WO2013118655A1 - ウレタン(メタ)アクリレートおよび防湿絶縁塗料 - Google Patents
ウレタン(メタ)アクリレートおよび防湿絶縁塗料 Download PDFInfo
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- WO2013118655A1 WO2013118655A1 PCT/JP2013/052383 JP2013052383W WO2013118655A1 WO 2013118655 A1 WO2013118655 A1 WO 2013118655A1 JP 2013052383 W JP2013052383 W JP 2013052383W WO 2013118655 A1 WO2013118655 A1 WO 2013118655A1
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- acrylate
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- proof insulating
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- TXVUSPOYTHMUGA-UHFFFAOYSA-N C=CC(OCCCCOC(NC1CCC(CC(CC2)CCC2NC(OCCCCOC(C=C)=O)=O)CC1)=O)=O Chemical compound C=CC(OCCCCOC(NC1CCC(CC(CC2)CCC2NC(OCCCCOC(C=C)=O)=O)CC1)=O)=O TXVUSPOYTHMUGA-UHFFFAOYSA-N 0.000 description 1
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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Definitions
- the present invention relates to a novel urethane (meth) acrylate, a moisture-proof insulating paint containing this urethane (meth) acrylate as an essential component, and an electronic component insulated using the moisture-proof insulating paint.
- Patent Document 1 Obtained by reacting a diol having a side chain with a straight chain having 3 to 7 carbon atoms, a polyester polyol composed of dimer acid, polyisocyanate, and (meth) acrylate having active hydrogen in Patent Document 1
- a urethane (meth) acrylate composition is disclosed.
- Patent Document 1 does not describe a urethane (meth) acrylate having a polyester polyol structural unit derived from hydrogenated dimer diol and hydrogenated dimer acid.
- Patent Document 2 discloses a urethane (meth) acrylate composition obtained by reacting a polyester polyol composed of a linear glycol having 2 to 7 carbon atoms with a dimer acid, a polyisocyanate, and a (meth) acrylate having active hydrogen. Things are disclosed. However, Patent Document 2 does not describe a urethane (meth) acrylate having a polyester polyol structural unit derived from hydrogenated dimer diol and hydrogenated dimer acid.
- Patent Document 3 discloses a polyester polyol having an organic polyisocyanate compound, dimer acid, dimer diol and a hydrogenated product thereof having at least one kind as a copolymerization component and a number average molecular weight of 8000 or less, and a hydroxyl group-containing (meth) acrylate A urethane (meth) acrylate composition obtained by reacting is disclosed.
- Patent Document 3 only describes a urethane (meth) acrylate having a polyester polyol structural unit derived from diethylene glycol and dimer acid, and a polyester derived from hydrogenated dimer diol and hydrogenated dimer acid. There is no description regarding urethane (meth) acrylate having a polyol structural unit.
- a urethane-modified acrylate resin composition obtained by reacting a polyester polyol compound, a polyolefin polyol compound or the like with a polyisocyanate and a hydroxyalkyl (meth) acrylate is known.
- Patent Document 4 discloses a photocurable moisture-proof insulating paint containing an acrylic-modified hydrogenated polybutadiene resin that has high adhesion to glass and exhibits excellent properties in moisture resistance evaluation.
- Patent Document 5 discloses a reaction mixture obtained by reacting 2-hydroxyethyl acrylate, hydrogenated polybutadiene diol and tolylene diisocyanate at a mixing ratio of hydroxyl group / isocyanate group> 1, isobornyl acrylate, lauryl acrylate and A photocurable moisture-proof insulating coating containing an alkoxysilane compound having an isocyanate group and a photopolymerization initiator is disclosed.
- Patent Document 6 discloses a reaction product obtained by reacting 2-hydroxyethyl acrylate, hydrogenated polybutadiene diol and tolylene diisocyanate, lauryl acrylate, bisphenol A propylene glycol adduct diacrylate, and an alkoxy having an isocyanate group.
- a photocurable moisture-proof insulating coating containing a silane compound is disclosed.
- urethane-modified acrylate resin compositions that use polyester polyol compounds generally have high moisture permeability
- urethane-modified acrylate resin compositions that use polyolefin polyol compounds have poor adhesion to substrate materials.
- the paint containing the composition has a problem in the reliability of electronic components when used as a moisture-proof insulating paint for a mounting circuit board.
- the resin composition disclosed in Patent Document 4 is attracting attention because the physical properties of the cured product vary depending on the structure and blending in addition to polymerization even when the oxygen concentration is high.
- this resin composition has a high viscosity at room temperature and has a handling problem.
- the urethane (meth) acrylate compounds disclosed in Patent Document 5 and Patent Document 6 are too viscous, and it is hoped that a large amount of monofunctional acrylates of 2-hydroxyethyl acrylate, isobornyl acrylate and lauryl acrylate will not be used. There was a problem that the viscosity could not be adjusted.
- the present invention has been made in view of the above-described problems of the prior art, has a low environmental load, is excellent in surface curability at a low irradiation dose, is hydrophobic, and has high adhesion to a substrate material.
- An object is to provide a photocurable moisture-proof insulating coating.
- Another object of the present invention is to provide a novel polymerizable compound suitable as a component of the photocurable moisture-proof insulating coating.
- an object of the present invention is to provide a highly reliable electronic component that is insulated with the photocurable moisture-proof insulating paint for the mounting circuit board.
- a photocurable composition containing a polyurethane having a specific (meth) acryloyl group having a specific structure has good handling properties and is photocurable. It has been found that a cured product obtained by curing the composition has high adhesion to a substrate such as glass or polyimide and is excellent in electrical insulating properties, and has completed the present invention.
- the present invention (I) (A) a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol,
- the present invention relates to a urethane (meth) acrylate obtained by reacting (b) a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate.
- the present invention (II) (1) The urethane (meth) acrylate of the present invention (I), and (2) a moisture-proof insulating paint containing a (meth) acryloyl group-containing compound not containing a silicon atom.
- the present invention (III) relates to an electronic component that has been insulated using the moisture-proof insulating paint of the present invention (II).
- the present invention relates to the following [1] to [15].
- [1] (a) a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol, (B) A urethane (meth) acrylate obtained by reacting a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate.
- [2] A structure in which the polyester polyol (a) contains a structural unit derived from a hydrogenated dimer acid in an amount of 80% by mass or more of the total amount of structural units derived from a polycarboxylic acid and is derived from a hydrogenated dimer diol.
- the polyisocyanate compound (b) is at least one selected from the group consisting of norbornane diisocyanate, isophorone diisocyanate, and methylenebis (4-cyclohexylisocyanate), according to [1] or [2] Urethane (meth) acrylate.
- a moisture-proof insulating paint comprising the urethane (meth) acrylate according to any one of [1] to [3], and (2) a (meth) acryloyl group-containing compound not containing a silicon atom.
- R 1 represents H or CH 3.
- the urethane (meth) acrylate of the present invention is excellent in moisture-proof insulating performance and adhesion to a substrate, and the moisture-proof insulating paint using this is a urethane-modified (meth) acrylate resin composition with low moisture permeability.
- the environmental impact is small, the adhesiveness with the substrate material is high, and by applying and curing the moisture-proof insulating paint, it is possible to produce highly reliable electronic components.
- FIG. 1 shows the 1H-NMR spectrum (solvent: CDCl 3 ) of urethane acrylate B obtained in Example Synthesis Example 2.
- FIG. 2 shows the IR spectrum of urethane acrylate B obtained in Example Synthesis Example 2.
- FIG. 3 shows the 1H-NMR spectrum (solvent: CDCl 3 ) of urethane acrylate C obtained in Example Synthesis Example 3.
- FIG. 4 shows the IR spectrum of urethane acrylate C obtained in Example Synthesis Example 3.
- FIG. 5 shows the 1H-NMR spectrum (solvent: CDCl 3 ) of urethane acrylate D obtained in Example Synthesis Example 4.
- FIG. 6 shows the IR spectrum of urethane acrylate D obtained in Example Synthesis Example 4.
- (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
- the present invention (I) is a urethane (meth) acrylate obtained by reacting the following components (a) to (c).
- the component (a) which is an essential raw material component of the urethane (meth) acrylate of the present invention (I) is a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. .
- “Dimer acid” means a fatty acid having 14 to 22 carbon atoms having 2 to 4 ethylenic double bonds (hereinafter referred to as “unsaturated fatty acid A”), preferably carbon having 2 ethylenic double bonds.
- a fatty acid having 14 to 22 fatty acids and a fatty acid having 14 to 22 carbon atoms having 1 to 4 ethylenic double bonds hereinafter referred to as “unsaturated fatty acid B”
- a dimer acid obtained by reacting a single fatty acid having 14 to 22 carbon atoms with a double bond portion.
- the unsaturated fatty acid A includes tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (linolenic acid, etc.), eicosatetraenoic acid ( Arachidonic acid and the like), and linoleic acid is most preferable.
- unsaturated fatty acid B tetradecenoic acid (tuzuic acid, sperm acid, myristoleic acid) as a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond in addition to those exemplified above , Hexadecenoic acid (such as palmitoleic acid), octadecenoic acid (such as oleic acid, elaidic acid, vaccenic acid), eicosenoic acid (such as gadoleic acid), docosenoic acid (such as erucic acid, cetreic acid, brassic acid), etc. Acid or linoleic acid is most preferred.
- the use ratio (molar ratio) of unsaturated fatty acid A and unsaturated fatty acid B is preferably about 1: 1.2 to 1.2: 1, and most preferably 1: 1.
- the dimerization reaction can be performed according to a known method, for example, a method described in JP-A-9-136861. That is, for example, an unsaturated fatty acid A and an unsaturated fatty acid B are mixed with a Lewis acid or Bronsted acid type liquid or solid catalyst, preferably montmorillonite activated clay, and the total amount of unsaturated fatty acid A and unsaturated fatty acid B is 100 parts by mass.
- the pressure during the reaction is usually a slightly pressurized state, but may be normal pressure.
- the reaction time varies depending on the amount of catalyst and the reaction temperature, but is usually 5 to 7 hours.
- the catalyst can be filtered off and then distilled under reduced pressure to distill off unreacted raw materials and isomerized fatty acids, and then dimer acid fraction can be distilled off.
- the dimerization reaction is thought to proceed through double bond transfer (isomerization) and Diels-Alder reaction, but the present invention is not limited thereto.
- the obtained dimer acid is usually a mixture of dimer acids having different structures depending on the bonding site or isomerization of the double bond, and may be used separately, but can be used as it is. Further, the obtained dimer acid contains a small amount of monomeric acid (for example, 6% by mass or less, particularly 4% by mass or less), trimer acid or higher polymer acid (for example, 6% by mass or less, particularly 4% by mass or less). May be.
