JP6664212B2 - Polyurethane resin, composition for overcoat, and method for producing polyurethane resin - Google Patents

Description

  The present invention relates to a polyurethane resin and an overcoat resin using the same. More specifically, the present invention relates to a polyurethane resin suitable for a protective film of a conductive pattern obtained by firing a metal ink, particularly a metal nanowire ink.

  The transparent conductive film is a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescent display, a transparent electrode of a solar cell (PV) and a touch panel (TP), an antistatic (ESD) film, and an electromagnetic wave shielding (EMI). It is used in various fields such as films. Conventionally, as these transparent conductive films, those using ITO (indium tin oxide) have been used. However, the supply stability of indium is low, the production cost is high, the flexibility is low, and a high temperature is required during film formation. Was necessary. Therefore, the search for a transparent conductive film instead of ITO has been actively promoted. Among them, transparent conductive films containing metal nanowires have excellent conductivity, optical properties, and flexibility, can be formed by a wet process, have low manufacturing costs, and require high temperatures during film formation. Therefore, it is most suitable as a transparent conductive film instead of ITO. For example, a transparent conductive film containing silver nanowires and having high conductivity, optical characteristics, and flexibility is known (see Patent Document 1).

  However, the transparent conductive film containing silver nanowires has a problem in that it has a large surface area per silver weight and easily reacts with various compounds, and thus lacks environmental resistance. The nanostructure is easily corroded due to the influence of the influence or the influence of oxygen or moisture in the air exposed during long-term storage, and the conductivity tends to decrease. In particular, in the case of applications such as electronic materials, a physical cleaning process using a brush or the like is often used in order to prevent the attachment or mixing of particulate impurities, dust, dust, etc. on the surface of the substrate. The problem is that the surface is also damaged by the process.

  In order to solve this, many attempts have been made to laminate a protective film on the surface of a transparent conductive film containing silver nanowires and to impart environmental resistance and scratch resistance to the transparent conductive film. As a protective film used for a transparent conductive film containing silver nanowires, a protective film for a transparent conductive film using a urethane resin or the like, and a protective film for various optical materials including a polyester polyamic acid and an epoxy resin have been used. And a protective film using an inorganic silicon oxide are known (see Patent Documents 1 to 5).

JP 2010-507199 A JP 2008-156546 A JP 2009-205924 A JP 2011-204649 A JP 2011-102003 A

  Conventional protective films used for transparent conductive films containing silver nanowires do not satisfy all of the properties such as environmental resistance, abrasion resistance, and suppression of warpage during curing, and further improvements are required.

  The present invention has been made in view of these problems, and an object of the present invention is to provide a resin for a protective film for metal nanowires that has excellent environmental resistance and abrasion resistance and has little warpage during curing.

One embodiment of the present invention is a polyurethane resin. The polyurethane resin comprises a carboxyl group-containing polyurethane skeleton (A) and an aliphatic oxide ring-opening addition section containing an alkene oxide ring-opening addition section represented by the following formula (p1) bonded to at least a part of the carboxyl group. (B1) a hydroxy-containing resin (P) and a carboxyl group-containing polyurethane skeleton (A) and a cycloalkene oxide ring-opening addition unit represented by the following formula (p2) bonded to at least a part of the carboxyl group. It is a reaction product (urethane) of at least one of the hydroxy-containing resin (P) having the aliphatic oxide ring-opening addition portion (B2) and the polyisocyanate compound (Q).
In the above formula (p1), n ₁ is an integer of ₁ to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
In the above formula (p2), n ₂ is an integer of 1 to 10, and A ¹ is an atom forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded. It is a group.

  In the polyurethane resin of the above embodiment, the polyurethane skeleton containing a carboxyl group (A) is a polyurethane skeleton based on a reaction product of (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group. It may be. The (a1) polyisocyanate compound may be an alicyclic compound having 6 to 30 carbon atoms other than carbon atoms in the isocyanate group (—NCO group). The (a2) polyol compound may be a polycarbonate diol or a polybutadiene polyol. (A3) the dihydroxy compound having a carboxyl group is a carboxylic acid or an aminocarboxylic acid having a molecular weight of 200 or less and having at least two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms. Is preferred. One or more of the group consisting of 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, and N, N-bishydroxyethylalanine may be used. .

In the above formula (p1), n ₁ is an integer of ₁ to 10, R ¹ and R ² are each independently a hydrogen atom or a methyl group, or at least one of R ¹ and R ² is a hydrogen atom and the other is An alkyl group having 1 to 10 carbon atoms or a phenyl group is preferred. In the formula (p2), n ₂ is preferably an integer of 1 to 3, and A ¹ is preferably an alicyclic structure having 6 to 12 carbon atoms.

  The polyisocyanate compound (Q) may be an aliphatic isocyanate compound or a blocked isocyanate derived therefrom. Further, the polyisocyanate compound (Q) may be one blocked with a compound having active hydrogen selected from the group consisting of caprolactam, ketoxime, phenol and secondary amine.

Another embodiment of the present invention is a composition for an overcoat. The overcoating composition comprises an aliphatic oxide-opening containing a carboxyl group-containing polyurethane skeleton (A) and an alkene oxide ring-opening addition portion represented by the following formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having a cycloaddition portion (B1), a polyurethane skeleton (A) having a carboxyl group, and a cycloalkene oxide represented by the following formula (p2) bonded to at least a part of the carboxyl group: It contains at least one of a hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition portion (B2) containing a ring addition portion, a polyisocyanate compound (Q), and a solvent.
In the above formula (p1), n ₁ is an integer of ₁ to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
In the above formula (p2), n ₂ is an integer of 1 to 10, and A ¹ is an atom forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded. It is a group.

Yet another embodiment of the present invention is a method for producing a polyurethane resin. The method for producing the polyurethane resin includes a method for preparing a carboxyl group contained in a polyurethane resin having a carboxyl group-containing polyurethane skeleton (A), an alkene oxide represented by the formula (x1), and a cycloalkene oxide represented by the formula (x2). And the step of reacting the hydroxy group-containing resin (P) obtained in the above step with a polyisocyanate compound (Q).
In Formula (x1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
(In the formula (x2), A ¹ represents an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded.)

  The alkene oxide represented by the formula (x1) may be ethylene oxide, propylene oxide, or styrene oxide. The cycloalkene oxide represented by the formula (x2) may be cyclohexene oxide.

  A combination of the above-described elements as appropriate may be included in the scope of the invention for which protection is sought by the present patent application.

  ADVANTAGE OF THE INVENTION According to this invention, the resin for protective films for metal nanowires which is excellent in environmental resistance and abrasion resistance and has little warpage during curing is provided.

9 is a ¹ H-NMR spectrum of a resin composition according to Synthesis Example 5. 9 is an IR spectrum of the resin composition according to Example 5. It is a figure showing the method of a warpage test.

  Hereinafter, embodiments of the present invention will be described.

The polyurethane resin according to the embodiment is an aliphatic oxide containing a polyurethane skeleton (A) having a carboxyl group and an alkene oxide ring-opening addition portion represented by the following formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having a ring-opening addition portion (B1), a carboxyl-containing polyurethane skeleton (A), and a cycloalkene oxide represented by the following formula (p2) bonded to at least a part of the carboxyl group: It is a reaction product of at least one of the hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition portion (B2) containing a ring-opening addition portion and a polyisocyanate compound (Q). The acid value of the polyurethane resin is preferably from 0 to 60.
In the formula (p1), n ₁ is an integer of ₁ to 50, preferably 1 to 30, and more preferably 1 to 10. When n ₁ is larger than 50, insulation reliability for moisture absorption is increased the higher the hydrophilicity is lowered. R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group, and in view of availability, preferably, R ¹ and R ² are each independently A hydrogen atom or a methyl group, or at least one of R ¹ and R ² is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms or a phenyl group.
Wherein (p2), _{n 2} is an integer of from 1 to 10, preferably 1 to 5, more preferably 1 to 3. A ¹ is an atomic group forming an alicyclic hydrocarbon group having 4 to 14, preferably 6 to 12 carbon atoms, including the two carbon atoms to which A ¹ is bonded.

<Polyurethane skeleton having carboxyl group (A) constituting hydroxy-containing resin (P)>
The number average molecular weight of the carboxyl group-containing polyurethane skeleton (A) is preferably from 1,000 to 100,000, and more preferably from 3,000 to 50,000. Here, the molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC). If the molecular weight is less than 1,000, the elongation, flexibility, and strength of the coating film after printing may be impaired. If the molecular weight is more than 100,000, the solubility of the polyurethane in the solvent becomes low, and However, since the viscosity is too high, there are cases where the restrictions in use are increased.

