JP6478742B2 - Urethane (meth) acrylate resin, UV curable resin composition, composition for overcoat, and method for producing urethane (meth) acrylate resin - Google Patents

Description

  The present invention relates to a urethane (meth) acrylate resin and a UV curable resin composition using the same. More specifically, the present invention relates to a polyurethane (meth) acrylate resin suitable for a protective film of a conductive pattern obtained by firing metal ink or metal nanowire ink.

  Transparent conductive films include liquid crystal displays (LCD), plasma display panels (PDP), organic electroluminescence displays, transparent electrodes for solar cells (PV) and touch panels (TP), antistatic (ESD) films, and electromagnetic shielding (EMI). It is used in various fields such as film. Conventionally, those using ITO (Indium Tin Oxide) have been used as these transparent conductive films. However, the supply stability of indium is low, the manufacturing cost is high, the flexibility is not high, and the temperature is high during film formation. There was a problem that was necessary. Therefore, a search for a transparent conductive film that replaces ITO has been actively pursued. Among them, the transparent conductive film containing metal nanowires has excellent conductivity, optical properties, and flexibility, can be formed by a wet process, has a low manufacturing cost, and requires a high temperature during film formation Therefore, it is optimal as an ITO alternative transparent conductive film. 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 that it has a large surface area per weight of silver and easily reacts with various compounds and thus lacks environmental resistance. The nanostructures easily corrode due to the influence and the influence of oxygen and moisture in the air exposed by long-term storage, etc., and the electrical conductivity tends to decrease. In particular, in applications such as electronic materials, a physical cleaning process using a brush or the like is often used in order to prevent adhesion of fine impurities, dust, and dust to the surface of the substrate. There is also a problem that the surface is 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 to impart environmental resistance and scratch resistance to the transparent conductive film. As protective films used for transparent conductive films containing silver nanowires, protective films for transparent conductive films using urethane resins and the like, and protective films for various optical materials including polyester polyamic acid and epoxy resins. Protective films using inorganic silicon oxides are known (see Patent Documents 1 to 5).

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

  However, these protective films do not satisfy all the above characteristics. In addition, when used as a protective film, it is desirable to cure quickly by radiation such as UV, not by heating in consideration of productivity, and the surface hardness should be higher considering the specification as a transparent conductive film. More desirable.

  The present invention has been made in view of these problems, and the object thereof is a protective film resin for metal nanowires that is excellent in environmental resistance and scratch resistance as a protective film for metal nanowires and can be cured by an electron beam such as UV. On offer.

One embodiment of the present invention is a urethane (meth) acrylate resin. The urethane (meth) acrylate resin includes a polyurethane skeleton containing a carboxyl group (A) represented by the following formula (p1) and an alkene oxide ring-opening addition moiety bonded to at least a part of the carboxyl group. Bonded to at least part of the carboxyl group and the hydroxy group-containing resin (P) having the aliphatic oxide ring-opening addition part (B1) and the polyurethane skeleton (A) represented by the following formula (p2) and containing the carboxyl group The compound (Q) having a (meth) acryloyl group and an isocyanato group is reacted with at least one of the hydroxy-containing resin (P) having the aliphatic oxide ring-opening addition part (B2) including the cycloalkene oxide ring-opening addition part. Obtained.
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 Z is an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which Z is bonded. .

  In the urethane (meth) acrylate resin of the above embodiment, the polyurethane skeleton (A) is a monomer comprising (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group. It may be a polyurethane skeleton synthesized as

  The (a1) polyisocyanate compound may be an alicyclic compound having 6 to 30 carbon atoms other than carbon atoms in the isocyanato group (—NCO group).

  The (a2) polyol compound may be a polycarbonate diol or a polybutadiene polyol.

  (A3) Even if the dihydroxy compound having a carboxyl group is a carboxylic acid or aminocarboxylic acid having a molecular weight of 200 or less and having any two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms Good.

  (A3) The dihydroxy compound having a carboxyl group comprises 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, and N, N-bishydroxyethylalanine. One type or two or more types of groups may be used.

N ₁ in the formula (p1) is 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 May be an alkyl group having 1 to 10 carbon atoms or a phenyl group.

In the formula (p2), n ₂ is an integer of 1 to 3, and Z is an atomic group forming an alicyclic hydrocarbon group having 6 to 12 carbon atoms including two carbon atoms to which the Z is bonded. It may be.

  The compound (Q) may be one in which the compound (Q) contains one or more (meth) acryloyl groups in one molecule and has one isocyanato group, or the isocyanato group is protected. . In addition, 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and 2- (0- [1′-methylpropylideneamino) methacrylate which is a block body thereof ] Carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate may be selected.

  Another embodiment of the present invention is a UV curable resin composition. The said UV curable resin composition contains the urethane (meth) acrylate resin of any one aspect mentioned above, and a photoinitiator.

  Yet another embodiment of the present invention is an overcoat composition. The overcoat composition contains the urethane (meth) acrylate resin or UV curable resin composition of any of the above-described embodiments.