- the “hydrogenated dimer acid” described in the present specification refers to a saturated dicarboxylic acid obtained by hydrogenating the carbon-carbon double bond of the dimer acid.
- the dimer acid having 36 carbon atoms produced from, for example, linoleic acid and linoleic acid or oleic acid is used as a raw material, the structure of the main component of the hydrogenated dimer acid is represented by the following formula (2 ) And formula (3).
- Examples of commercially available hydrogenated dimer acid include PRIPOL (registered trademark) 1009 (manufactured by Croda), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF).
- the “hydrogenated dimer diol” described in the present specification means a reduction of at least one of the dimer acid, the hydrogenated dimer acid and the lower alcohol ester thereof in the presence of a catalyst,
- the main component is a diol obtained by hydrogenating the double bond.
- a hydrogenated dimer diol is produced by reducing a hydrogenated dimer acid containing a compound having a structure represented by formula (2) or formula (3) as a main component, the main component of the hydrogenated dimer diol is reduced.
- the structure is a structure represented by the following formulas (4) and (5).
- Examples of commercially available hydrogenated dimer diol include PRIPOL (registered trademark) 2033 (manufactured by Croda) and Sovermol (registered trademark) 908 (manufactured by BASF).
- the component can be produced by performing a condensation reaction in the presence of an esterification catalyst. Since the esterification reaction removes water, the reaction is generally performed at a reaction temperature of about 150 to 250 ° C. In general, the reaction is performed under normal pressure or reduced pressure.
- the polyol component can be produced also by conducting a transesterification reaction in the presence of a transesterification catalyst. In the transesterification reaction, alcohol is removed, so that the reaction is generally performed at a reaction temperature of about 120 to 230 ° C. In general, the reaction is performed under normal pressure or reduced pressure.
- an acid other than hydrogenated dimer acid can be used as necessary as long as the physical properties are not impaired.
- the hydrogenated dimer acid is preferably used in an amount of 80% by mass or more, more preferably 90% by mass or more based on the total amount of the acid component as a raw material for the polyester polyol.
- polyols other than hydrogenated dimer diol can be used as a raw material of the polyester polyol as needed, as long as the physical properties are not impaired.
- the hydrogenated dimer diol is preferably used in an amount of 80% by mass or more, more preferably 90% by mass or more based on the total amount of the polyol component as a raw material for the polyester polyol.
- component (a) when component (a) is synthesized, 8 parts by mass of the hydrogenated dimer diol remains in 100 parts by mass of the synthesized product, and 5 parts by mass of the hydrogenated dimer diol is further added to the present invention (I When the urethane (meth) acrylate is produced, the component (a) is not included in the component (a) and the raw material hydrogenated dimer diol remaining during the synthesis and the hydrogenated dimer diol added thereafter are not included in the component (a). means.
- the urethane (meth) acrylate of the present invention (I) is a component (a) (that is, a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol, as long as the physical properties are not impaired.
- Polyols other than (polyester polyols) can be used. Examples of polyols other than these components (a) include hydrogenated dimer diol (chain-like), 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentane.
- Examples of commercially available (poly) carbonate diols include trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, manufactured by Daicel Chemical Co., Ltd., and Kuraray Co., Ltd. Trade name Kuraray Polyol C-590, C-1065N, C-1015N, C-2015N, etc. manufactured by the same company may be mentioned.
- hydrogenated dimer diol chain-like
- 2-methyl-1,8-octanediol 1 to maintain electrical insulation performance high and maintain viscosity relatively low
- 9-nonanediol 2-ethyl-2-butyl-1,3-propanediol
- 2,4-diethyl-1,5-pentanediol 1,10-decanediol, 1,12-dodecanediol, etc.
- a chain aliphatic diol having 9 or more carbon atoms having 9 or more carbon atoms, a hydrogenated dimer diol (having an alicyclic structure), an ⁇ , ⁇ -poly (1,6-hexylene carbonate) diol, an ⁇ , ⁇ -poly ( 3-methyl-1,5-pentylene carbonate) diol, ⁇ , ⁇ -poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, ⁇ , ⁇ - It has a structural unit derived from a chain aliphatic polyol having 6 or more carbon atoms of (poly) carbonate diol such as poly [(1,9-nonylene: 2-methyl-1,8-octylene) carbonate] diol (poly ) Carbonate diol.
- (poly) carbonate of (poly) carbonate diol in the present specification means that the molecule has one or more carbonate bonds. Therefore, “(poly) carbonate diol” means a compound having at least one carbonate bond and two alcoholic hydroxyl groups in the molecule.
- Component (b) which is an essential raw material component of the urethane (meth) acrylate of the present invention (I) is a polyisocyanate compound.
- Component (b) is a compound having two or more isocyanato groups (—NCO).
- 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. , It may be used in combination of these alone, or two
- Component (c) which is an essential raw material component of the urethane (meth) acrylate of the present invention (I) is a hydroxyl group-containing (meth) acrylate.
- the “hydroxyl group-containing (meth) acrylate” is not particularly limited as long as it is a (meth) acrylate having a hydroxyl group in the molecule.
- 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 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, etc. Door can be.
- 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl are preferable.
- 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.
- urethane (meth) acrylate of the present invention hydrogenated dimer acid and hydrogenated dimer diol are used in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate.
- a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate.
- Synthesis can be performed by reacting the polyester polyol, polyisocyanate compound, and hydroxyl group-containing (meth) acrylate contained as a copolymerization component.
- the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time.
- the amount used contains hydrogenated dimer acid and hydrogenated dimer diol as copolymer components.
- the total amount of polyester polyol, polyisocyanate compound and hydroxyl group-containing (meth) acrylate is preferably 0.001 to 1 part by mass.
- the urethanization catalyst catalyzes a hydrolysis reaction of the alkoxysilyl group when the moisture-proof insulating coating of the present invention (II) described later contains an alkoxysilyl group.
- Parts and more preferably 0.005 to 0.15 parts by mass.
- the amount is less than 0.001 part by mass, the effect of adding a catalyst is hardly exhibited, and when it is used more than 1 part by mass, the physical property value at the time of actual use as a cured film is adversely affected as described above. There is.
- Polyester polyol having a structural unit derived from hydrogenated dimer acid and a structural unit derived from hydrogenated dimer diol at 140 ° C., preferably 60 ° C. to 120 ° C., and if necessary, a polyol component other than this polyester polyol Are sequentially added, and then these are reacted at a temperature in the reactor of 50 to 160 ° C., preferably 60 to 140 ° C. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C.
- the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
- Charge molar ratio of raw materials that is, (the number of hydroxyl groups in the polyester polyol having a structural unit derived from hydrogenated dimer acid and a structural unit derived from hydrogenated dimer diol and a polyol component other than this polyester polyol) / ( The number of isocyanate groups in the polyisocyanate compound / (number of hydroxyl groups in the hydroxyl group-containing (meth) acrylate)) is adjusted according to the molecular weight of the target polyurethane.
- the number of isocyanate groups in the polyisocyanate compound is greater than the number of hydroxyl groups in the polyester polyol having a structural unit derived from hydrogenated dimer acid and a structural unit derived from hydrogenated dimer diol, and the polyol component other than this polyester polyol. Need to be more.
- the feed molar ratio of the raw material is not particularly limited, and the polyester polyol having the number of isocyanate groups in the polyisocyanate compound, the structural unit derived from the hydrogenated dimer acid, and the structural unit derived from the hydrogenated dimer diol, and
- the ratio of the total number of hydroxyl groups in the polyol component other than the polyester polyol is preferably in the range of 4: 1 to 1.5: 1.
- this ratio is larger than 4: 1, the abundance of structural units derived from hydrogenated dimer acid or structural units of hydrogenated dimer diol is reduced, which may be undesirable in terms of moisture resistance and electrical insulation reliability.
- it is smaller than 1.4: 1 the molecular weight becomes too large, and when used in the moisture-proof insulating paint of the present invention (II) described later, the viscosity may become too high.
- an acryloyl group-containing urethane compound having no structural unit derived from a hydrogenated dimer acid and no structural unit derived from a hydrogenated dimer diol is also produced.
- the acryloyl group-containing urethane compound having no structural unit derived from the hydrogenated dimer acid and no structural unit derived from the hydrogenated dimer diol is the urethane (meta) of the present invention (I). ) It is defined not to be contained in acrylate.
- a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol an organic polyisocyanate compound
- the urethane (meth) acrylate of the present invention (I) is produced using 1,3-bis (isocyanatomethyl) cyclohexane as the hydroxy group and 2-hydroxyethyl acrylate as the hydroxyl group-containing (meth) acrylate
- the hydrogenated dimer diol A compound of formula (6) which is an acryloyl group-containing urethane compound having no structural unit derived from is also produced.
- the compound of the formula (6) does not have a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. It means not contained in (meth) acrylate.
- the present invention (II) is a moisture-proof insulating paint having the following components (1) and (2) as essential components.
- Component (1) Urethane (meth) acrylate of the present invention
- Component (2) (meth) acryloyl group-containing compound containing no silicon atom
- Component (1) of the moisture-proof insulating paint of the present invention (II) is the above-described urethane (meth) acrylate of the present invention (I).
- Component (2) is a (meth) acryloyl group-containing compound that does not contain a silicon atom in the structural formula, is preferably liquid at room temperature, and has a viscosity at 25 ° C. of 1 Pa ⁇ s or less. It is preferable in terms of dispersibility improvement in the moisture-proof insulating paint and ease of application of the moisture-proof insulating paint.
- the (meth) acryloyl group containing compound which does not contain a silicon atom means that the silane coupling agent of the below-mentioned component (3) is not included. Examples of the component (2) include the following compounds.
- (meth) acryloyl group-containing compounds having a cyclic ether group such as glycidyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl Acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, di Cyclopentanylethyl methacrylate, 4-tert-butyl Monofunctional (meth) acrylo
- cyclohexyl acrylate isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxy.
- Monofunctional (meth) acryloyl groups having cyclic aliphatic groups such as ethyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate Containing compounds, lauryl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert Monofunctional (meth) having a chain aliphatic group such as butyl acrylate, isooctyl acrylate, isoamyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, iso
- the content of component (1) in the moisture-proof insulating paint of the present invention (II) is preferably 25 to 70% by mass, more preferably 30 to 60% by mass, based on the total polymerizable components. More preferably, it is 30 to 55% by mass.