In the present specification, unless otherwise specified, the measurement conditions of GPC are as follows.
Apparatus name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804
Mobile phase: tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume: 100 μL sample loop Sample concentration: adjusted to about 0.1% by mass

  The acid value of the carboxyl group-containing polyurethane skeleton (A) is preferably from 10 to 140 mgKOH / g, and more preferably from 15 to 130 mgKOH / g. If the acid value is less than 10 mgKOH / g, the number of reaction points with the aliphatic oxide described below is small, and the effect of adding the aliphatic oxide is poor. If it exceeds 140 mgKOH / g, the solubility as a urethane resin containing a carboxyl group in a solvent is low, and even if it is dissolved, the viscosity becomes too high and handling is difficult.

  In this specification, the acid value of the resin is a value measured by the following method.

About 0.2 g of the sample is precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / toluene = 1/2 (mass ratio) is added to dissolve it. Further, 1 to 3 drops of a phenolphthalein ethanol solution is added to this container as an indicator, and the mixture is sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1 N potassium hydroxide-ethanol solution, and the end point of the neutralization is defined as the point at which the indicator remains slightly red for 30 seconds. The value obtained from the result using the following calculation formula is defined as the acid value of the resin.
Acid value (mgKOH / g) = [B × f × 5.611] / S
B: Usage amount of 0.1 N potassium hydroxide-ethanol solution (ml)
f: Factor of 0.1N potassium hydroxide-ethanol solution S: Sample collection amount (g)

  More specifically, the polyurethane skeleton (A) containing a carboxyl group is synthesized using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as monomers. That is, it has a skeleton based on a reaction product of (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group. In other words, (a1) a reaction product (urethane bond) unit of a polyisocyanate compound and (a3) a dihydroxy compound having a carboxyl group, and (a2) a reaction product of a polyol compound and (a3) a dihydroxy compound having a carboxyl group ( (Urethane bond) unit. Hereinafter, each monomer will be described in more detail.

(A1) Polyisocyanate Compound As the (a1) polyisocyanate compound, a diisocyanate having two isocyanato groups per molecule is usually used. Examples of the polyisocyanate compound include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an araliphatic polyisocyanate. As long as the carboxyl group-containing polyurethane skeleton (A) does not gel, a small amount of a polyisocyanate having three or more isocyanate groups such as triphenylmethane triisocyanate can also be used.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,2′-diethyl ether diisocyanate, dimer acid diisocyanate and the like.

  Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and 3-isocyanatomethyl-3,3,5- Examples include trimethylcyclohexane (IPDI, isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), hydrogenated (1,3- or 1,4-) xylylene diisocyanate, norbornane diisocyanate, and the like.

  Examples of the aromatic polyisocyanate include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (1 , 2,1,3 or 1,4) -xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 1,5- Naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, and the like.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and 3,3′-methylene ditolylene -4,4'-diisocyanate and the like. These diisocyanates can be used alone or in combination of two or more.

  (A1) By using an alicyclic compound having 6 to 30 carbon atoms other than carbon atoms in the isocyanate group (—NCO group) as the polyisocyanate compound, the polyurethane resin according to the embodiment described below can be used. The formed protective film has high reliability particularly at high temperature and high humidity, and is suitable for a member of an electronic device component.

  The alicyclic compound is contained in the (a1) polyisocyanate compound in an amount of 10 mol% or more, preferably 20 mol%, more preferably 30 mol% or more based on the total amount (100 mol%) of the (a1) polyisocyanate compound. It is desirable.

  Examples of the alicyclic compound include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, and 1,4-bis (isocyanatomethyl) cyclohexane. .

(A2) Polyol compound The number average molecular weight of the (a2) polyol compound (however, the (a2) polyol compound does not include the (a3) dihydroxy compound having a carboxyl group described below) is usually 250 to 50,000. Yes, preferably from 400 to 10,000, more preferably from 500 to 5,000. This molecular weight is a value in terms of polystyrene measured by GPC under the conditions described above.

  (A2) Polyol compounds include, for example, polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polybutadiene polyols, hydroxyl-terminated polysilicones, and hydroxyl groups containing oxygen atoms only and having 18 to 72 carbon atoms. It is a polyol compound. Among these, polycarbonate polyol and polybutadiene polyol are preferable in consideration of the balance between water resistance as a protective film, insulation reliability, and adhesion to a substrate.

The polycarbonate polyol can be obtained by reacting a diol having 3 to 18 carbon atoms with a carbonate or phosgene, and is represented by the following structural formula (1).
In formula (1), ^{R 3} is a group given by removing hydroxyl groups from the corresponding diol ^{(HO-R 3 -OH),} n 3 is a positive integer, preferably from 2 to 50.

  Specifically, the polycarbonate polyol represented by the formula (1) includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1 1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10 -Can be produced by using decamethylene glycol or 1,2-tetradecanediol as a raw material.

  The polycarbonate polyol may be a polycarbonate polyol having a plurality of alkylene groups in its skeleton (copolycarbonate polyol). Use of the copolymerized polycarbonate polyol is often advantageous from the viewpoint of preventing crystallization of the polyurethane skeleton (A) containing a carboxyl group. In consideration of solubility in a solvent, it is preferable to use a polycarbonate polyol having a branched skeleton and having a hydroxyl group at a terminal of the branched chain.

The polyether polyol is obtained by dehydration condensation of a diol having 2 to 12 carbon atoms, or ring-opening polymerization of an oxirane compound having 2 to 12 carbon atoms, an oxetane compound, or a tetrahydrofuran compound. Is represented by the structural formula (2).
In the formula (2), R ⁴ is a residue obtained by removing a hydroxyl group from the corresponding diol (HO—R ⁴ —OH), and n ₄ is a positive integer, preferably ₄ to 50. The diol having 2 to 12 carbon atoms may be used alone to form a homopolymer, or may be used as a copolymer by using two or more kinds in combination.

  As the polyether polyol represented by the above formula (2), specifically, polyethylene glycol, polypropylene glycol, poly-1,2-butylene glycol, polytetramethylene glycol (poly-1,4-butanediol), poly And polyalkylene glycols such as -3-methyltetramethylene glycol and polyneopentyl glycol. For the purpose of improving the compatibility of the (polyether polyol) and the hydrophobicity of the (polyether polyol), a copolymer thereof, for example, 1,4-butanediol-neopentyl glycol can also be used.

The polyester polyol is obtained by subjecting a dicarboxylic acid and a diol to dehydration condensation or transesterification of an esterified product of a lower alcohol of a dicarboxylic acid and a diol, and is represented by the following structural formula (3), for example. .
In the formula (3), R ⁵ is a residue obtained by removing a hydroxyl group from the corresponding diol (HO-R ⁵ -OH), and R ⁶ is two carboxyl groups from the corresponding dicarboxylic acid (HOCO-R ⁶ -COOH). a residue obtained by removing, _{n 5} is a positive integer, preferably from 2 to 50.

Examples of the diol ^(HO-R 5 -OH), specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, Butylethylpropanediol, 1,3-cyclohexanedimethanol, 3-xylylene glycol, 1,4-xy Glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and the like.

As the dicarboxylic acid ^(HOCO-R 6 -COOH), specifically, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid, hexa Hydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendmethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4- Examples include naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.

The polylactone polyol is obtained by a condensation reaction between a ring-opened polymer of lactone and a diol or a condensation reaction between a diol and a hydroxyalkanoic acid, and is represented by, for example, the following structural formula (4).
In the formula (4), R ⁷ is a residue obtained by removing a hydroxyl group and a carboxyl group from a corresponding hydroxyalkanoic acid (HO-R ⁷ -COOH), and R ⁸ is a residue from a corresponding diol (HO-R ⁸ -OH). It is a residue excluding a hydroxyl group, and n ₆ is a positive integer, preferably 2 to 50.

Examples of the hydroxy alkanoic acid ^(HO-R 7 -COOH), specifically, 3-hydroxybutanoic acid, 4-hydroxy-pentanoic acid, 5-hydroxy hexanoic acid.

  The polybutadiene polyol is, for example, a diol obtained by polymerizing butadiene or isoprene by anionic polymerization and introducing hydroxyl groups to both ends by terminal treatment, and a diol obtained by hydrogenating the double bond thereof.

  As the polybutadiene polyol, specifically, hydroxylated polybutadiene mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)), hydroxylated hydrogenation Polybutadiene (for example, Polytail (registered trademark) H, Polytail (registered trademark) HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene having mainly 1,2-repeating units (for example, G-1000, G-2000, G-3000 (produced by Nippon Soda Co., Ltd.), hydroxylated hydrogenated polybutadiene (for example, GI-1000, GI-2000, GI-3000 (produced by Nippon Soda Co., Ltd.)), and hydroxylated polyisoprene (for example, Poly IP ( Idemitsu Kosan Co., Ltd.)), hydroxylated hydrogenated polyisoprene (for example, EPOL (registered trademark, manufactured by Idemitsu Kosan Co., Ltd.)), and the like.

The double-ended hydroxylated silicone is represented by, for example, the following structural formula (5).
In the formula (5), R ⁹ is independently a divalent aliphatic hydrocarbon residue or a divalent aromatic hydrocarbon residue having 2 to 50 carbon atoms, and n ₇ is a positive integer, preferably 2 to 50. It is. These may include an ether group, and a plurality of R ¹⁰ are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 12 carbon atoms.

