatings B1 to B6, C1, D1, E1, and F1 were applied to a polyimide film (trade name: Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) to have a thickness of 1 mm. Using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) using an LED-UV lamp (wavelength: 365 nm), ultraviolet rays were irradiated under conditions of an illuminance of 400 mW/cm ² and an exposure amount of 300 mJ/cm ² , and the wipe was removed and coated. The case where the thickness of the hardened portion after the uncured liquid portion of the wet insulating coating was 500 μm or more was evaluated as ○, and the case where the thickness was less than 500 μm was evaluated as ×. The results are shown in Table 1.

<Production of test piece for light-shielding evaluation>

The moisture-proof insulating coatings B1 to B6, C1, D1, E1, and F1 were respectively applied to a glass plate (50 mm × 50 mm × 0.7 mm, glass) by a thickness of 500 μm using a bar coating device. In the product name "EAGLE XG" (registered trademark) and CORNING, the same type of glass is placed on the coated surface, and an ultraviolet ray irradiation device (manufactured by Eye Graphics Co., Ltd.) using an LED-UV lamp (wavelength: 365 nm) is used. Under the conditions of an illuminance of 400 mW/cm ² and an exposure amount of 300 mJ/cm ² , ultraviolet rays were irradiated from both surfaces, and each moisture-proof insulating coating was completely cured to obtain a test piece. Using this test piece, the following measurement of the transmittance of the visible light wavelength and the measurement of the total light transmittance were carried out.

<Measurement of the transmittance of visible light wavelength>

The test piece for the evaluation of the light-shielding property was placed between two glass plates (50 mm × 50 mm × 0.7 mm, glass type: trade name "EAGLE XG" (registered trademark), manufactured by CORNING), and 500 μm thick distilled water was added. The transmittance of each wavelength was measured in a wavelength range of 400 to 700 nm using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation) as a reference. The case where the transmittance is less than 10% in the entire wavelength range of 400 to 700 nm is ◎, and the total of the wavelength range of the transmittance of 10% or more in the wavelength range of 400 to 700 nm is 50 nm or less. In the case of ○, the total of the wavelength ranges in which the transmittance is 10% or more in the wavelength range of 400 to 700 nm is more than 50 nm is evaluated as ×. The results are shown in Table 1.

<Measurement of total light transmittance>

The test piece for the evaluation of the light-shielding property was placed between two glass plates (50 mm × 50 mm × 0.7 mm, glass type: trade name "EAGLE XG" (registered trademark), manufactured by CORNING), and 500 μm thick distilled water was added. The reference is used as a reference, and the total light transmittance is measured in accordance with JIS K 7361-1. The case where the total light transmittance was less than 10% was rated as ○, and the case where 10% or more was evaluated as ×. The results are shown in Table 1.

As can be seen from Table 1, the moisture-proof insulating coating materials B1 to 3, C1, D1, E1, and F1 containing two or more types of dyes have high deep curing property and light blocking property. Further, it is known that the moisture-proof insulating coatings B4 to B6 containing only one type of dye are inferior in either of the deep hardenability and the light-shielding property. In other words, it is understood that the moisture-proof insulating coating of the present invention (I) has high deep-curing property and light-shielding property as compared with a moisture-proof insulating coating material which does not contain an existing dye or a dye containing only one type of dye.

[Industrial availability]

The moisture-proof insulating coating of the present invention (I) has both high deep curing property and light blocking property. Further, the moisture-proof insulating coating of the present invention (I) and the sealing treatment by the LED-UV lamp and the insulating treatment have a low environmental load and are low in cost. The electronic component which is subjected to the sealing treatment by the moisture-proof insulating coating of the present invention (I) is highly reliable, and can suppress light leakage, and is provided with a mounting circuit board for mounting a microcomputer or various components.