- the content of the component (1) is less than 25% by mass with respect to the total polymerizable component, the moisture-proof performance of the photocurable moisture-proof insulating coating may be deteriorated, which is not preferable.
- the content of the component (1) is more than 70% by mass relative to the total polymerizable component, the viscosity of the photocurable moisture-proof insulating coating becomes too high, which is not preferable for handling.
- the content of the component (2) in the moisture-proof insulating paint of the present invention (II) is preferably 30 to 75% by mass, more preferably 40 to 70% by mass with respect to the total polymerizable components. More preferably, it is 45 to 70% by mass. If the content of the component (2) is more than 75% by mass with respect to the total polymerizable component, the moisture-proof performance of the photocurable moisture-proof insulating coating may be lowered, which is not preferable. Moreover, when content of a component (2) will be less than 30 mass% with respect to all the polymerizable components, the viscosity of a photocurable moisture-proof insulating coating material will become high too much, and it cannot be said that it is preferable on handling.
- a silicon atom having a chain aliphatic hydrocarbon group having 9 or more carbon atoms such as lauryl acrylate, isononyl acrylate, lauryl methacrylate, isononyl methacrylate, etc.
- a polymerization inhibitor may be added in order to increase storage stability and is preferable.
- the polymerization inhibitor is not particularly limited.
- the polymerization inhibitor is preferably added in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of all polymerizable components.
- polymerizable component described in the present specification means a compound that can be polymerized by radical polymerization, and the “total polymerizable component” means the total amount of the polymerizable component. Both component (1) and component (2) are included in the polymerizable component.
- the moisture-proof insulating paint of the present invention (II) further contains a silane coupling agent (hereinafter referred to as “component (3)”) for the purpose of imparting adhesion to glass, metal or metal oxide. It is possible.
- Component (3) is an organosilicon compound having a functional group reactively bonded to an organic material and a functional group reactively bonded to an inorganic material in the molecule, and the structure is generally represented by the formula (7).
- Y is a functional group reactively bonded to an organic material, and representative examples thereof include a vinyl group, an epoxy group, an amino group, a substituted amino group, a (meth) acryloyl group, a mercapto group, and the like.
- X is a functional group that reacts with an inorganic material and is hydrolyzed by water or moisture to produce silanol. This silanol reacts with the inorganic material.
- Representative examples of X include an alkoxy group, an acetoxy group, a chloro atom, and the like.
- R 10 is a divalent organic group, and R 11 represents an alkyl group.
- i represents an integer of 1 to 3
- silane coupling agent examples include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldi Toxisilane, 3-methacryloyloxyprop
- Y is a compound having reactivity with the component (1), and among them, p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltri Ethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacrylic Iloxypropylmethyldiethoxysilane is preferred, and more preferably 3-acryloyloxypropyl
- the component (3) is preferably in the range of 0.01 to 8 parts by mass, more preferably 0 to 100 parts by mass of the total polymerizable component in the moisture-proof insulating paint of the present invention (II).
- the range is from 1 to 5 parts by mass. In the case of less than 0.01 part by mass with respect to 100 parts by mass of all polymerizable components in the moisture-proof insulating paint of the present invention (II), adhesion to glass, metal or metal oxide may not be sufficiently exhibited. It is not preferable.
- the moisture-proof insulating paint of the present invention (II) can further contain a tackifier (component (4)) for the purpose of imparting adhesion to the substrate.
- the tackifier used in the present invention (II) is a substance that is added to urethane acrylate or a polymer compound to give an adhesive function, and is a compound in an oligomer region having a molecular weight of several hundred to several thousand.
- those having the property of not exhibiting rubber elasticity by themselves in a glass state at room temperature are preferable.
- tackifier (4) petroleum resin tackifier, terpene resin tackifier, rosin resin tackifier, coumarone indene resin tackifier, styrene resin tackifier, etc. are used. Can do.
- Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product.
- the synthetic petroleum resin may be C5 or C9.
- terpene resin tackifier examples include ⁇ -pinene resin, ⁇ -pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. Many of these terpene resins are resins having no polar group. Rosin resin tackifiers include rosins such as gum rosin, tall oil rosin, wood rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as maleated rosin; rosin glycerin ester, hydrogenated rosin ester, water Examples thereof include rosin esters such as rosin glycerol ester. These rosin resins have polar groups.
- tackifiers can be used alone or in combination of two or more.
- it preferably contains at least one petroleum resin tackifier and a terpene resin tackifier, and more preferably at least one petroleum resin tackifier. It contains the agent.
- the total amount of component (4) is 0.1 to 35 parts by mass with respect to 100 parts by mass of all polymerizable components.
- the total amount of the component (4) is less than 0.1 parts by mass with respect to 100 parts by mass of the total polymerizable component, it is not preferable that the effect of adding the tackifier is hardly expressed.
- the total amount of component (4) is more than 35 parts by mass with respect to 100 parts by mass of all polymerizable components, the moisture-proof insulating paint of the present invention (II) may become cloudy or the viscosity may become too high. This is not desirable because of its properties.
- the moisture-proof insulating paint of the present invention (II) can and preferably contains a photopolymerization initiator (component (5)).
- component (5) which is an essential component of the moisture-proof insulating paint of the present invention (II), is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays. There is no particular limitation.
- photopolymerization initiator examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane.
- bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzo
- a metallocene compound can be used as a photopolymerization initiator.
- the metallocene compound the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound,
- An example is bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.
- photopolymerization initiators can be used alone or in combination of two or more.
- a preferable photopolymerization initiator used in the present invention is a compound represented by the formula (1).
- R 1 represents H or CH 3.
- the compound represented by the formula (1) is, for example, when R 1 is H, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and R 1 is methyl In the case of a group, it is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.
- the content of the component (5) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the total photopolymerizable component. These photopolymerization initiators may be used alone or in combination of two or more. When the content of the component (5) is less than 0.1 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, it is not preferable because the photopolymerization initiation performance is hardly expressed. Moreover, when content of a component (5) becomes more than 10 mass parts with respect to 100 mass parts of all photopolymerizable components, it may have a bad influence on the physical property of hardened
- a radical chain transfer agent can be used for the moisture-proof insulating paint of this invention (II) as needed.
- a radical chain transfer agent a compound that has a function of reactivating a polymerization active species trapped by an inert radical scavenger such as oxygen and contributes to an improvement in surface curability can be used without limitation.
- Examples of the compound serving as a chain transfer agent include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N -Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl -4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di ( 2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-
- the content thereof is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable component.
- radical chain transfer agents may be used alone or in combination of two or more.
- the moisture-proof insulating paint of the present invention (II) preferably has a viscosity at 25 ° C. of 2000 mPa ⁇ s or less. More preferably, the viscosity at 25 ° C. is 1600 mPa ⁇ s or less.
- the viscosity at 25 ° C. is higher than 2000 mPa ⁇ s, when the curable composition is applied by a drawing application method using a dispenser, the spread after application is suppressed, and as a result, the thickness after curing is more than necessary. May be higher.
- a filler, a modifier, an antifoaming agent, a colorant, and the like can be added as necessary within a range that does not adversely affect fluidity and photocurability. .
- filler examples include fine powder silicon oxide, magnesium oxide, aluminum hydroxide, calcium carbonate and the like.
- the modifier examples include a leveling agent for improving leveling properties.
- a leveling agent for example, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, etc. can be used. . These may be used alone or in combination of two or more. 0.01 to 10 parts by mass can be added to 100 parts by mass of all polymerizable components. When the amount is less than 0.01 part by mass, the effect of adding the leveling agent may not be exhibited. On the other hand, when the amount is more than 10 parts by mass, depending on the type of leveling agent used, there is a possibility of surface tack or deterioration of electrical insulation characteristics.
- the antifoaming agent is not particularly limited as long as it literally has an action of eliminating or suppressing bubbles generated or remaining when the moisture-proof insulating coating of the present invention (II) is applied.
- antifoaming agents used in the moisture-proof insulating coating of the present invention (II) include known antifoaming agents such as silicone oils, fluorine-containing compounds, polycarboxylic acid compounds, polybutadiene compounds, and acetylenic diol compounds. .
- Specific examples thereof include, for example, BYK-077 (manufactured by Big Chemie Japan Co., Ltd.), SN deformer 470 (manufactured by San Nopco Co., Ltd.), TSA750S (manufactured by Momentive Performance Materials LLC), silicone oil SH-203 (Toray Industries, Inc.) -Silicone defoaming agents such as Dow Corning Co., Ltd., Dappo SN-348 (San Nopco Co., Ltd.), Dappo SN-354 (San Nopco Co., Ltd.), Dappo SN-368 (San Nopco Co., Ltd.), Disparon 230HF Acetylendiols such as acrylic polymer antifoaming agents (manufactured by Enomoto Kasei Co., Ltd.), Surfynol DF-110D (Nisshin Chemical Industry Co., Ltd.), Surfynol DF-37 (Nisshin Chemical Industry Co., Ltd.
- Defoaming agent fluorine-containing silicon such as FA-630 Emissions-based anti-foaming agents, and the like can be mentioned. These may be used alone or in combination of two or more. Usually, 0.001 to 5 parts by mass can be added to 100 parts by mass of all polymerizable components. If the amount is less than 0.01 parts by mass, the effect of adding the antifoaming agent may not be exhibited. On the other hand, when the amount is more than 5 parts by mass, depending on the type of antifoaming agent to be used, surface tack may occur or electrical insulation characteristics may be deteriorated.
- colorant examples include known inorganic pigments, organic pigments, organic dyes, and the like, and each is blended according to a desired color tone. These may be used alone or in combination of two or more.
- the present invention (III) is an electronic component which has been insulated using the moisture-proof insulating paint of the present invention (II).
- the electronic component include a microcomputer, a transistor, a capacitor, a resistor, a relay, a transformer, and a mounting circuit board on which these are mounted, and also includes a lead wire, a harness, a film substrate, and the like that are joined to these electronic components. be able to.
- the signal input part of flat panel display panels such as a liquid crystal display panel, a plasma display panel, an organic electroluminescent panel, and a field emission display panel, are also mentioned as an electronic component.
- a moisture-proof insulating paint can be preferably used for the peripheral part of an IC such as a display substrate for electronic parts or a panel bonding part.
- the electronic component of the present invention (III) can be produced by applying the moisture-proof insulating paint of the present invention (II) to the electronic component, and then curing the applied moisture-proof insulating paint to insulate it.
- the above-mentioned moisture-proof insulating paint is applied to the electronic component by a generally known method such as a dipping method, a brush coating method, a spray method, or a drawing method. Apply to.