  Commercial products of the above-mentioned hydroxyl group-terminated polysilicone include, for example, "X-22-160AS, KF6001, KF6002, KF-6003" manufactured by Shin-Etsu Chemical Co., Ltd. Specific examples of the above-mentioned "polyol compound containing an oxygen atom only in a hydroxyl group and having 18 to 72 carbon atoms" include a diol compound having a skeleton obtained by hydrogenating dimer acid. And "SOVERMOL (registered trademark) 908" manufactured by Cognis.

  Further, as long as the effects of the present invention are not impaired, a diol having a molecular weight of 300 or less having no repeating unit can be used as the (a2) polyol compound. Specific examples of such a low molecular weight diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol , 1,3-cyclohexanedimethanol, 1,3-xylylene glycol, 1,4-xylylene Call, diethylene glycol, triethylene glycol or dipropylene glycol.

(A3) Carboxyl group-containing dihydroxy compound (a3) Carboxyl group-containing dihydroxy compound has a molecular weight of 200 having two of two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms. The following carboxylic acids or aminocarboxylic acids are preferred in that the crosslinking point can be controlled. Specific examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine and the like. From the viewpoint of solubility, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred. These (a3) dihydroxy compounds containing a carboxyl group can be used alone or in combination of two or more.

  The aforementioned polyurethane resin having a carboxyl group-containing polyurethane skeleton (A) can be synthesized only from the above three components ((a1), (a2) and (a3)). (A4) a monohydroxy compound and / or (a5) a monoisocyanate compound for the purpose of imparting properties or cationic polymerizability, or for the purpose of suppressing the influence of the isocyanate group or hydroxyl residue at the end of the polyurethane. Can be synthesized.

(A4) Monohydroxy compound (a4) As the monohydroxy compound, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, each of the above (meth) ) Caprolactone or alkylene oxide adduct of acrylate, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acryl Compounds having a radical polymerizable double bond such as acrylate, allyl alcohol and allyloxyethanol, and compounds having a carboxylic acid such as glycolic acid and hydroxypivalic acid. It is below.

  (A4) The monohydroxy compound can be used alone or in combination of two or more. Further, among these compounds, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, glycolic acid, and hydroxypivalic acid are preferable, and 2-hydroxyethyl (meth) acrylate is preferred. ) Acrylates and 4-hydroxybutyl (meth) acrylate are more preferred.

  In addition, (a4) monohydroxy compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, amyl alcohol, hexyl alcohol, octyl alcohol and the like.

(A5) Monoisocyanate compound (a5) Examples of the monoisocyanate compound include (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and diisocyanate compound. Cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each of the above (meth) acrylates, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Radiation of mono-adducts of (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxyethanol, etc. Le carbon - include compounds having a carbon-carbon double bond.

  Examples of the monoisocyanate hydroxy compound used for the purpose of suppressing the influence of the terminal hydroxyl residue include phenyl isocyanate, hexyl isocyanate, and dodecyl isocyanate.

  The aforementioned polyurethane resin having a carboxyl group-containing polyurethane skeleton (A) is prepared using the above-mentioned (a1) using a suitable organic solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate. Can be synthesized by reacting a) a polyisocyanate compound, (a2) a polyol compound, (a3) a dihydroxy compound having a carboxyl group, and (a4) a monohydroxy compound or (a5) a monoisocyanate compound as required. The reaction with a catalyst is preferred because it is not necessary to consider the mixing of tin or the like in the end.

  The organic solvent is not particularly limited as long as it has low reactivity with the isocyanate compound, but does not contain a basic functional group such as an amine, and has a boiling point of 110 ° C or higher, preferably 150 ° C or higher, more preferably 200 ° C or higher. Certain solvents are preferred. Examples of such a solvent include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and propylene glycol monoethyl ether monoacetate. , Dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, Acetone, methyl ethyl ketone, cyclohexyl Non, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, can be mentioned chloroform and methylene chloride.

  Considering that an organic solvent having low solubility of the produced polyurethane resin is not preferable and that polyurethane is used as a raw material for an ink in electronic material applications, among these, propylene glycol monomethyl ether monoacetate and propylene glycol are particularly preferable. Monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, and γ-butyrolactone are preferred.

  The order of charging the raw materials is not particularly limited, but usually, (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group are first charged and dissolved in a solvent. At 60 to 120 ° C, the (a1) polyisocyanate compound is added dropwise, and then these are reacted at 30 to 160 ° C, more preferably 50 to 130 ° C.

  The charged molar ratio of the raw materials is adjusted according to the molecular weight and the acid value of the target polyurethane resin. However, when the (a4) monohydroxy compound is introduced into the polyurethane resin, the terminal of the polyurethane molecule is an isocyanate group. In addition, it is necessary to use (a1) a polyisocyanate compound in excess (so that the isocyanate group is greater than the total of the hydroxyl groups) than (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group.

  Specifically, these charged molar ratios are such that (a1) the isocyanate group of the polyisocyanate compound: ((a2) the hydroxyl group of the polyol compound + (a3) the hydroxyl group of the dihydroxy compound having a carboxyl group) is 0.5 to 1 0.5: 1, preferably 0.8 to 1.2: 1, more preferably 0.95 to 1.05: 1.

  Further, (a2) the hydroxyl group of the polyol compound: (a3) the hydroxyl group of the dihydroxy compound having a carboxyl group is 1: 0.1 to 30, preferably 1: 0.3 to 10.

  When the (a4) monohydroxy compound is used, the molar number of the (a1) polyisocyanate compound is set to be larger than the molar number of ((a2) the polyol compound + (a3) the dihydroxy compound having a carboxyl group), and (a4) The monohydroxy compound is preferably used in a molar amount of 0.5 to 1.5 times, preferably 0.8 to 1.2 times the molar number of the excess isocyanato group.

  When (a5) a monoisocyanate compound is used, the molar number of ((a2) polyol compound + (a3) a dihydroxy compound having a carboxyl group) is made to be an excess of the molar number of (a1) a polyisocyanate compound, and It is preferably used in a molar amount of 0.5 to 1.5 times, preferably 0.8 to 1.2 times the molar number of the molar number.

  In order to introduce the (a4) monohydroxy compound into the polyurethane skeleton (A) containing a carboxyl group, the reaction of (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group with (a1) a polyisocyanate compound. At the time of completion, the (a4) monohydroxy compound is added to the reaction solution in order to react the (a4) monohydroxy compound with the isocyanate groups remaining at both ends of the polyurethane skeleton (A) containing a carboxyl group. Is added dropwise at 20 to 150 ° C, more preferably 70 to 120 ° C, and then kept at the same temperature to complete the reaction.

  In order to introduce the (a5) monoisocyanate compound into the carboxyl group-containing polyurethane skeleton (A), the reaction between (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group and (a1) a polyisocyanate compound is performed. At the time when the reaction is almost completed, (a5) the monoisocyanate compound is added to the reaction solution at 20 to 150 ° C. in order to react the (A5) monoisocyanate compound with the hydroxyl groups remaining at both ends of the polyurethane skeleton. More preferably, the mixture is added dropwise at 50 to 120 ° C., and then the temperature is maintained at the same temperature to complete the reaction.

<The aliphatic oxide ring-opening addition portions (B1) and (B2) constituting the hydroxy-containing resin (P)>
The aliphatic oxide ring-opening addition portions (B1) and (B2) are represented by the following formula (x1) in the carboxyl group (—COOH) contained in the polyurethane resin having the carboxyl group-containing polyurethane skeleton (A). And an aliphatic oxide containing a cycloalkene oxide represented by the formula (x2). It is also possible to react a predetermined ratio of a mixture of the two. In this case, a hydroxy-containing resin (P) in which the unit represented by the formula (p1) and the unit represented by the formula (p2) are mixed is obtained. In addition, both the alkene oxide represented by the following formula (x1) and the cycloalkene oxide represented by the formula (x2) may be addition-polymerized to the same carboxyl group of the polyurethane skeleton (A).
Wherein ^(x1), R 1, ^{R 2} is equal to ^R 1, ^{R 2} in the formula (p1), i.e., each independently, a hydrogen atom, an alkyl group having a carbon number of 1 to 16 or a phenyl group, Represents In terms of easy availability, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, or at least one of R ¹ and R ² is a hydrogen atom, and the other has 1 to 10 carbon atoms. And those having an alkyl group or a phenyl group are preferred. Specifically, examples of the alkene oxide represented by the above formula (x1) include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.
Wherein (x2), A ¹ is equal to A ¹ in the formula (p2), i.e., a monocyclic aliphatic hydrocarbon group or N-cyclic aliphatic hydrocarbon group having 2 to 12 carbon atoms, An alicyclic structure having 4 to 14 carbon atoms is formed. From the viewpoint of easy availability, those having an alicyclic structure having 6 to 12 carbon atoms are preferable. Specifically, examples of the cycloalkene oxide represented by the formula (x2) include cycloalkene oxides such as cyclohexene oxide, cyclooctene oxide, cyclodothene oxide, and monooxide of dicyclopentadiene.