Claims (15)

A moisture-proof insulating coating characterized by comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) two or more kinds of dyes; and a thickness obtained by hardening the coating material The total light transmittance of the cured film of 500 μm is less than 10%, and the total wavelength range of the transmittance of 10% or more in the wavelength range of 400 to 700 nm is 50 nm or less, and the illuminance at a wavelength of 365 nm is 400 mW/cm. ^2. The thickness of the cured film obtained by applying ultraviolet rays to the coating material having a thickness of 1 mm or more under the condition of an exposure amount of 300 mJ/cm ² is 500 μm or more. The moisture-proof insulating coating of claim 1, wherein the cured film having a thickness of 500 μm obtained by hardening the coating has a total light transmittance of less than 10%, and the transmittance is not in the entire wavelength range of 400 to 700 nm. 10% full. The moisture-proof insulating coating material of claim 1 or 2, wherein at least two of the dyes (3) are respectively subjected to UV-visible light transmittance measurement under conditions of forming a butyl acetate solution and having an optical path length of 10 mm A dye having a transmittance at a maximum wavelength absorbed to a concentration of 10% is adjusted to have a transmittance of 50% or more at a wavelength of 365 nm. The moisture-proof insulating coating according to any one of claims 1 to 3, wherein at least one of the dyes (3) has a maximum absorption wavelength in a range of 450 nm or more and less than 550 nm when the butyl acetate solution is formed, and The absorption maximum wavelength of at least one of the other types in the butyl acetate solution is in the range of 550 nm or more and 700 nm or less. A moisture-proof insulating coating characterized by comprising (1) a (meth)acryl-containing fluorenyl compound, (2) a photopolymerization initiator, and (3) two or more kinds of dyes; at least two kinds of dyes (3) When the UV-visible light transmittance is measured under the condition that the butyl acetate solution is prepared and the optical path length is 10 mm, the solution at which the transmittance at the absorption maximum wavelength is adjusted to a concentration of 10% is at a wavelength of 365 nm. A dye having a penetration rate of 50% or more. The moisture-proof insulating coating of claim 5, wherein at least one of the dyes (3) has a maximum absorption wavelength in the range of 450 nm or more and less than 550 nm when the butyl acetate solution is formed, and at least one of the other types is The maximum absorption wavelength in the case of forming a butyl acetate solution is in the range of 550 nm or more and 700 nm or less. The moisture-proof insulating coating according to any one of claims 1 to 6, wherein at least two of the dyes (3) are lanthanide dyes. The moisture-proof insulating coating according to any one of claims 1 to 7, wherein the photopolymerization initiator (2) is a compound represented by the formula (1) or a benzyldimethylketal; (wherein R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are a hydrocarbon group). The moisture-proof insulating coating according to any one of claims 1 to 8, wherein the (meth)acryl fluorenyl compound (1) is selected from the group consisting of poly (poly) poly (meth) acrylate, epoxy (methyl) At least one of an acrylate, a urethane (meth) acrylate, and a (meth) acryl fluorenyl monomer. The moisture-proof insulating coating according to any one of claims 1 to 9, wherein the (meth)acryl fluorenyl compound (1) is selected from the group consisting of poly (poly) poly (meth) acrylate, epoxy (methyl) At least one of an acrylate and a (meth) acrylonitrile-based monomer, and a urethane (meth) acrylate. A moisture-proof insulating coating according to claim 9 or 10, wherein the urethane (meth) acrylate is a structure derived from a polyester polyol having a derivatized by a hydrogenated dimer acid The structural unit and the structural unit derived from the hydrogenated dimer diol. The moisture-proof insulating coating according to any one of claims 1 to 11, which further comprises (4) a decane coupling agent. The moisture-proof insulating coating according to any one of claims 1 to 12, further comprising (5) an adhesion-imparting agent. A method for sealing or insulating an electronic component, comprising applying the moisture-proof insulating coating according to any one of claims 1 to 13 to an electronic component, and curing the coating portion by illuminating the LED-UV lamp The steps. An electronic component which is subjected to a sealing treatment or an insulation treatment by the moisture-proof insulating coating material according to any one of claims 1 to 13.