- an electronic component is obtained by irradiating ultraviolet rays using a high-pressure mercury lamp, a metal halide lamp, an LED or the like as a light source and curing the coating film of the moisture-proof insulating coating applied to the electronic component.
- moisture-proof insulating paint is applied to IC peripheral parts and panel bonding parts such as display panel substrates for electronic parts with a dispenser device, etc., and uses a lamp-type and LED-type UV irradiation device to irradiate a necessary amount of ultraviolet rays. And then cured.
- Example 1 In a reaction vessel equipped with a stirrer and a water separator, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5% by mass) 27.00 g, EMPOL (registered trademark) 1008 (hydrogenated by BASF) Dimer acid, hydrogenated dimer acid purity 92.0%) 17.10 g, Neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) 0.01 g were charged, and condensed water was allowed to flow out at about 240 ° C. under normal pressure.
- polyester polyol A a mixture of a polyester polyol and a hydrogenated dimer diol belonging to component (a) , Described as “polyester polyol A”).
- Example 2 In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, polyester polyol A 45.00 g, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5% by mass) 17.94 g Nonion (registered trademark) L-2 (polyethylene glycol monolaurate manufactured by NOF Corporation), Irganox (registered trademark) 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-) manufactured by BASF 4-hydroxyphenyl)] propionate) 0.12 g, neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) and polyisocyanate compound belonging to component (b), VESTANAT® H12MDI (Evo Kkudegusa
- composition b contains 14.5 mass% of compounds represented by Formula (8).
- composition c contains 14.8 mass% of compounds represented by Formula (9).
- Example 4 In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, polyester polyol A 45.00 g, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5% by mass) 17.94 g Nonion (registered trademark) L-2 (polyethylene glycol monolaurate manufactured by NOF Corporation), Irganox (registered trademark) 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-) manufactured by BASF 4-hydroxyphenyl)] propionate) 0.12 g, neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) and polyisocyanate compound belonging to component (b), Cosmonate (registered trademark) NBDI ( Mitsui
- composition d contains 14.6 mass% of compounds represented by Formula (10).
- polyester polyol E a polyester polyol having a hydroxyl value of 56 mgKOH / g and a number average molecular weight of 2000
- urethane acrylate F urethane acrylate
- Example formulation 1 10.00 g of the composition b, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 11.00 g, 3.75 g of Blemmer LA (lauryl acrylate manufactured by NOF Corporation), A-DCP (Shin Nakamura Chemical Co., Ltd.) 0.25 g of tricyclodecane diacrylate) and Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.69 g as a photopolymerization initiator, As an antifoaming agent, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) (0.06 g) was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable moisture-proof insulating paint B1.
- Example of formulation 2 10.00 g of the composition b, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 11.00 g, 3.75 g of Blemmer LA (lauryl acrylate manufactured by NOF Corporation), A-DCP (Shin Nakamura Chemical Co., Ltd.) 0.25 g of tricyclodecane diacrylate) and Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.69 g as a photopolymerization initiator, DISPARON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) 0.06 g as an antifoaming agent and 0.03 g of methacryloyloxypropyltrimethoxysilane as a silane coupling agent (Made by rotation / revolution mixer). This blend was designated as a photoplastic solvent
- Example formulation 3 10.00 g of the composition b, IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 11.00 g, 3.75 g of Blemmer LA (lauryl acrylate manufactured by NOF Corporation), A-DCP (Shin Nakamura Chemical Co., Ltd.) 0.25 g of tricyclodecane diacrylate) and Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.69 g as a photopolymerization initiator, Narataro Awatori 0.06g DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent and 1.00g Imabu S-110 (hydrogenated petroleum resin manufactured by Idemitsu Kosan Co., Ltd.) as a tackifier Mixing was performed using
- Example formulation 4 10.00 g of the composition c, 11.00 g of IBXA (Osaka Organic Chemical Co., Ltd. isobornyl acrylate), 3.75 g of Blemmer LA (lauryl acrylate manufactured by NOF Corporation), A-DCP (Shin Nakamura Chemical Co., Ltd.) 0.25 g of tricyclodecane diacrylate) and Irgacure (registered trademark) 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.69 g as a photopolymerization initiator, As an antifoaming agent, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) (0.06 g) was mixed using Awatori Rentaro ARE-310 (Sinky Co., Ltd. rotation / revolution mixer). This blend was designated as a photocurable moisture-proof insulating paint C1.
- Example formulation 5 9.25 g of the composition d, IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 12.00 g, 3.75 g of Blemmer LA (lauryl acrylate manufactured by NOF CORPORATION), and Irgacure (registered trademark) as a photopolymerization initiator 369 (BASF 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.69 g, DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent 0.06 g was mixed using Awatori Rentaro ARE-310 (Sinky Corporation rotation / revolution mixer). This blend was designated as a photocurable moisture-proof insulating paint D1. The viscosity of the photocurable moisture-proof insulating coating material D1 at 25 ° C. was 290 mPa ⁇
- Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 manufactured by BASF) was added and stirred and dissolved to obtain a photocurable composition.
- 3.00 g of Y-5187 ( ⁇ -isocyanatopropylmethoxysilane manufactured by Momentive Performance Materials Japan GK) was added and stirred and dissolved.
- 0.50 g of TSA750S (Momentive Performance Materials antifoaming agent) was added and mixed using a spatula, and this composition was designated as a photocurable composition F1.
- TEAI-1000 (acrylic modified hydrogenated polybutadiene resin manufactured by Nippon Soda Co., Ltd., number average molecular weight: about 1000, hydrogenation rate: 97%) 50.00 g and BP-4PA (manufactured by Kyoeisha Chemical Co., Ltd.) were added to this solution.
- 10.00 g of bisphenol A propylene glycol adduct diacrylate) and 5.00 g of Y-5187 ( ⁇ -isocyanatopropylmethoxysilane manufactured by Momentive Performance Materials Japan GK) were added and stirred at 90 ° C. for 140 minutes. .
- 0.50 g of TSA750S (Momentive Performance Materials antifoaming agent) was added and mixed using a spatula to make this composition a photocurable composition F2.
- the viscosity was measured by the following method. Using a sample of 10 mL, using a viscometer (manufactured by Brookfield, model: DV-II + Pro), using a small sample adapter and a spindle of model number C4-31, at a temperature of 25.0 ° C. and a rotation speed of 20 rpm The value when the viscosity became almost constant was measured.
- the adhesion to glass was evaluated by the following method.
- Photocurable moisture-proof insulating coatings B1 to B3, C1 and D1 and photocurable compositions E1 to E2 and F1 to F2 were applied on glass so that the thickness after drying was 150 ⁇ m, and a high pressure mercury lamp was used.
- a conveyor type ultraviolet irradiation device manufactured by GS Yuasa Lighting Co., Ltd., trade name: CSN2-40
- the irradiation amount is 1500 mJ / cm 2 ( The film was cured by irradiation with ultraviolet rays under the condition of 365 nm), heated at 50 ° C. for 6 hours, and then allowed to stand at room temperature for 12 hours. About these coating films, only the end of the cured film for evaluation tests was peeled off, and a test piece for measuring adhesive strength having a width of 2.5 mm was produced.
- the adhesive force is fixed to a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE) so that the cured film peeled off from the polyimide film forms an angle of 180 degrees, the initial chuck distance is 10 mm, and 23 ° C. was measured by measuring 180 degree peeling strength at a speed of 50 mm / min. The results are shown in Table 1.
- a substrate having a fine comb pattern shape described in JPCA-ET01, manufactured by etching a flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd., grade name: Esperflex, copper thickness: 8 ⁇ m, polyimide thickness: 38 ⁇ m) (Copper wiring width / copper wiring width 15 ⁇ m / 15 ⁇ m) on a flexible wiring board subjected to tin plating, photocurable moisture-proof insulating coatings B1 to B3, C1, D1 and photocurable compositions E1 to E2, F1 to F2 was applied to a thickness of 150 ⁇ m after drying, and using a conveyor type ultraviolet irradiation device (trade name: CSN2-40, manufactured by GS Yuasa Lighting Co., Ltd.) using a high-pressure mercury lamp, an irradiation amount of 1500 mJ / cm 2 and then cured by irradiation with
- Photo-curable moisture-proof insulating paints B1 to B3, C1 and D1 and photocurable compositions E1 to E2 are formed on a patterned electrode in which a comb-pattern-shaped ITO wiring having a line / space of 40 ⁇ m / 10 ⁇ m is formed on a glass substrate.
- F1 to F2 were each applied to a thickness of 150 ⁇ m after drying, and the amount of irradiation was measured using a conveyor type ultraviolet irradiation device (trade name: CSN2-40, manufactured by GS Yuasa Lighting Co., Ltd.) using a high-pressure mercury lamp.
- the photocurable moisture-proof insulating coatings B1 to B3, C1, and D1 have good adhesion to glass and polyimide and have high long-term insulation reliability.
- the photocurable compositions E1 to E2 have extremely low long-term insulation reliability.
- the photocurable compositions F1 to F2 have remarkably low adhesion strength to polyimide.
- the photocurable moisture-proof insulating paints B1 to B3, C1, and D1 have a viscosity suitable for application using a dispenser, the handling property is also good.
- the photocurable moisture-proof insulating paint of the present invention (II) produced using the urethane (meth) acrylate of the present invention (I) has good handling properties, and the photocurable moisture-proof insulating paint is cured.
- the cured film Compared with a cured film obtained by curing a photocurable composition produced from an existing urethane (meth) acrylate, the cured film has not only good adhesion to glass and polyimide, but also at a high level. The long-term insulation reliability was revealed.
- the photo-curable moisture-proof insulating paint of the present invention (II) manufactured using the urethane (meth) acrylate of the present invention (I) has a low environmental load, high long-term insulation reliability, and is sufficient for the substrate material. Have good adhesion.
- the electronic component characterized in that it is insulated using the moisture-proof insulating paint of the present invention (II) of the present invention (III) has high reliability, and is mounted on a circuit board mounted with a microcomputer and various components. Useful.