  Conditions for reacting the above-mentioned carboxyl group-containing polyurethane skeleton (A) with the above-mentioned aliphatic oxide include a catalyst for accelerating a reaction between an epoxy group and a carboxylic acid in a solution in which a carboxyl group-containing polyurethane skeleton (A) is synthesized. And heated to 50 to 160 ° C., more preferably 80 to 140 ° C. for reaction. If the reaction temperature is too low, the speed will be too slow, and if the reaction temperature is too high, gelation may occur. The reaction time is 2 to 48 hours, preferably 3 to 24 hours, more preferably 4 to 12 hours.

  The amount of the polyurethane skeleton (A) containing a carboxyl group and the amount of the above-mentioned aliphatic oxide to be used are such that the epoxy group of the aliphatic oxide is 0.5 equivalent to the carboxyl group in the polyurethane skeleton (A) containing the carboxyl group. The amount is preferably 50 equivalents, more preferably 0.7 equivalents to 20 equivalents, and still more preferably 1 equivalents to 10 equivalents. If the above equivalent is less than 0.5, the concentration of the generated hydroxyl group becomes low, and the reaction point with the isocyanato group becomes low, which is not preferable. When the above-mentioned equivalent exceeds 50 equivalents, adverse effects such as a decrease in the moisture absorption of the resin itself appear.

It is obtained by reacting the aforementioned carboxyl group-containing polyurethane skeleton (A) with an alkene oxide represented by the above formula (x1) and an aliphatic oxide containing at least one of the cycloalkene oxide represented by the formula (x2). The resulting hydroxy-containing resin (P) may also contain some unreacted carboxyl groups. By having an unreacted carboxyl group, the adhesion to the base material or the metal wiring may be improved in some cases. The reaction is performed so that the amount of unreacted carboxyl groups becomes 50% or less, preferably 20% or less, more preferably 10% with respect to the amount of the original carboxyl groups, and the acid value is 0 to 50 mg-KOH / g. Preferably, a hydroxy-containing polyurethane resin of 0 to 30 mg-KOH / g, more preferably 0 to 10 mg-KOH / g, can be obtained. The resulting hydroxy-containing polyurethane resin has a structure represented by the formula (p1) or (p2).
In the formula, R ¹ , R ² , and A ¹ are the same as those of the above formula (x1) or (x2). n ₁ is an integer of ₁ to 50, n ₂ is an integer of 1 to 10, preferred n ₁ is an integer of ₁ to 30, preferred n ₂ is an integer of 1 to 5, and more preferred n ₁ is 1 to 10 integer, and more preferably _{n 2} is an integer of 1 to 3. The hydroxy-containing polyurethane resin has a structure in which an integer number of units shown in parentheses are bonded to a carboxyl group in the polyurethane skeleton (A) as shown by the formula (p1) or (p2). It is not necessary that the unit shown in parentheses be attached to the carboxyl group. That is, the number of units indicated by parentheses bonded to each carboxyl group does not need to be the same, and may have an unreacted carboxyl group not bonded as described above. Since the number of units shown in parentheses attached to each carboxyl group cannot be confirmed, the average value is calculated in the examples described later. By reacting in an amount to epoxy group is 0.5 equivalent to 50 equivalents of an aliphatic oxide relative to the carboxyl groups of the polyurethane backbone (A) having a carboxyl group, the average value of n ₁ and n ₂ are theoretically Although it can be 0.5 to 50, it is actually smaller than the theoretical value. preferred average value of n ₁ is 0.4 to 10, and more preferably 0.5 to 5. preferred average value of n ₂ is 0.4 to 10, and more preferably 0.5 to 5.

  Since the hydroxy-containing resin (P) thus obtained has a hydroxyl group, the number of functional groups can be determined by measuring the hydroxyl group concentration as a hydroxyl value. The preferred range of the hydroxyl value is 10 to 140 mg-KOH / g, more preferably 20 to 140 mg-KOH / g, even more preferably including the case where the original urethane resin has a terminal hydroxyl group. 30-140 mg-KOH / g.

  In addition, the above reaction can be performed in an inert gas or air atmosphere, but in the case of a highly flammable compound such as ethylene oxide, it is necessary to perform the reaction in an inert gas atmosphere, and the boiling point is very low. Since it is low, it is necessary to carry out the reaction under pressure.

  As the reaction catalyst, the carboxyl group contained in the carboxyl group-containing polyurethane skeleton (A) also acts as a catalyst, but a basic compound can be added for the purpose of further increasing the reaction rate or the degree of polymerization. Examples of the basic compound include a tertiary amine, a phosphine compound, and a quaternary ammonium hydroxide. More specifically, as a tertiary amine, triethylamine, tributylamine, trioctylamine, DBU (registered trademark) (1,8-diazabicyclo [5,4,0] undecene-7), DBN (1,5-diazabicyclo) [4,3,0] nonene-5) and 2,4,6-trisdimethylaminomethylphenol. Examples of the phosphine compound include triphenylphosphine, triphenylphosphite, trimethylphosphine, and trimethylphosphite. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide. If the amount is too small, the effect of the addition is not obtained. If the amount is too large, the electrical insulation of the obtained polyurethane resin is reduced. Therefore, based on the total mass of the carboxyl group-containing polyurethane skeleton (A) and the aliphatic oxide, 0.1 to 5% by mass, more preferably 0.5 to 3% by mass.

<Polyisocyanate compound (Q)>
Next, the thus obtained aliphatic skeleton containing a carboxyl group-containing polyurethane skeleton (A) and the alkene oxide ring-opening addition portion represented by the formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having an oxide ring-opening addition portion (B1), and a cycloalkene oxide represented by the formula (p2) bonded to at least a part of a carboxyl group and a polyurethane skeleton (A) having a carboxyl group. A polyisocyanate compound (Q) is reacted with at least one of the hydroxy group-containing resins (P) having an aliphatic oxide ring-opening addition portion (B2) containing a ring-opening addition portion.

  It is desirable that the hydroxyl group in the hydroxy group-containing resin (P) is reacted with the isocyanate group in the polyisocyanate compound (Q) in an equivalent amount. It can be used if the deviation from it is within -20% to + 20%.

  Examples of such a polyisocyanate compound include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an araliphatic polyisocyanate.

  Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, And dimer acid diisocyanate.

  Examples of the alicyclic polyisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (IPDI, isophorone diisocyanate) ), Bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, and the like.

  Examples of the aromatic polyisocyanate include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Examples include 3′-dimethyl-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate diphenylmethane, 1,5-naphthylene diisocyanate, and the like.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α, α, α ′, α′-tetramethyl xylylene diisocyanate.

  Examples of the polyisocyanate compound (Q) other than the above include, for example, an isocyanate group-terminated compound obtained by a reaction between an isocyanate compound and an active hydrogen group-containing compound, a reaction product of these compounds (for example, an adduct-type polyisocyanate, an allophanate-forming reaction, Carbodiimidization reaction, uretdionation reaction, isocyanuration reaction, uretoniminization reaction, isocyanate modified product by biuretization reaction, etc.), or a mixture thereof.

  These polyisocyanate compounds (Q) may be used alone or in combination of two or more.

  Further, these polyisocyanate compounds (Q) may be prepolymers obtained by reacting the starting polyisocyanate compound such that an excess of isocyanate remains with respect to the hydroxyl groups of the starting polyol compound.

  The polyol compound for obtaining the prepolymer refers to a compound containing two or more hydroxyl groups reactive to isocyanato groups, and specifically, for example, an acrylic polyol, a polyester polyol, a polyether polyol, an epoxy polyol And the like.

  The acrylic polyol includes, for example, a copolymer of a polymerizable monomer having at least one active hydrogen (hydroxyl group) in one molecule and a monomer copolymerizable therewith.

  Examples of the polymerizable monomer having one or more active hydrogens in one molecule include acrylic acid hydroxy esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate. Methacrylic acid hydroxyesters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, acrylate monoester or methacrylate monoester of glycerin, and acrylic acid of trimethylolpropane Monoesters and methacrylic acid monoesters, and monomers obtained by ring-opening polymerization of ε-caprolactone to these hydroxyl groups, and the like can be mentioned.

  Examples of monomers copolymerizable with the polymerizable monomer include acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and methyl methacrylate. Methacrylates such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid And unsaturated carboxylic acids such as maleic acid and itaconic acid, unsaturated amides such as acrylamide, N-methylolacrylamide and diacetoneacrylamide, styrene, vinyltoluene, vinyl acetate, acrylonitrile and the like. It is.

  Examples of the polyester polyol include a condensation polyester polyol, a polycarbonate polyol, and a polylactone polyol.

  Examples of the condensed polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Diols such as hexanediol, neopentyl glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and succinic acid, adipic acid, azelaic acid, sebacic acid, Dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dical Reaction products of dicarboxylic acids such as phosphate and the like.

  Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopenthylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly (polytetramethylene ether) ) Adipate-based condensed polyester diols such as adipate diol and the like, and azelate-based condensed polyester diols such as polyethylene azelate diol and polybutylene azelate diol.

  Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Reaction products of diols such as diol, neopentyl glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, and tripropylene glycol, and dialkyl carbonates such as dimethyl carbonate. Can be Specifically, polytetramethylene carbonate diol, poly-3-methylpentamethylene carbonate diol, polyhexamethylene carbonate diol and the like are exemplified.

  Examples of the polylactone polyol include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and a ring-opening polymer of a mixture of two or more thereof. Specific examples include polycaprolactone diol.

  Examples of the polyether polyol include activities such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, hydroquinone, and bisphenol A. A reaction product obtained by addition-polymerizing a monomer such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclohexylene using a compound containing two or more hydrogen atoms as an initiator is exemplified. In the case of a reaction product obtained by addition polymerization of two or more monomers, block addition, random addition, or a mixture of both may be used. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like are exemplified.

  Examples of epoxy polyols include novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycol ether type, epoxy type of aliphatic unsaturated compound, epoxidized fatty acid ester type, polycarboxylic acid ester type, amino acid Epoxy polyols such as glycidyl type, halogenated type and resorcinol type are exemplified.

  The polyisocyanate compound (Q) only needs to have a plurality of isocyanate groups, and at least one of these isocyanato groups may be blocked with a compound having active hydrogen.

  Examples of the compound in which the isocyanate group is blocked include, for example, known blocking agents such as alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol, phenol, cresol, and the like. Nitrophenol, chlorophenol, phenols such as resorcinol, thiols such as benzenethiol, caprolactams such as ε-caprolactam, carbamates such as ethyl carbamate, keto enols such as acetylacetone, ketooximes such as methyl ethyl ketone oxime, diisopropylamine, Using secondary amines such as triazole and 3,5-dimethylpyrazole, bisulfite and the like, the above-mentioned polyisocyanate compound or a modified product thereof, Mer may include compounds obtained by blocking. Among these, compounds having active hydrogen selected from the group consisting of caprolactam, ketoxime, phenol and secondary amine are preferred from the viewpoint of the balance between stability at room temperature and the curing rate at which the protective group is removed at high temperature and cured.

  In order to promote the urethanization reaction between the polyisocyanate compound (Q) and the hydroxy group-containing resin (P), a curing acceleration catalyst such as dibutyltin laurate can be used.

  As such a curing promoting catalyst, in addition to a tin compound, a salt of a strongly basic amine such as DBU with phenol or a carboxylic acid compound, a special amine compound, a non-tin based metal such as acetylacetone metal complex, bismuth, aluminum or zirconium complex, or the like. Compounds can be used.

  Examples of the tin compound for the curing acceleration catalyst include Dabco (registered trademark) T-12 and Dabco T-120 manufactured by Air Products, such as Neostan U-100, Neostan U-130, and Neostan U-200 manufactured by Nitto Kasei Corporation. , Dabco T-125 and the like.

  As a non-tin compound for a curing acceleration catalyst, for example, K-KAT (registered trademark) manufactured by Kusumoto Kasei Co., Ltd., such as U-CAT SA1, U-CAT SA 102, and U-CAT SA 102-50 manufactured by Sun Apro Co., Ltd. ), 348, K-KATXC-C227, K-KATXK-628, and the like, and Nasem aluminum, Nasem chrome, Nasem second cobalt manufactured by Nippon Kasei Sangyo Co., Ltd., and the like.

<Polyurethane resin>
It has a polyurethane skeleton (A) containing a carboxyl group and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part represented by the formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) and an aliphatic oxide opening containing a cycloalkene oxide ring-opening addition moiety represented by the formula (p2) bonded to at least a part of the carboxyl group-containing polyurethane skeleton (A); By reacting at least one of the hydroxy-containing resin (P) having a ring addition portion (B2) with the polyisocyanate compound (Q), the aliphatic oxide ring-opening addition portion (B1) of the hydroxy group-containing resin (P) And at least a part of (B2) react with the isocyanato group of the polyisocyanate compound (Q) In addition, it has a (* 1) -O-CONH-(* 2) (* 1 represents a residue of the hydroxy group-containing resin (P) and * 2 represents a residue of the polyisocyanate compound (Q)). A polyurethane resin as a reaction product (hereinafter, referred to as a polyurethane resin) is generated.

  The polyurethane resin has a carboxyl group-containing polyurethane skeleton (A) and an aliphatic oxide ring-opening addition section containing the alkene oxide ring-opening addition section represented by the above formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having (B1), a polyurethane skeleton (A) containing a carboxyl group, and a cycloalkene oxide ring-opening addition unit represented by the formula (p2) bonded to at least a part of the carboxyl group. One or a mixture of two or more obtained by reacting a polyisocyanate compound (Q) with at least one of the hydroxy-containing resins (P) having an aliphatic oxide ring-opening addition portion (B2) may be used. . In the latter case, a polyurethane skeleton containing a carboxyl group (A) and an aliphatic oxide ring-opening addition unit containing the alkene oxide ring-opening addition unit represented by the above formula (p1) bonded to at least a part of the carboxyl group. A reaction product of a hydroxy-containing resin (P) having (B1), a carboxyl group-containing polyurethane skeleton (A) and a polyisocyanate compound (Q), and a formula (p2) bonded to at least a part of the carboxyl group A mixture of a reaction product of a hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition portion (B2) containing a cycloalkene oxide ring-opening addition portion represented by and a polyisocyanate compound (Q) may be used. .

The obtained reaction products include, for example, those represented by the following structural formula.
In the above formula, R represents a residue obtained by removing an isocyanato group or a block isocyanato group from the polyisocyanate compound (Q). In the above formula, as the polyisocyanate compound (Q), a structure in which both isocyanate groups at both ends of the diisocyanate compound have reacted is shown, but a structure in which only one of the isocyanate groups has reacted may be included. Further, the reaction product may include a variety of structures including other structures (for example, a reaction precursor), and a specific structure constituting the reaction product (polyurethane resin) and a compounding ratio thereof may be determined. It is difficult to specify.

  An overcoating composition according to another embodiment of the present invention includes an alkene oxide represented by the formula (p1) bonded to at least a part of the carboxyl group-containing polyurethane skeleton (A) described above. A hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition part (B1) containing a ring-opening addition part, and a polyurethane skeleton (A) containing a carboxyl group and a formula (p2) bonded to at least a part of the carboxyl group. A) a hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition portion (B2) containing a cycloalkene oxide ring-opening addition portion represented by formula (I), a polyisocyanate compound (Q), and a solvent. Including. The above-mentioned carboxyl group-containing polyurethane skeleton (A) and the aliphatic oxide ring-opening addition portion (B1) containing the alkene oxide ring-opening addition portion represented by the formula (p1) bonded to at least a part of the carboxyl group are provided. Having a hydroxy-containing resin (P) and a polyurethane skeleton (A) having a carboxyl group and a cycloalkene oxide ring-opening addition portion represented by the formula (p2) bonded to at least a part of the carboxyl group: At least one of the hydroxy-containing resin (P) having the ring-opening addition portion (B2) and the polyisocyanate compound (Q) are dissolved in an appropriate solvent, and if necessary, a curing acceleration catalyst and a printing or coating are used. Additives can be blended to form an overcoat composition (protective film ink). The overcoat composition (protective film ink) is applied to a substrate on which a conductive pattern is formed, formed into a film, and then cured to obtain an overcoat film (protective film) made of the polyurethane resin of the present embodiment. Can be

  The solvent used in the overcoat composition (protective film ink) is a carboxyl group-containing polyurethane skeleton (A) and an alkene oxide ring-opening addition represented by the formula (p1) bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition portion (B1) containing a carboxylic acid moiety, or a polyurethane skeleton (A) containing a carboxyl group and a formula (p2) bonded to at least a part of the carboxyl group. The solvent used for the synthesis of the hydroxy-containing resin (P) having the aliphatic oxide ring-opening addition portion (B2) containing the cycloalkene oxide ring-opening addition portion represented can be used as it is, and the viscosity and printability can be used. Other solvents can be added for adjustment. Also, other solvents can be used. When another solvent is used, the reaction solvent may be distilled off before and after addition of a new solvent to replace the solvent.

  However, in view of the complexity of the operation and energy cost, it is preferable to use the solvent used for the synthesis of the hydroxy-containing resin as it is.

  Solvents that can be used for adjusting the viscosity and printability vary depending on the printing mode, but are not particularly limited as long as they have low reactivity with the isocyanate compound, but do not include a basic functional group such as an amine, Solvents having a boiling point of at least 60 ° C, preferably at least 110 ° C, are preferred. Examples of such a solvent include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and propylene glycol monoethyl ether monoacetate. , Dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, Acetone, methyl ethyl ketone, cyclohexyl Non, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, can be mentioned chloroform and methylene chloride.

  When the above-mentioned isocyanate blocking compound is used as the polyisocyanate compound (Q), methanol, ethanol, isopropanol, cyclohexanol, benzyl alcohol or the like which reacts with isocyanate can also be used as the solvent.