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Abstract
Description
しかしなから、特許文献1には、水添ダイマージオールおよび水添ダイマー酸から誘導されたポリエステルポリオール構造単位を有するウレタン(メタ)アクリレートに関する記載はない。
しかしなから、特許文献2には、水添ダイマージオールおよび水添ダイマー酸から誘導されたポリエステルポリオール構造単位を有するウレタン(メタ)アクリレートに関する記載はない。
しかしなから、特許文献3には、ジエチレングリコールとダイマー酸から誘導されたポリエステルポリオール構造単位を有するウレタン(メタ)アクリレートに関する記載があるのみで、水添ダイマージオールおよび水添ダイマー酸から誘導されたポリエステルポリオール構造単位を有するウレタン(メタ)アクリレートに関する記載はない。
しかし、これらの防湿絶縁塗料は、塗装の際に大気中に有機溶剤が排出されるため、大気汚染の原因となっており、また、これらの有機溶剤が火災を引き起こす危険性も高く、環境への負荷が高いものとなっている。
また、特許文献5および特許文献6で開示されているウレタン(メタ)アクリレート化合物は粘度が高すぎ、2-ヒドロキシエチルアクリレート、イソボルニルアクリレート、ラウリルアクリレートの単官能アクリレートを多量に用いないと希望の粘度に調整できないという問題点があった。
また、本発明は、上記光硬化性防湿絶縁塗料の成分として好適な新規の重合性化合物を提供することを目的とする。
さらに、本発明は、上記実装回路板用の光硬化性防湿絶縁塗料により絶縁処理された信頼性の高い電子部品を提供することを目的とする。
(a)水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオール、
(b)ポリイソシアネート化合物、および
(c)水酸基含有(メタ)アクリレート
を反応させることにより得られるウレタン(メタ)アクリレートに関する。
本発明(II)は、
(1)本発明(I)のウレタン(メタ)アクリレート、および
(2)珪素原子を含まない(メタ)アクリロイル基含有化合物
を含む防湿絶縁塗料に関する。
本発明(III)は、本発明(II)の防湿絶縁塗料を用いて絶縁処理された電子部品に関する。
[1] (a)水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオール、
(b)ポリイソシアネート化合物、および
(c)水酸基含有(メタ)アクリレート
を反応させることにより得られるウレタン(メタ)アクリレート。
[2] ポリエステルポリオール(a)が、水添ダイマー酸から誘導される構造単位を、ポリカルボン酸から誘導される構造単位の総量の80質量%以上含み、かつ水添ダイマージオールから誘導される構造単位を、ポリオールから誘導される構造単位の総量の80質量%以上含むことを特徴とする[1]に記載のウレタン(メタ)アクリレート。
[3] ポリイソシアネート化合物(b)が、ノルボルナンジイソシアネート、イソホロンジイソシアネート、およびメチレンビス(4-シクロヘキシルイソシアネート)からなる群より選ばれる少なくとも1種であることを特徴とする[1]または[2]に記載のウレタン(メタ)アクリレート。
[4] (1)[1]~[3]のいずれか1項に記載のウレタン(メタ)アクリレート、および
(2)珪素原子を含まない(メタ)アクリロイル基含有化合物
を含む防湿絶縁塗料。
[5] さらに、
(3)シランカップリング剤
を含む[4]に記載の防湿絶縁塗料。
[6] さらに、
(4)粘着付与剤
を含む[4]または[5]に記載の防湿絶縁塗料。
[7] さらに、
(5)光重合開始剤
を含む[4]~[6]のいずれか1つに記載の防湿絶縁塗料。
[8] 珪素原子を含まない(メタ)アクリロイル基含有化合物(2)の総量に対して、炭素数9以上の鎖状脂肪族炭化水素基を有する、珪素原子を含まない(メタ)アクリロイル基含有化合物と、炭素数9以上の環状脂肪族炭化水素基を有する、珪素原子含まない液状(メタ)アクリロイル基含有化合物の総量が50質量%以上であることを特徴とする[4]~[7]のいずれか1つに記載の防湿絶縁塗料。
[9] 粘着付与剤(4)が石油樹脂系粘着付与剤を含むことを特徴とする[6]~[8]のいずれか1つに記載の防湿絶縁塗料。
[10] 光重合開始剤(5)が、式(1)
で表される化合物であることを特徴とする[7]~[9]のいずれか1つに記載の防湿絶縁塗料。
[11] 珪素原子を含まない(メタ)アクリロイル基含有化合物(2)を、全重合性成分に対して、30~75質量%含有する[4]~[10]のいずれか1つに記載の防湿絶縁塗料。
[12] シランカップリング剤(3)を、全重合性成分100質量部に対して、0.01~8質量部含有する[5]~[11]のいずれか1つに記載の防湿絶縁塗料。
[13] 粘着付与剤(4)を、全重合性成分100質量部に対して、0.1~35質量部含有する[6]~[12]のいずれか1つに記載の防湿絶縁塗料。
[14] 光重合開始剤(5)を、全重合性成分100質量部に対して、0.1~10質量部含有する[7]~[13]のいずれか1つに記載の防湿絶縁塗料。
[15] 25℃の粘度が2000mPa・s以下であることを特徴とする[4]~[14]のいずれか1つに記載の防湿絶縁塗料。
[16] [4]~[15]のいずれか1つに記載の防湿絶縁塗料を用いて絶縁処理された電子部品。
なお、本明細書における「(メタ)アクリロイル基」とは、アクリロイル基および/またはメタクリロイル基を意味する。
本発明(I)は、下記成分(a)~(c)を反応させることにより得られるウレタン(メタ)アクリレートである。
成分(a):水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオール
成分(b):ポリイソシアネート化合物
成分(c):水酸基含有(メタ)アクリレート
本発明(I)のウレタン(メタ)アクリレートの必須原料成分である成分(a)は、水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオールである。
上記ダイマー酸として、例えばリノール酸とリノール酸もしくはオレイン酸とから製造される炭素数36のダイマー酸を原料として用いた場合には、水添ダイマー酸の主成分の構造は、以下の式(2)および式(3)で表される構造である。
例えば、式(2)および式(3)で表される構造の化合物を主成分とする水添ダイマー酸を還元して水添ダイマージオールを製造した場合には、水添ダイマージオールの主成分の構造は、以下の式(4)および式(5)で表される構造である。
上記エステル化反応は、水を除去するので、150~250℃程度の反応温度で反応を行うことが一般的である。反応時の圧力は、常圧または減圧条件下で反応することが一般的である。
上記エステル交換反応は、アルコールを除去するので、120~230℃程度の反応温度で反応を行うことが一般的である。反応時の圧力は、常圧または減圧条件下で反応することが一般的である。
また、ポリエステルポリオールの原料として、物性を損なわない範囲で、必要に応じて、水添ダイマージオール以外のポリオールを用いることができる。しかし、ポリエステルポリオールの原料としてのポリオール成分全量に対して、水添ダイマージオールが80質量%以上使用されることが好ましく、90質量%以上使用されることがより好ましい。
即ち、水添ダイマージオールと水添ダイマー酸からなるポリエステルポリオール中に、8質量%の水添ダイマージオールが残存している場合、この水添ダイマージオールは成分(a)に含まれないことを意味する。
また、成分(a)中に含まれる水添ダイマージオールの他に新たにダイマージオールを加えて本発明(I)のウレタン(メタ)アクリレートが製造された場合、この加えられたダイマージオールも成分(a)に含まれないと定義する。
即ち、成分(a)を合成した際に、合成品100質量部中に8質量部の原料である水添ダイマージオールが残存し、さらに、水添ダイマージオール5質量部を加えて本発明(I)のウレタン(メタ)アクリレートが製造された場合、成分(a)を合成の際に残存した原料水添ダイマージオール、およびその後加えた水添ダイマージオールもともに成分(a)に含まれないことを意味する。
本発明(I)のウレタン(メタ)アクリレートの必須原料成分である成分(b)は、ポリイソシアネート化合物である。
成分(b)は、イソシアナト基(-NCO)を2個以上有する化合物である。具体的には、例えば、1,4-シクロヘキサンジイソシアネート、イソホロンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,4-ビス(イソシアナトメチル)シクロヘキサン、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、ジフェニルメタン-4,4′-ジイソシアネート、1,3-キシリレンジイソシアネート、1,4-キシリレンジイソシアネート、リシントリイソシアネート、リシンジイソシアネート、ヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサンメチレンジイソシアネートおよびノルボルナンジイソシアネート等を挙げることができ、これらを単独で、または2種以上組合せて使用することができる。
本発明(I)のウレタン(メタ)アクリレートの必須原料成分である成分(c)は、水酸基含有(メタ)アクリレートである。「水酸基含有(メタ)アクリレート」とは、分子中に水酸基を有する(メタ)アクリレートであれば特に制限はない。具体的には、例えば、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、3-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルアクリレート、2-ヒドロキシエチルアクリルアミド、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルメタクリレート、3-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、2-ヒドロキシ-3-フェノキシプロピルメタクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルメタクリレート等を挙げることができる。
この比が4:1よりも大きくなると、水添ダイマー酸から誘導される構造単位や水添ダイマージオールの構造単位の存在率が少なくなり防湿特性や電気絶縁信頼性の面で好ましくない場合を生じることがある。また、1.4:1よりも小さい場合には、分子量が大きくなりすぎ、後述の本発明(II)の防湿絶縁塗料に使用した場合には、粘度が高くなりすぎる場合がある。
本発明(II)は、下記成分(1)および成分(2)を必須成分とする防湿絶縁塗料である。
成分(1):本発明(I)のウレタン(メタ)アクリレート
成分(2):珪素原子を含まない(メタ)アクリロイル基含有化合物
成分(2)は、構造式の中に珪素原子を含まない(メタ)アクリロイル基含有化合物であり、常温で液状であることが好ましく、25℃での粘度が1Pa・s以下であることが、防湿絶縁塗料の中での分散性向上や防湿絶縁塗料の塗工容易性の点で好ましい。また、珪素原子を含まない(メタ)アクリロイル基含有化合物は、後述の成分(3)のシランカップリング剤を含まないことを意味する。
成分(2)としては以下の化合物を挙げることができる。
例えば、グリシジルアクリレート、テトラヒドロフルフリルアクリレート、グリシジルメタクリレート、テトラヒドロフルフリルメタクリレート等の環状エーテル基を有する(メタ)アクリロイル基含有化合物、シクロヘキシルアクリレート、イソボルニルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニルオキシエチルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンタニルエチルアクリレート、4-tert-ブチルシクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、ジシクロペンテニルメタクリレート、ジシクロペンテニルオキシエチルメタクリレート、ジシクロペンタニルメタクリレート、ジシクロペンタニルエチルメタクリレート、4-tert-ブチルシクロヘキシルメタクリレート等の環状脂肪族基を有する単官能(メタ)アクリロイル基含有化合物、ラウリルアクリレート、イソノニルアクリレート、2-エチルヘキシルアクリレート、イソブチルアクリレート、tert-ブチルアクリレート、イソオクチルアクリレート、イソアミルアクリレート、ラウリルメタクリレート、イソノニルメタクリレート、2-エチルヘキシルメタクリレート、イソブチルメタクリレート、tert-ブチルメタクリレート、イソオクチルメタクリレート、イソアミルメタクリレート等の鎖状脂肪族基を有する単官能(メタ)アクリロイル基含有化合物、ベンジルアクリレート、フェノキシエチルアクリレート、ベンジルメタクリレート、フェノキシエチルメタクリレート、2-ヒドロキシ-3-フェノキシプロピルメタクリレート等の芳香環を有する単官能(メタ)アクリロイル基含有化合物を挙げることができる。
なお、この重合禁止剤としては、特に限定されるものではないが、例えば、ヒドロキノン、p-メトキシフェノール、p-ベンゾキノン、ナフトキノン、フェナンスラキノン、トルキノン、2,5-ジアセトキシ-p-ベンゾキノン、2,5-ジカプロキシ-p-ベンゾキノン、2,5-アシロキシ-p-ベンゾキノン、2,5-ジ-tert-ブチル-3-メチルフェノール、p-t-ブチルカテコール、2,5-ジ-t-ブチルヒドロキノン、p-tert-ブチルカテコール、モノ-t-ブチルヒドロキノン、2,5-ジ-t-アミルヒドロキノン、ジ-t-ブチル・パラクレゾールヒドロキノンモノメチルエーテル、アルファナフトール、アセトアミジンアセテート、アセトアミジンサルフェート、フェニルヒドラジン塩酸塩、ヒドラジン塩酸塩、トリメチルベンジルアンモニウムクロライド、ラウリルピリジニウムクロライド、セチルトリメチルアンモニウムクロライド、フェニルトリメチルアンモニウムクロライド、トリメチルベンジルアンモニウムオキザレート、ジ(トリメチルベンジルアンモニウム)オキザレート、トリメチルベンジルアンモニウムマレート、トリメチルベンジルアンモニウムタータレート、トリメチルベンジルアンモニウムグリコレート、フェニル-β-ナフチルアミン、パラベンジルアミノフェノール、ジ-β-ナフチルパラフェニレンジアミン、ジニトロベンゼン、トリニトロトルエン、ピクリン酸、シクロヘキサノンオキシム、ピロガロール、タンニン酸、レゾルシン、トリエチルアミン塩酸塩、ジメチルアニリン塩酸塩およびジブチルアミン塩酸塩等が挙げられる。
これらは単独でも、あるいは2種以上を適宜組み合わせて使用することができる。
これらの中でも、ヒドロキノン、p-メトキシフェノール、p-ベンゾキノン、ナフトキノン、フェナンスラキノン、トルキノン、2,5-ジアセトキシ-p-ベンゾキノン、2,5-ジカプロキシ-p-ベンゾキノン、2,5-アシロキシ-p-ベンゾキノン、p-t-ブチルカテコール、2,5-ジ-t-ブチルヒドロキノン、p-tert-ブチルカテコール、モノ-t-ブチルヒドロキノン、2,5-ジ-t-アミルヒドロキノン、ジ-t-ブチル・パラクレゾールヒドロキノンモノメチルエーテルおよびフェノチアジンが好適に用いられる。
通常、この重合禁止剤は、全重合性成分100質量部に対し、0.01~10質量部添加することが好ましい。
成分(3)は分子内に有機材料と反応結合する官能基、および無機材料と反応結合する官能基を同時に有する有機ケイ素化合物で、一般的にその構造は式(7)のように示される。
本発明(II)に用いられる粘着付与剤とは、ウレタンアクリレートや高分子化合物に配合して粘着機能を持たせるための物質であり、分子量数百~数千のオリゴマー領域の化合物であることが好ましく、室温ではガラス状態でそのもの自体ではゴム弾性を示さない性質を有するものが好ましい。
粘着付与剤(4)としては、一般に、石油系樹脂粘着付与剤、テルペン系樹脂粘着付与剤、ロジン系樹脂粘着付与剤、クマロンインデン樹脂粘着付与剤、スチレン系樹脂粘着付与剤などを用いることができる。
石油系樹脂粘着付与剤としては、脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族-芳香族共重合系石油樹脂、脂環族系石油樹脂、ジシクロペンタジエン樹脂およびこれらの水添物等の変性物が挙げられる。合成石油樹脂は、C5系でも、C9系でもよい。
テルペン系樹脂粘着付与剤としては、β-ピネン樹脂、α-ピネン樹脂、テルペン-フェノール樹脂、芳香族変性テルペン樹脂、水添テルペン樹脂などが挙げられる。これらのテルペン系樹脂の多くは、極性基を有しない樹脂である。
ロジン系樹脂粘着付与剤としては、ガムロジン、トール油ロジン、ウッドロジンなどのロジン;水添ロジン、不均化ロジン、重合ロジン、マレイン化ロジンなどの変性ロジン;ロジングリセリンエステル、水添ロジンエステル、水添ロジングリセリンエステルなどのロジンエステルなどが挙げられる。これらのロジン系樹脂は、極性基を有するものである。
これらの粘着付与剤は、それぞれ単独で、あるいは2種以上を組み合わせて使用することができる。
これらの粘着付与剤の中で、少なくとも1種以上の石油系樹脂粘着付与剤、テルペン系樹脂粘着付与剤を含んでいることが好ましく、さらに、好ましくは、少なくとも1種以上の石油系樹脂粘着付与剤を含んでいることである。
本発明(II)の防湿絶縁塗料の必須成分である成分(5)は、近赤外線、可視光線、紫外線等の光の照射により、ラジカル重合の開始に寄与するラジカルを発生する化合物であれば、特に制限はない。
本発明に使用される光重合開始剤として好ましいものは、式(1)で表される化合物である。
式(1)で表される化合物は、例えば、R1がHの場合には、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-1-ブタノンであり、R1がメチル基の場合には、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノンである。
ラジカル連鎖移動剤としては、酸素等の不活性なラジカル捕捉剤にトラップされた重合活性種を再活性化させる働きを持ち、表面硬化性の向上に寄与する化合物を際限なく使用することができる。連鎖移動剤となる化合物として、例えば、N,N-ジメチルアニリン、N,N-ジメチル-p-トルイジン、N,N-ジメチル-m-トルイジン、N,N-ジエチル-p-トルイジン、N,N-ジメチル-3,5-ジメチルアニリン、N,N-ジメチル-3,4-ジメチルアニリン、N,N-ジメチル-4-エチルアニリン、N,N-ジメチル-4-イソプロピルアニリン、N,N-ジメチル-4-t-ブチルアニリン、N,N-ジメチル-3,5-ジ-t-ブチルアニリン、N,N-ビス(2-ヒドロキシエチル)-3,5-ジメチルアニリン、N,N-ジ(2-ヒドロキシエチル)-p-トルイジン、N,N-ビス(2-ヒドロキシエチル)-3,4-ジメチルアニリン、N,N-ビス(2-ヒドロキシエチル)-4-エチルアニリン、N,N-ビス(2-ヒドロキシエチル)-4-イソプロピルアニリン、N,N-ビス(2-ヒドロキシエチル)-4-t-ブチルアニリン、N,N-ビス(2-ヒドロキシエチル)-3,5-ジ-イソプロピルアニリン、N,N-ビス(2-ヒドロキシエチル)-3,5-ジ-t-ブチルアニリン、4-N,N-ジメチルアミノ安息香酸エチルエステル、4-N,N-ジメチルアミノ安息香酸メチルエステル、N,N-ジメチルアミノ安息香酸n-ブトキシエチルエステル、4-N,N-ジメチルアミノ安息香酸2-(メタクリロイルオキシ)エチルエステル、4-N,N-ジメチルアミノベンゾフェノン、トリメチルアミン、トリエチルアミン、N-メチルジエタノールアミン、N-エチルジエタノールアミン、N-n-ブチルジエタノールアミン、N-ラウリルジエタノールアミン、トリエタノールアミン、2-(ジメチルアミノ)エチルメタクリレート、N-メチルジエタノールアミンジメタクリレート、N-エチルジエタノールアミンジメタクリレート、トリエタノールアミンモノメタクリレート、トリエタノールアミンジメタクリレート、トリエタノールアミントリメタクリレート等が挙げられるが、特に好適なアミン類としては、2-エチルへキシル-4-ジメチルアミノベンゾエートである。
本発明(II)の防湿絶縁塗料に使用される消泡剤としては、シリコーン系オイル、フッ素含有化合物、ポリカルボン酸系化合物、ポリブタジエン系化合物、アセチレンジオール系化合物など公知の消泡剤が挙げられる。その具体例としては、例えば、BYK-077(ビックケミー・ジャパン株式会社製)、SNデフォーマー470(サンノプコ株式会社製)、TSA750S(モメンティブ・パフォーマンス・マテリアルズ合同会社製)、シリコーンオイルSH-203(東レ・ダウコーニング株式会社製)等のシリコーン系消泡剤、ダッポーSN-348(サンノプコ株式会社製)、ダッポーSN-354(サンノプコ株式会社製)、ダッポーSN-368(サンノプコ株式会社製)、ディスパロン230HF(楠本化成株式会社製)等のアクリル重合体系消泡剤、サーフィノールDF-110D(日信化学工業株式会社製)、サーフィノールDF-37(日信化学工業株式会社製)等のアセチレンジオール系消泡剤、FA-630等のフッ素含有シリコーン系消泡剤等を挙げることができる。これらは、単独で使用しても、2種以上組み合わせて使用してもよい。通常、全重合性成分100質量部に対し、0.001~5質量部添加することができる。0.01質量部未満の場合には、消泡剤の添加効果が発現しない可能性がある。また、5質量部より多い場合には、使用する消泡剤の種類によっては、表面タックが生じたり、電気絶縁特性を劣化させる可能性がある。
本発明(III)は、本発明(II)の防湿絶縁塗料を用いて絶縁処理された電子部品である。電子部品としては、マイクロコンピュータ、トランジスタ、コンデンサ、抵抗、リレー、トランス等、およびこれらを搭載した実装回路板などが挙げられ、さらにこれら電子部品に接合されるリード線、ハーネス、フィルム基板等も含むことができる。
また、液晶ディスプレイパネル、プラズマディスプレイパネル、有機エレクトロルミネッセンスパネル、フィールドエミッションディスプレイパネル等のフラットパネルディスプレイパネルの信号入力部等も、電子部品として挙げられる。特に、電子部品用ディスプレイ用基板等のIC周辺部やパネル張り合わせ部等に、防湿絶縁塗料を好ましく使用できる。
本発明(III)の電子部品の具体的な製造方法としては、まず、一般に知られている浸漬法、ハケ塗り法、スプレー法、線引き塗布法等の方法によって上述した防湿絶縁塗料を上記電子部品に塗布する。次に、高圧水銀灯、メタルハライドランプ、LED等を光源として紫外線を照射し、電子部品に塗布した防湿絶縁塗料の塗膜を硬化することにより、電子部品が得られる。特に、防湿絶縁塗料は、電子部品用ディスプレイパネル用基板等のIC周辺部やパネル貼り合せ部にディスペンサー装置等で塗布され、ランプ方式およびLED方式のUV照射装置を用い、必要量の紫外線を照射し硬化させて製造される。