  The solid content concentration in the protective film ink varies depending on the desired film thickness and printing method, but is preferably from 20 to 90% by mass, and more preferably from 30 to 80% by mass.

  The prepared protective film ink forms a printing pattern on a substrate with a conductive pattern by a printing method such as a screen printing method, a gravure printing method, or an ink jet method, and after distilling off the solvent as necessary, the printing pattern is formed. By performing heat treatment, light irradiation, or microwave heating, the film is cured to form a protective film for the conductive pattern.

  Examples of the substrate on which the conductive pattern is formed include a polyimide film, a polyester film, a ZEONOR (registered trademark) film, and a polycarbonate film.

  Examples of the conductive pattern include those in which particles of a metal and / or a metal oxide such as silver or copper, nanowires, nanotubes, and the like are formed into an ink to form a printed pattern on a base material, and the printed pattern is converted into a conductor. In particular, when a transparent conductive pattern is prepared using silver nanoparticle ink or silver nanowire ink, the surface area per unit mass of silver is large, and fine wiring and the like have low insulation reliability at high temperature and high humidity. The protection is effective by the protective film resin according to the embodiment.

  Hereinafter, examples of the present invention will be described. However, these examples are merely examples for suitably describing the present invention, and do not limit the present invention in any way.

Synthesis example of polyurethane skeleton (A) containing carboxyl group [Synthesis example 1]
In a 2 L three-necked flask equipped with a stirrer, a thermometer and a condenser, C-1015N (polycarbonate diol, manufactured by Kuraray Co., Ltd., raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8-octane) as a polyol compound Diol = 15:85, molecular weight 964) 211 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei) 40.0 g as a dihydroxyl compound having a carboxyl group, and γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent 379 g), and the 2,2-dimethylolbutanoic acid was dissolved at 90 ° C.

  The temperature of the reaction solution was lowered to 70 ° C., and 128 g of Desmodur (registered trademark) -W (methylenebis (4-cyclohexylisocyanate), manufactured by Sumika Bayer Urethane Co., Ltd.) was dropped as a polyisocyanate over 30 minutes using a dropping funnel. . After completion of the dropwise addition, the reaction was carried out at 80 ° C. for 1 hour, then at 100 ° C. for 1 hour, and then at 120 ° C. for 2 hours. After confirming that the isocyanate had almost disappeared by IR, the reaction was continued at 120 ° C. for 1.5 hours. Was done. The number average molecular weight of the obtained carboxyl group-containing polyurethane was 34100, and the acid value of the solid content was 40.2 mgKOH / g.

<Product identification>
1 g of the reaction solution after the above synthesis was added dropwise to 10 g of methanol, allowed to stand, and the supernatant was removed by decantation. 10 g of methanol was added again, and the mixture was allowed to stand and the supernatant was removed three times. Finally, the residue was concentrated under reduced pressure to obtain a solid resin. The obtained resin was identified using ¹ H-NMR measurement (JNM-EX270 manufactured by JEOL, dissolved in deuterated chloroform and measured), and IR measurement (Nicolet 6700, measured by applying to an AgCl plate). The polyurethane skeleton (A) containing a carboxyl group was confirmed.

[Synthesis Example 2]
Using the same apparatus as in Synthesis Example 1, 211 g of G-1000 (manufactured by Nippon Soda Co., Ltd., hydroxyl-terminated polybutadiene (1,2-skeleton 90%), molecular weight 1539) as a polyol compound, 211 g of dihydroxy having a carboxyl group 63.4 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei) as a compound, 400 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel) as a solvent, and Desmodur (registered trademark) -I (isophorone) as a polyisocyanate The reaction was carried out in the same manner as in Synthesis Example 1 using 125 g of diisocyanate) and Sumika Bayer Urethane Co., Ltd.). The number average molecular weight of the obtained carboxyl group-containing polyurethane was 10,900, and the acid value of the solid content was 60.3 mgKOH / g.

[Synthesis Example 3]
Using the same apparatus as in Synthesis Example 1, 117 g of PTXG-1000 (1,4-butanediol-neopentyl glycol polyether copolymer (manufactured by Asahi Kasei Fibers, Ltd.)) having a carboxyl group as a polyol compound was used. 64.1 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei) as a dihydroxyl compound, 304 g of diethylene glycol monoethyl ether monoacetate (manufactured by Daicel) as a solvent, and Desmodur (registered trademark)-as a polyisocyanate The reaction was carried out using 122 g of I (isophorone diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd.) in the same manner as in Synthesis Example 1. The number average molecular weight of the obtained carboxyl group-containing polyurethane was 6120, and the acid value of the solid content was 79.8mgKOH It was g.

[Synthesis Example 4]
Using the same apparatus as in Synthesis Example 1, as a polyol compound, Kuraray polyol C-1090 (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 3-methyl-1,5-pentanediol + 1,6-hexanediol raw material 90) 10, molecular weight 992) 206 g, 2,3-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxyl compound having a carboxyl group, 63.4 g, diethylene glycol monoethyl ether acetate (manufactured by Daicel) 400 g as a solvent, A reaction was carried out in the same manner as in Synthesis Example 1 using 131 g of NBDI (norbornane diisocyanate, manufactured by Mitsui Chemicals Fine Co., Ltd.) as a polyisocyanate. The number average molecular weight of the obtained carboxyl group-containing polyurethane was 6570, and the acid value of the solid content was 60.6 mgKOH / g.

Hydroxy having a polyurethane skeleton containing a carboxyl group (A) and an aliphatic oxide ring-opening addition portion (B1) containing an alkene oxide ring-opening addition portion represented by the formula (p1) bonded to at least a part of the carboxyl group. Resin-containing resin (P) or a carboxyl group-containing polyurethane skeleton (A) and an aliphatic oxide containing a cycloalkene oxide ring-opening addition portion represented by the formula (p2) bonded to at least a part of the carboxyl group. Synthesis Example of Hydroxy-Containing Resin (P) Having Cycloaddition Unit (B2) [Synthesis Example 5]
100 g of the carboxyl group-containing polyurethane solution (solid content concentration: 50% by mass, acid value: 40.2 mg-KOH / g) obtained in Synthesis Example 1 was transferred to a 300 ml autoclave, purged with nitrogen gas, and then subjected to a nitrogen gas pressure of 0.5 MPa. Then, the temperature was raised to 80 ° C., and 4.84 g of ethylene oxide (manufactured by Mitsubishi Chemical Corporation) was introduced into the autoclave via a mass flow controller, and the temperature was raised to 120 ° C. and reacted for 6 hours. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 3. The obtained resin composition (hereinafter referred to as resin composition 1) had a number average molecular weight of 22,700 solids, an acid value of 0.2 mg-KOH / g, a hydroxyl value of 37.1 mg-KOH / g, and a solid concentration. Was 52% by mass.

<Product identification>
1 g of the reaction solution after the above synthesis was added dropwise to 10 g of methanol, and after standing, the supernatant was removed. Methanol was added again, and the mixture was allowed to stand and the supernatant was removed three times. Finally, the residue was concentrated under reduced pressure to obtain a liquid resin. The obtained resin was identified by ¹ H-NMR measurement and IR measurement, a proton peak at which an epoxy ring was opened was confirmed at around 2.4 ppm in NMR measurement, and CH at around 1040 cm ⁻¹ was confirmed by IR measurement. From the peak strength based on the -OH stretching and the increase in the peak strength based on the OH stretching vibration near 3300 cm- ¹ , it was confirmed that the obtained resin was a polyurethane resin to which ethylene oxide was grafted. Further, ethylene oxide reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 0.8 ppm to 2.5 ppm in NMR measurement and a proton ratio of 2.5 ppm to 5.0 ppm (n ₁ in the formula (p1)) Was 2.5. 1 and 2 show a ¹ H-NMR spectrum and an IR spectrum of the resin composition 1 obtained in Synthesis Example 5, respectively.

[Synthesis Example 6]
100 g of the carboxyl group-containing polyurethane solution (solid content concentration: 50% by mass, acid value: 40.2 mg-KOH / g) obtained in Synthesis Example 1 was transferred to a 300 ml autoclave, and after purging with nitrogen gas, propylene oxide (Tokyo Kasei Co., Ltd.) 8.32 g (purchased from a company) was introduced into the autoclave by a pump, and the temperature was raised to 120 ° C. while applying a nitrogen gas pressure of 0.5 MPa, followed by a reaction for 6 hours. In this reaction, the molar ratio of propylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter referred to as resin composition 2) had a number average molecular weight of solids of 28,000, an acid value of almost zero, a hydroxyl value of 38.4 mg-KOH / g, and a solids concentration of 54% by mass. there were.