攪拌機、水分離器付き反応容器中にSovermol(登録商標)908(BASF製水添ダイマージオール、水添ダイマージオール純度97.5質量%)27.00g、EMPOL(登録商標)1008(BASF製水添ダイマー酸、水添ダイマー酸純度92.0%)17.10g、ネオスタンU-810(日東化成株式会社製ジオクチル錫ジラウレート)0.01gを仕込み、約240℃、常圧下から始めて縮合水を流出させながら減圧しつつ脱水エステル化反応を行い、水酸基価59mgKOH/g、数平均分子量2000で、水添ダイマージオールを15質量%含む、成分(a)に属するポリエステルポリオールと水添ダイマージオールの混合物(以下、「ポリエステルポリオールA」と記す。)を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、ポリエステルポリオールA45.00g、Sovermol(登録商標)908(BASF製水添ダイマージオール、水添ダイマージオール純度97.5質量%)17.94g、ノニオン(登録商標)L-2(日油株式会社製モノラウリン酸ポリエチレングリコール)0.82g、Irganox(登録商標)1010(BASF製ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)]プロピオネート)0.12g、ネオスタンU-810(日東化成株式会社製ジオクチル錫ジラウレート)0.01gおよび、成分(b)に属するポリイソシアネート化合物として、VESTANAT(登録商標)H12MDI(エボニックデグサ製メチレンビス(4-シクロヘキシルイソシアネート))32.62gを投入し、撹拌しながら、オイルバスを用いて75~80℃に昇温した。その後、2.5時間撹拌しながら反応を継続した。その後、成分(c)に属する水酸基含有(メタ)アクリレートとして、4-HBA(大阪有機化学工業株式会社製4-ヒドロキシブチルアクリレート)20.69gを反応容器内に投入し、撹拌を継続しながら反応容器内の温度が80℃±5℃の範囲に保ったまま、10時間反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認し、反応を終了し、本発明(I)に属するウレタンアクリレート(以下、「ウレタンアクリレートB」と記す。)を含む組成物(以下、「組成物b」と記す。)を得た。なお、この組成物bは、式(8)で表される化合物を14.5質量%含む。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、ポリエステルポリオールA45.00g、Sovermol(登録商標)908(BASF製水添ダイマージオール、水添ダイマージオール純度97.5質量%)17.94g、ノニオン(登録商標)L-2(日油株式会社製モノラウリン酸ポリエチレングリコール)0.82g、Irganox(登録商標)1010(BASF製ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)]プロピオネート)0.12g、ネオスタンU-810(日東化成株式会社製ジオクチル錫ジラウレート)0.01gおよび、成分(b)に属するポリイソシアネート化合物として、VESTANAT(登録商標)IPDI(エボニックデグサ製3-イソシアナトメチル-3,5,5-トリメチルシクロヘキシルイソシアネート)27.64gを投入し、撹拌しながら、オイルバスを用いて75~80℃に昇温した。その後、2.5時間撹拌しながら反応を継続した。その後、成分(c)に属する水酸基含有(メタ)アクリレートとして、4-HBA(大阪有機化学工業株式会社製4-ヒドロキシブチルアクリレート)20.69gを反応容器内に投入し、撹拌を継続しながら反応容器内の温度が80℃±5℃の範囲に保ったまま、10時間反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認し、反応を終了し、本発明(I)に属するウレタンアクリレート(以下、「ウレタンアクリレートC」と記す。)を含む組成物(以下、「組成物c」と記す。)を得た。なお、この組成物cは、式(9)で表される化合物を14.8質量%含む。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、ポリエステルポリオールA45.00g、Sovermol(登録商標)908(BASF製水添ダイマージオール、水添ダイマージオール純度97.5質量%)17.94g、ノニオン(登録商標)L-2(日油株式会社製モノラウリン酸ポリエチレングリコール)0.82g、Irganox(登録商標)1010(BASF製ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)]プロピオネート)0.12g、ネオスタンU-810(日東化成株式会社製ジオクチル錫ジラウレート)0.01gおよび、成分(b)に属するポリイソシアネート化合物として、コスモネート(登録商標)NBDI(三井化学株式会社製2,5(2,6)-ビス(イソシアナトメチル)ジシクロ[2,2,1]ヘプタン)25.64gを投入し、撹拌しながら、オイルバスを用いて75~80℃に昇温した。その後、2.5時間撹拌しながら反応を継続した。その後、成分(c)に属する水酸基含有(メタ)アクリレートとして、4-HBA(大阪有機化学工業株式会社製4-ヒドロキシブチルアクリレート)20.69gを反応容器内に投入し、撹拌を継続しながら反応容器内の温度が80℃±5℃の範囲に保ったまま、10時間反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認し、反応を終了し、本発明(I)に属するウレタンアクリレート(以下、「ウレタンアクリレートD」と記す。)を含む組成物(以下、「組成物d」と記す。)を得た。なお、この組成物dは、式(10)で表される化合物を14.6質量%含む。
攪拌機、水分離器付き反応容器中に1,6-ヘキサンジオール(東京化成工業株式会社製)6.60g、EMPOL(登録商標)1008(BASF製水添ダイマー酸、水添ダイマー酸純度92.0%)25.00g、ラウリン酸(東京化成工業株式会社製)1.25g、ジブチル錫ジラウレート(東京化成工業株式会社製)0.5mgを仕込み、約240℃、常圧下から始めて縮合水を流出させながら減圧しつつ脱水エステル化反応を行い、水酸基価56mgKOH/g、数平均分子量2000のポリエステルポリオール(以下、「ポリエステルポリオールE」と記す。)を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、ポリエステルポリオールE50.00g、Irganox(登録商標)1010(BASF製ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)]プロピオネート)0.05g、ジブチル錫ジラウレート(東京化成工業株式会社製)6mgおよび、デュラネート50M-HDI(旭化成株式会社製ヘキサメチレンジイソシアネート)6.3g、FA-512AS(日立化成工業株式会社製ジシクロペンタジエンオキシエチルアクリレート)59.20gを投入し、撹拌しながら、オイルバスを用いて75~80℃に昇温した。その後、5時間撹拌しながら反応を継続した。その後、HEA(大阪有機化学工業株式会社製2-ヒドロキシエチルアクリレート)2.90g、ハイドロキノンモノメチルエーテル(和光純薬工業株式会社製)0.06g、ジブチル錫ジラウレート(東京化成工業株式会社製)24mgを反応容器内に投入し、撹拌を継続しながら反応容器内の温度が80℃±5℃の範囲に保ったまま、2時間反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認した。その後、Irgacure(登録商標)184(BASF製1-ヒドロキシシクロヘキシルフェニルケトン)3.56g、Irgacure(登録商標)819(BASF製ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド)1.19gを加えて攪拌し、ウレタンアクリレートを含む光硬化性組成物E1を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、TESLAC(登録商標)2470(日立化成ポリマー株式会社製、ジエチレングリコールとダイマー酸を主成分とするポリエステルポリオール)55.00g、ミリオネート(登録商標)MT(日本ポリウレタン製ジフェニルメタンジイソシアネート)12.50gを投入し、窒素雰囲気下で撹拌しながら、オイルバスを用いて110℃に昇温した。その後、2時間撹拌しながら反応を継続した。その後、HEA(大阪有機化学工業株式会社製2-ヒドロキシエチルアクリレート)4.65gを反応容器内に投入し、酸素雰囲気下で撹拌しながら反応容器内の温度を110℃に保ったまま、2時間反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認した。その後、Irgacure(登録商標)184(BASF製1-ヒドロキシシクロヘキシルフェニルケトン)2.15gを加えて攪拌し、ウレタンアクリレートを含む光硬化性組成物E2を得た。
撹拌機、温度計、冷却管および空気ガス導入管を装備した反応容器に空気ガスを導入させた後、HEA(大阪有機化学工業株式会社製2-ヒドロキシエチルアクリレート)53.00g、GI-1000(日本曹達株式会社製水添ポリブタジエンジオール、数平均分子量:約1,500)600.00gおよびヒドロキノンモノメチルエーテル(和光純薬工業株式会社製)0.50gを投入し、オイルバスを用いて70℃に昇温した。その後、攪拌しながら70~75℃で30分間保温し、これに、コロネート(登録商標)T-65(日本ポリウレタン工業株式会社製トリレンジイソシアネート)70.00gを3時間で均一滴下した。滴下完了後、攪拌しながら70~75℃で約5時間保温し、反応を継続した。その後、赤外吸収スペクトルを測定し、イソシアネート基の吸収が消失していることを確認し、反応を終了し、ウレタンアクリレート(以下、ウレタンアクリレートFと記す。)を得た。
前記組成物b10.00g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)11.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)3.75g、A-DCP(新中村化学工業株式会社製トリシクロデカンジアクリレート)0.25gおよび光重合開始剤としてIrgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)0.69g、消泡剤としてDISPALON L-1982N(楠本化成株式会社製アクリル共重合物)0.06gをあわとり錬太郎ARE-310(株式会社シンキー製自転・公転ミキサー)を用いて混合した。この配合物を光硬化性防湿絶縁塗料B1とした。光硬化性防湿絶縁塗料B1の25℃での粘度は600mPa・sであった。
前記組成物b10.00g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)11.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)3.75g、A-DCP(新中村化学工業株式会社製トリシクロデカンジアクリレート)0.25gおよび光重合開始剤としてIrgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)0.69g、消泡剤としてDISPALON L-1982N(楠本化成株式会社製アクリル共重合物)0.06g、シランカップリング剤としてメタクリロイロキシプロピルトリメトキシシラン0.03gをあわとり錬太郎ARE-310(株式会社シンキー製自転・公転ミキサー)を用いて混合した。この配合物を光硬化性防湿絶縁塗料B2とした。光硬化性防湿絶縁塗料B2の25℃での粘度は590mPa・sであった。
前記組成物b10.00g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)11.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)3.75g、A-DCP(新中村化学工業株式会社製トリシクロデカンジアクリレート)0.25gおよび光重合開始剤としてIrgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)0.69g、消泡剤としてDISPALON L-1982N(楠本化成株式会社製アクリル共重合物)0.06g、粘着付与剤としてアイマーブS-110(出光興産株式会社製水添石油樹脂)1.00gをあわとり錬太郎ARE-310(株式会社シンキー製自転・公転ミキサー)を用いて混合した。この配合物を光硬化性防湿絶縁塗料B3とした。光硬化性防湿絶縁塗料B3の25℃での粘度は650mPa・sであった。
前記組成物c10.00g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)11.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)3.75g、A-DCP(新中村化学工業株式会社製トリシクロデカンジアクリレート)0.25gおよび光重合開始剤としてIrgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)0.69g、消泡剤としてDISPALON L-1982N(楠本化成株式会社製アクリル共重合物)0.06gをあわとり錬太郎ARE-310(株式会社シンキー製自転・公転ミキサー)を用いて混合した。この配合物を光硬化性防湿絶縁塗料C1とした。光硬化性防湿絶縁塗料C1の25℃での粘度は500mPa・sであった。
前記組成物d9.25g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)12.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)3.75g、および光重合開始剤としてIrgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)0.69g、消泡剤としてDISPALON L-1982N(楠本化成株式会社製アクリル共重合物)0.06gをあわとり錬太郎ARE-310(株式会社シンキー製自転・公転ミキサー)を用いて混合した。この配合物を光硬化性防湿絶縁塗料D1とした。光硬化性防湿絶縁塗料D1の25℃での粘度は290mPa・sであった。
撹拌機、温度計、冷却管および空気ガス導入管を装備した反応容器に空気ガスを導入させた後、ウレタンアクリレートF40.00g、A-9550(新中村化学工業社製ジペンタエリスリトールヘキサアクリレート)5.00g、IBXA(大阪有機化学工業株式会社製イソボルニルアクリレート)50.00g、ブレンマーLA(日油株式会社製ラウリルアクリレート)5.00gを仕込み、70℃に昇温後、70~75℃で3時間保温し、均一に攪拌・混合させた。さらに、Irgacure(登録商標)369(BASF製2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1)4.00gを加え攪拌・溶解し、光硬化性組成物を得た。さらに、Y-5187(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製γ-イソシアネートプロピルメトキシシラン)3.00gを加え攪拌・溶解した。その後、TSA750S(モメンティブ・パフォーマンス・マテリアルズ社製消泡剤)0.50gを加え、スパチュラを用いて混合し、この配合物を光硬化性組成物F1とした。
撹拌機、温度計、冷却管および空気ガス導入管を装備した反応容器に空気ガスを導入させた後、ブレンマーLA(日油株式会社製ラウリルアクリレート)40.00g、Irgacure(登録商標)651(BASF製ベンジルジメチルケタール)2.50gを投入し、110℃で45分間攪拌して溶解させた。その後、この溶液に、TEAI-1000(日本曹達株式会社製アクリル変性水素添加ポリブタジエン樹脂、数平均分子量:約1000、水素添加率:97%)50.00gと、BP-4PA(共栄社化学株式会社製ビスフェノールAプロピレングリコール付加物ジアクリレート)10.00g、Y-5187(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製γ-イソシアネートプロピルメトキシシラン)5.00gを加え、90℃で140分間攪拌、混合した。その後、TSA750S(モメンティブ・パフォーマンス・マテリアルズ社製消泡剤)0.50gを加え、スパチュラを用いて混合し、この配合物を光硬化性組成物F2とした。
粘度は以下の方法により測定した。
試料10mLを使用して、粘度計(Brookfield社製、型式:DV-II+Pro)を用いて、少量サンプルアダプターおよび型番C4-31のスピンドルを使用し、温度25.0℃、回転数20rpmの条件で粘度がほぼ一定になったときの値を測定した。
ガラスへの密着性は以下の方法により評価した。
光硬化性防湿絶縁塗料B1~B3、C1、D1および光硬化性組成物E1~E2、F1~F2を、それぞれガラス上に乾燥後の厚みが150μmになるよう塗布し、高圧水銀ランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:CSN2-40)を用い、照射量1500mJ/cm2(365nmの値)の条件で紫外線を照射して硬化させ、50℃で6時間加熱後、室温で12時間放置した。これらの塗膜について、評価試験用の硬化膜の一端のみを剥離して、幅2.5mmの接着力測定用試験片を作製した。接着力は、ガラス板と剥離した硬化フィルムが90度の角度を成すように引張り試験機(株式会社島津製作所製、EZ Test/CE)に固定し、最初のチャック間距離を7mmとし、23℃において50mm/minの速度で90度引き剥がし強さを測定して求めた。結果を表1に示す。
ポリイミドフィルムへの密着性は以下の方法により評価した。
光硬化性防湿絶縁塗料B1~B3、C1、D1および光硬化性組成物E1~E2、F1~F2を、それぞれポリイミドフィルム(商品名:カプトン(登録商標)150EN、東レ・デュポン株式会社製)上に乾燥後の厚みが150μmになるよう塗布し、高圧水銀ランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:CSN2-40)を用い、照射量1500mJ/cm2(365nmの値)の条件で紫外線を照射して硬化させ、50℃で6時間加熱後、室温で12時間放置した。これらの塗膜について、評価試験用の硬化膜の一端のみを剥離して、幅2.5mmの接着力測定用試験片を作製した。接着力は、ポリイミドフィルムと剥離した硬化フィルムが180度の角度を成すように引張り試験機(株式会社島津製作所製、EZ Test/CE)に固定し、最初のチャック間距離を10mmとし、23℃において50mm/minの速度で180度引き剥がし強さを測定して求めた。結果を表1に示す。
フレキシブル銅張り積層板(住友金属鉱山株式会社製、グレード名:エスパーフレックス、銅厚:8μm、ポリイミド厚:38μm)をエッチングして製造した、JPCA-ET01に記載の微細くし形パターン形状の基板(銅配線幅/銅配線間幅=15μm/15μm)に錫メッキ処理を施したフレキシブル配線板に、光硬化性防湿絶縁塗料B1~B3、C1、D1および光硬化性組成物E1~E2、F1~F2を、それぞれ乾燥後の厚みが150μmになるよう塗布し、高圧水銀ランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:CSN2-40)を用い、照射量1500mJ/cm2(365nmの値)の条件で紫外線を照射して硬化させ、50℃で6時間加熱後、室温で12時間放置した。
この試験片を用いて、バイアス電圧30Vを印加し、温度85℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG-8600(IMV社製)を用いて行った。上記温湿度定常試験をスタートしてから1000時間後の抵抗値を表1に記す。
ガラス基板上にライン/スペースが40μm/10μmである櫛形パターン形状のITO配線を形成したパターン電極上に、光硬化性防湿絶縁塗料B1~B3、C1、D1および光硬化性組成物E1~E2、F1~F2を、それぞれ乾燥後の厚みが150μmになるよう塗布し、高圧水銀ランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:CSN2-40)を用い、照射量1500mJ/cm2(365nmの値)の条件で紫外線を照射して硬化させ、50℃で6時間加熱後、室温で12時間放置した。
この試験片を用いて、バイアス電圧30Vを印加し、温度85℃、湿度85%RHの条件での温湿度定常試験を、MIGRATION TESTER MODEL MIG-8600(IMV社製)を用いて行った。上記温湿度定常試験をスタート初期およびスタートしてから1000時間後の抵抗値を表1に記す。
Claims (15)
- (a)水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオール、
(b)ポリイソシアネート化合物、および
(c)水酸基含有(メタ)アクリレート
を反応させることにより得られるウレタン(メタ)アクリレート。 - ポリエステルポリオール(a)が、水添ダイマー酸から誘導される構造単位を、ポリカルボン酸から誘導される構造単位の総量の80質量%以上含み、かつ水添ダイマージオールから誘導される構造単位を、ポリオールから誘導される構造単位の総量の80質量%以上含むことを特徴とする請求項1に記載のウレタン(メタ)アクリレート。
- ポリイソシアネート化合物(b)が、ノルボルナンジイソシアネート、イソホロンジイソシアネート、およびメチレンビス(4-シクロヘキシルイソシアネート)からなる群より選ばれる少なくとも1種であることを特徴とする請求項1または2に記載のウレタン(メタ)アクリレート。
- (1)請求項1~3のいずれか1項に記載のウレタン(メタ)アクリレート、および
(2)珪素原子を含まない(メタ)アクリロイル基含有化合物
を含む防湿絶縁塗料。 - さらに、
(3)シランカップリング剤
を含む請求項4に記載の防湿絶縁塗料。 - さらに、
(4)粘着付与剤
を含む請求項4または5に記載の防湿絶縁塗料。 - さらに、
(5)光重合開始剤
を含む請求項4~6のいずれか1項に記載の防湿絶縁塗料。 - 珪素原子を含まない(メタ)アクリロイル基含有化合物(2)の総量に対して、炭素数9以上の鎖状脂肪族炭化水素基を有する、珪素原子を含まない(メタ)アクリロイル基含有化合物と、炭素数9以上の環状脂肪族炭化水素基を有する、珪素原子含まない液状(メタ)アクリロイル基含有化合物の総量が50質量%以上であることを特徴とする請求項4~7のいずれか1項に記載の防湿絶縁塗料。
- 粘着付与剤(4)が石油樹脂系粘着付与剤を含むことを特徴とする請求項6~8のいずれか1項に記載の防湿絶縁塗料。
- 珪素原子を含まない(メタ)アクリロイル基含有化合物(2)を、全重合性成分に対して、30~75質量%含有する請求項4~10のいずれか1項に記載の防湿絶縁塗料。
- シランカップリング剤(3)を、全重合性成分100質量部に対して、0.01~8質量部含有する請求項5~11のいずれか1項に記載の防湿絶縁塗料。
- 粘着付与剤(4)を、全重合性成分100質量部に対して、0.1~35質量部含有する請求項6~12のいずれか1項に記載の防湿絶縁塗料。
- 光重合開始剤(5)を、全重合性成分100質量部に対して、0.1~10質量部含有する請求項7~13のいずれか1項に記載の防湿絶縁塗料。
- 請求項4~14のいずれか1項に記載の防湿絶縁塗料を用いて絶縁処理された電子部品。
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JP (1) | JPWO2013118655A1 (ja) |
KR (1) | KR20140107508A (ja) |
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JPWO2013118655A1 (ja) | 2015-05-11 |
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