<Product identification>
The solid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak at which an epoxy ring was opened at around 2.4 ppm in NMR measurement was confirmed. from IR measurement, the CH-OH stretching near 1040 cm ^-1 Motozukupi - Motozukupi the OH stretching vibration in the vicinity of click intensity and 3300 cm ^-1 - the increase of the click intensity, that propylene oxide is a polyurethane resin grafted confirmed. Average of propylene oxide (n ₁ in the formula (p1)) reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 0.8 ppm to 2.5 ppm and a proton ratio of 2.5 ppm to 5.0 ppm in NMR measurement. The value was confirmed to be 1.6.

[Synthesis Example 7]
100 g of the carboxyl group-containing polyurethane solution (solid content concentration: 50% by mass, acid value: 60.3 mg-KOH / g) obtained in Synthesis Example 2 was transferred to a 300 ml autoclave, purged with nitrogen gas, and then subjected to a nitrogen gas pressure of 0.5 MPa. The temperature was raised to 80 ° C., and 9.68 g of ethylene oxide was introduced into the autoclave via a mass flow controller, and the temperature was raised to 120 ° C. and reacted for 6 hours. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter referred to as resin composition 3) had a number average molecular weight of 6800 solids, an acid value of 0.2 mg-KOH / g, a hydroxyl value of 57.8 mg-KOH / g, and a solid concentration. Was 53% by mass.

<Product identification>
The liquid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak having an epoxy ring opened at around 2.4 ppm in NMR measurement was confirmed. measurements from, Motozukupi the CH-OH stretching near 1040 cm ^-1 - click strength and 3300cm Motozukupi the OH stretching vibration in the vicinity of ^-1 - from increased click strength, confirmed that ethylene oxide is a polyurethane resin grafted Was done. In addition, ethylene oxide reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 5.0 ppm to 6.5 ppm and a proton ratio of 0.8 ppm to 4.9 ppm in NMR measurement (n ₁ in the formula (p1)) Was confirmed to be 3.5.

[Synthesis Example 8]
100 g of the carboxyl group-containing polyurethane solution (solid content concentration: 50% by mass, acid value: 79.8 mg-KOH / g) obtained in Synthesis Example 3 was transferred to a 300 ml autoclave, purged with nitrogen gas, and then subjected to a nitrogen gas pressure of 0.5 MPa. Then, the temperature was raised to 80 ° C., and 12.8 g of ethylene oxide was introduced into the autoclave via a mass flow controller, and the temperature was raised to 120 ° C. and reacted for 6 hours. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter, referred to as resin composition 4) had a number average molecular weight of 7400 solids, an acid value of 0.5 mg-KOH / g, a hydroxyl value of 73.6 mg-KOH / g, and a solid concentration. Was 56% by mass.

<Product identification>
The liquid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak having an epoxy ring opened at around 2.4 ppm in NMR measurement was confirmed. measurements from, Motozukupi the CH-OH stretching near 1040 cm ^-1 - click strength and 3300cm Motozukupi the OH stretching vibration in the vicinity of ^-1 - from increased click strength, confirmed that ethylene oxide is a polyurethane resin grafted Was done. Further, ethylene oxide reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 0.8 ppm to 2.5 ppm in NMR measurement and a proton ratio of 2.5 ppm to 5.0 ppm (n ₁ in the formula (p1)) Was found to be 3.7.

[Synthesis Example 9]
100 g of the carboxyl group-containing polyurethane solution (solid content concentration: 50% by mass, acid value: 60.6 mg-KOH / g) obtained in Synthesis Example 4 was transferred to a 300 ml autoclave, purged with nitrogen gas, and then subjected to a nitrogen gas pressure of 0.5 MPa. Then, the temperature was raised to 80 ° C., and 9.73 g of ethylene oxide was introduced into the autoclave via a mass flow controller, and the temperature was raised to 120 ° C. and reacted for 6 hours. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter referred to as resin composition 5) had a number average molecular weight of 8900 solids, an acid value of 0.1 mg-KOH / g, a hydroxyl value of 60.1 mg-KOH / g, and a solid concentration. Was 54% by mass.

<Product identification>
The liquid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak having an epoxy ring opened at around 2.4 ppm in NMR measurement was confirmed. measurements from, Motozukupi the CH-OH stretching near 1040 cm ^-1 - click strength and 3300cm Motozukupi the OH stretching vibration in the vicinity of ^-1 - from increased click strength, confirmed that ethylene oxide is a polyurethane resin grafted Was done. Further, ethylene oxide reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 0.8 ppm to 2.5 ppm in NMR measurement and a proton ratio of 2.5 ppm to 5.0 ppm (n ₁ in the formula (p1)) Was found to be 3.6.

[Synthesis Example 10]
3.52 g of cyclohexene oxide (purchased from Wako Pure Chemical Industries, Ltd.) was added to 100 g of the carboxyl group-containing polyurethane solution (solid content concentration 50% by mass, acid value 40.2 mg-KOH / g) obtained in Synthesis Example 1, and Phenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd.) (0.05 g) was added, the mixture was transferred to a 300 ml autoclave, and purged with nitrogen gas. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 1. The obtained resin composition (hereinafter referred to as resin composition 6) had a number average molecular weight of 30100 solids, an acid value of 4.5 mg-KOH / g, a hydroxyl value of 32.3 mg-KOH / g, and a solid concentration. Was 52% by mass.

<Product identification>
The liquid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak with an epoxy ring opened at about 3.1 ppm in NMR measurement was confirmed. measurements from, Motozukupi the CH-OH stretching near 1040 cm ^-1 - click strength and 3300 cm ^-1 Motozukupi the OH stretching vibration in the vicinity of - the increase of the click intensity, confirmed that cyclohexene oxide is a polyurethane resin grafted Was done. Further, cyclohexene oxide reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 0.8 ppm to 2.5 ppm in NMR measurement and a proton ratio of 2.5 ppm to 5.0 ppm (n ₂ in the formula (b2)) Was found to be 0.6.

[Synthesis Example 11]
6.48 g of styrene oxide (purchased from Tokyo Chemical Industry Co., Ltd.) in 100 g of the carboxyl group-containing polyurethane solution (solid content concentration 50% by mass, acid value 40.2 mg-KOH / g) obtained in Synthesis Example 1, and triphenyl as a catalyst Phosphine (manufactured by Hokuko Chemical Co., Ltd.) (0.05 g) was added, the mixture was transferred to a 300 ml autoclave and purged with nitrogen gas. In this reaction, the molar ratio of ethylene oxide (epoxy group) to carboxyl group in the polyurethane skeleton (A) ((Epoxy) / (Acid)) is 1. The obtained resin composition (hereinafter referred to as resin composition 7) had a number average molecular weight of 28100 solids, an acid value of 1.6 mg-KOH / g, a hydroxyl value of 35.3 mg-KOH / g, and a solid concentration. Was 53% by mass.

<Product identification>
The liquid resin obtained by the same purification as in Synthesis Example 5 was identified by ¹ H-NMR measurement and IR measurement, and a proton peak derived from a benzene ring was confirmed at about 7.3 ppm in NMR measurement. , Motozukupi the CH-OH stretching near 1040 cm ^-1 - click strength and 3300 cm ^-1 Motozukupi the OH stretching vibration in the vicinity of - the increase of the click intensity, styrene oxide was confirmed to be polyurethane resin grafted . Styrene reacted with a carboxyl group in the urethane resin calculated from a proton ratio of 7.0 ppm to 7.5 ppm (excluding peaks derived from heavy chloroform) in NMR measurement and a proton ratio of 0.8 ppm to 5.0 ppm. It was confirmed that the average value of the oxide (n ₁ in the formula (p1)) was 0.8.

The measurement of the hydroxyl value was performed as follows.
About 2.0 g of a sample is precisely weighed in a 200 ml eggplant-shaped flask using a precision balance, and 5 ml of an acetylation reagent is added thereto using a pipette. Attach a Dimroth cooling tube and heat for 1 hour in an oil bath adjusted from 95 ° C to 100 ° C. After standing to cool, 1 ml of pure water was used to wash the liquid attached to the wall of the flask, and the flask was shaken well, and further heated for 10 minutes in an oil bath fitted with a Dimroth and adjusted to 5 ° C to 100 ° C. After cooling, the walls of the flask are washed with 5 ml of ethanol. A few drops of the phenolphthalein solution are added as an indicator, and titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution.
In addition, the above test shall be performed without any sample, and shall be a blank test.
The value obtained by using the following formula from the result is defined as the hydroxyl value of the resin.
Hydroxyl value (mgKOH / g) = [(B−C) × f × 28.05] / S + D
B: Amount (ml) of 0.5 mol / L potassium hydroxide-ethanol solution used for blank test
C: Amount (ml) of 0.5 mol / L potassium hydroxide-ethanol solution used for titration
f: Factor of 0.5 mol / L potassium hydroxide-ethanol solution S: Sample collection amount (g)
D: Acid value As the acetylating reagent, 25 g of acetic anhydride was placed in a 100 ml brown volumetric flask, and pyridine was added to make 100 ml.

Preparation of Silver Nanowire Coated Film Silver nanowires (wire diameter: about 40 nm, length: about 10 μm) are dispersed in ethanol (0.25% by mass), and this solution is drop-coated on Lumirror (registered trademark) 125U98 (manufactured by Toray Industries, Inc.). Then, the silver nanowires were deposited by applying three drops and air-drying for 6 hours. Next, using a Xenon irradiator Pulse Forge 3300 manufactured by NovaCentrix, the pulsed light was irradiated at a drive voltage of a light source of 600 V and an irradiation time of 60 μs to form a transparent conductive pattern. The surface resistance was approximately 10Ω.

Examples 1 to 10 and Comparative Examples 1 and 2 <Evaluation as protective film resin>
Polyisocyanate compound (Q) (Desmodur (registered trademark) -I,), blocked isocyanate (Desmodur (registered trademark) BL4265SN, duranate (registered trademark) SBB-70P, duranate (registered trademark) 17B shown in Table 1 -60P), using a Dabco T-12 catalyst (dibutyltin dilaurate, DBTDL) and mixing according to the formulation shown in Table 2, and then using a rotation / revolution vacuum mixer Awatori Naritaro ARV-310 (manufactured by Shinky Corporation). After mixing (500 rotations and 1500 revolutions for 5 minutes), inks for coating (Examples 1 to 10) were prepared.

The obtained ink was applied to a silver nanowire coating film coated on a Lumirror (registered trademark) 125U98 (manufactured by Toray Industries, Inc.) using a bar coater so that the surface resistance became approximately 100Ω, and air-dried at 120 ° C. for 1 hour. To cure the resin. Comparative Example 1 shows a case where the ink is not coated, and Comparative Example 2 shows a commercially available overcoat resin (JELCON IN-10C: an overcoat resin manufactured by Jujo Chemical Co., Ltd., cured by UV irradiation (200 mj at room temperature using a halogen lamp). / Cm ² ))).

<Evaluation of warpage>
After depositing the silver nanowires on the base material, the film before curing obtained by applying the inks of Examples 1 to 10 (forming a protective film) is cut into 10 cm × 5 cm, and cured at 120 ° C. for 1 hour with the coated surface facing upward. (Comparative Example 2 was performed by UV irradiation at room temperature). The cured film was placed on a base surface (reference surface), and the warpage of the film edge was measured as shown in FIG.

<Adhesion evaluation>
Using a cutter knife with a new blade, 11 cuts were made in the cured film at intervals of 1 mm, and after changing the direction of 90 °, 11 more cuts were formed to form 100 1-mm squares. A cellophane adhesive tape was attached so as to adhere to the cut printing surface, and the cellophane adhesive tape was rubbed with an eraser to adhere the tape to the coating film. One to two minutes after the tape was applied, the tape was held at a right angle to the printing surface with the edge of the tape held, and the tape was instantaneously peeled off and judged according to the old JIS K5400. Table 2 shows the results.

<Reliability test>
The coating film having the components shown in Table 2 was placed in a high-temperature bath at 100 ° C. and a constant-temperature and constant-humidity bath controlled at 85 ° C. and a relative humidity of 85%, and the surface resistance was measured before and after 500 hours. Table 2 shows the obtained results. The surface resistance was measured using a non-contact resistance meter (EC-80P manufactured by Napson Corporation).

Claims (13)

It has a polyurethane skeleton (A) containing a carboxyl group and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part represented by the following formula (p1) bonded to at least a part of the carboxyl group. An aliphatic oxide containing a hydroxy-containing resin (P) and a carboxyl group-containing polyurethane skeleton (A) and a cycloalkene oxide ring-opening addition unit represented by the following formula (p2) bonded to at least a part of the carboxyl group: and at least one hydroxy-containing resin (P) having a ring-opening addition portion (B2), I the reaction product der with the polyisocyanate compound (Q),
The polyurethane skeleton (A) is a polyurethane skeleton synthesized using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as a monomer,
Wherein (a2) polyol - Le compounds, polycarbonate polyols, polyester polyols, polylactone polyols, polybutadiene polyols, and polysilicone having hydroxyl groups at both ends or der polyurethane resins characterized by Rukoto of.
In the above formula (p1), n ₁ is an integer of ₁ to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
In the above formula (p2), n ₂ is an integer of 1 to 10, and A ¹ is an atom forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded. It is a group. It has a polyurethane skeleton (A) containing a carboxyl group and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part represented by the following formula (p1) bonded to at least a part of the carboxyl group. An aliphatic oxide containing a hydroxy-containing resin (P) and a carboxyl group-containing polyurethane skeleton (A) and a cycloalkene oxide ring-opening addition unit represented by the following formula (p2) bonded to at least a part of the carboxyl group: A reaction product of at least one of the hydroxy-containing resin (P) having the ring-opening addition portion (B2) and the polyisocyanate compound (Q),
The polyurethane skeleton (A) is a polyurethane skeleton synthesized using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as a monomer,
Wherein (a2) the polyurethane resin polyol compound characterized in that it is a polycarbonate diol or polybutadiene polyols.
In the above formula (p1), n ₁ is an integer of ₁ to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
In the above formula (p2), n ₂ is an integer of 1 to 10, and A ¹ is an atom forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded. It is a group.   The polyurethane resin according to claim 1 or 2, wherein the (a1) polyisocyanate compound is an alicyclic compound having 6 to 30 carbon atoms other than carbon atoms in the isocyanato group (-NCO group).   (A3) The dihydroxy compound having a carboxyl group is a carboxylic acid or aminocarboxylic acid having a molecular weight of 200 or less and having at least two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms. Item 4. The polyurethane resin according to any one of Items 1 to 3. (A3) The dihydroxy compound having a carboxyl group is selected from the group consisting of 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, and N, N-bishydroxyethylalanine. The polyurethane resin according to claim 4 , wherein the polyurethane resin is at least one kind. In the formula (p1), n ₁ is ₁ to 10, and R ¹ and R ² are each independently a hydrogen atom or a methyl group, or at least one of R ¹ and R ² is a hydrogen atom, and Is a C1-C10 alkyl group or a phenyl group, The polyurethane resin as described in any one of Claims 1 thru | or 5 . Formula (p2) is an integer n ₂ is 1 to 3 in the carbon atoms of A ¹ has included two carbon atoms to which the A ¹ are bonded form a 6-12 alicyclic hydrocarbon group The polyurethane resin according to any one of claims 1 to 6 , which is an atomic group. The polyurethane resin according to any one of claims 1 to 7 , wherein the polyisocyanate compound (Q) is an aliphatic isocyanate compound or a blocked isocyanate derived therefrom. The polyisocyanate compound (Q) is caprolactam, ketoximes, phenols, according to any one of claims 1 to 8 comprising the isocyanato groups which are blocked with a compound having active hydrogen selected from the group consisting of secondary amine Polyurethane resin. It has a polyurethane skeleton (A) containing a carboxyl group and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part represented by the following formula (p1) bonded to at least a part of the carboxyl group. An aliphatic oxide containing a hydroxy-containing resin (P) and a carboxyl group-containing polyurethane skeleton (A) and a cycloalkene oxide ring-opening addition unit represented by the following formula (p2) bonded to at least a part of the carboxyl group: At least one of a hydroxy-containing resin (P) having a ring-opening addition portion (B2);
A polyisocyanate compound (Q),
A solvent;
An overcoat composition comprising:
In the above formula (p1), n ₁ is an integer of ₁ to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
In the above formula (p2), n2 is an integer of from 1 to 10, ^{A 1} is an atomic group number of carbon atoms including the two carbon atoms to which the ^{A 1} are attached to form an alicyclic hydrocarbon group having 4 to 14 It is. A step of reacting a carboxyl group contained in a polyurethane resin having a carboxyl group-containing polyurethane skeleton (A) with at least one of an alkene oxide represented by the formula (x1) and a cycloalkene oxide represented by the formula (x2) When,
Reacting a polyisocyanate compound (Q) with the hydroxy group-containing resin (P) obtained in the above step;
Equipped with a,
The polyurethane skeleton (A) is a polyurethane skeleton synthesized using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as a monomer,
Wherein (a2) polyol - Le compounds, polycarbonate polyols, polyester polyols, polylactone polyols, polybutadiene polyols, and the manufacturing method of a polyurethane resin which either der wherein Rukoto of polysilicone having hydroxyl groups at both ends.
In Formula (x1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
(In the formula (x2), A ¹ represents an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded.) A step of reacting a carboxyl group contained in a polyurethane resin having a carboxyl group-containing polyurethane skeleton (A) with at least one of an alkene oxide represented by the formula (x1) and a cycloalkene oxide represented by the formula (x2) When,
Reacting a polyisocyanate compound (Q) with the hydroxy group-containing resin (P) obtained in the above step;
With
A method for producing a polyurethane resin, wherein the alkene oxide represented by the formula (x1) is ethylene oxide, propylene oxide or styrene oxide.
In Formula (x1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.
(In the formula (x2), A ¹ represents an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which A ¹ is bonded.) The method for producing a polyurethane resin according to claim 11 or 12 , wherein the cycloalkene oxide represented by the formula (x2) is cyclohexene oxide.