Yet another embodiment of the present invention is a method for producing a urethane (meth) acrylate resin. The production method includes at least one of a carboxyl group and an alkene oxide represented by the formula (x1) and a cycloalkene oxide represented by the formula (x2) contained in the polyurethane resin having a polyurethane skeleton (A) containing a carboxyl group. And a step of reacting the hydroxy group-containing resin (P) obtained in the above step with a compound (Q) having a (meth) acryloyl group and an isocyanato group.
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), Z represents an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which the Z is bonded.)

  In the production method described above, 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 can also be included in the scope of the invention for which patent protection is sought by this patent application.

  According to the present invention, when used as a protective film for conductive patterns such as wiring and electrodes printed with metal ink, it is possible to obtain a highly reliable conductive pattern with little decrease in conductive characteristics, In particular, it is useful for conductive patterns with low reliability of conductive properties such as silver nanowires.

2 is a ¹ H-NMR spectrum of a resin composition according to Synthesis Example 5. 4 is an IR spectrum of the resin composition according to Example 5. 1 is a ¹ H-NMR spectrum of a urethane acrylate resin according to Example 1. 2 is an IR spectrum of the urethane acrylate resin according to Example 1.

  Embodiments of the present invention will be described below. In the present specification, (meth) acrylate means acrylate or methacrylate, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylic acid means acrylic acid or methacrylic acid.

The urethane (meth) acrylate resin according to the embodiment includes a polyurethane skeleton (A) represented by (p1) and an alkene oxide ring-opening addition moiety bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition part (B1) containing, and a polyurethane skeleton (A) containing a carboxyl group represented by the following formula (p2) and at least a part of the carboxyl group A compound (Q) having a (meth) acryloyl group and an isocyanato group on at least one of the hydroxy-containing resin (P) having an aliphatic oxide ring-opening addition part (B2) including a cycloalkene oxide ring-opening addition part bonded to It is a resin obtained by reacting. The compound (Q) preferably contains one or more (meth) acryloyl groups and one isocyanato group in one molecule.
Wherein (p1), _{n 1} is an integer from 1 to 50, preferably 1 to 30, more preferably from 1 to 10. When n ₁ is larger than 50, the hydrophilicity is increased and the moisture absorption rate is increased, so that the insulation reliability 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. In consideration of availability, R ¹ and R ² are preferably 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. Z is an atomic group that forms an alicyclic hydrocarbon group having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, together with the two carbon atoms to which Z is bonded.

<Polyurethane skeleton (A) having a carboxyl group constituting the hydroxy-containing resin (P)>
The number average molecular weight of the polyurethane skeleton (A) containing a carboxyl group is preferably 1,000 to 100,000, and more preferably 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 coated film after printing may be impaired. If the molecular weight exceeds 100,000, the solubility of the polyurethane in the solvent becomes low and the coating dissolves. However, since the viscosity becomes too high, restrictions may be increased in terms of use.

In this specification, unless otherwise specified, the GPC measurement conditions are as follows.
Device 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 amount: sample loop 100 μl Sample concentration: prepared to about 0.1% by mass

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

In the present specification, the acid value of the resin is a value measured by the following method.
About 0.2 g of a sample is precisely weighed with a precision balance in a 100 ml Erlenmeyer flask, and 10 ml of a mixed solvent of ethanol / toluene = 1/2 (mass ratio) is added and dissolved therein. Further, 1 to 3 drops of phenolphthalein ethanol solution as an indicator is added to this container, and the sample is sufficiently stirred until it becomes uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is when the indicator is 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 (mg-KOH / g) = [B × f × 5.611] / S
B: Amount of 0.1N potassium hydroxide-ethanol solution used (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 obtained by using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as a monomer. It is a skeleton of a polyurethane resin to be synthesized. Hereinafter, each monomer will be described in more detail.

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

  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, Examples include lysine diisocyanate, 2,2'-diethyl ether diisocyanate, and dimer acid diisocyanate.

  Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and 3-isocyanate. Tomethyl-3,3,5-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, and 2,4-trimethyl. Range isocyanate, 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 di- And isocyanate.

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

  (A1) The polyisocyanate compound is formed from the polyurethane resin according to the embodiment by using an alicyclic compound having 6 to 30 carbon atoms other than carbon atoms in the isocyanato group (-NCO group). The protective film is highly reliable especially at high temperatures and high humidity, and is suitable for electronic device parts.

  In the (a1) polyisocyanate compound, the alicyclic compound is 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. Desirably included.

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

The number average molecular weight of (a2) polyol compound (a2) polyol compound (however, (a2) polyol compound does not include (a3) dihydroxy compound having a carboxyl group described later) is usually used. It is 250-50,000, Preferably it is 400-10,000, More preferably, it is 500-5,000. 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, hydroxylated polysiloxanes at both ends, and It is a polyol compound having an oxygen atom only in the hydroxyl group and 18 to 72 carbon atoms. Among these, polycarbonate polyol and polybutadiene polyol are preferable in consideration of the balance of water resistance as a protective film, insulation reliability, and adhesion to a substrate.

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

  Specific examples of the polycarbonate polyol represented by the formula (1) include 1,3-propanediol, 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 -L, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecandiol or the like can be used as a raw material.

  The polycarbonate polycarbonate may be a polycarbonate polyol (copolymer polycarbonate polyol) having a plurality of types of alkylene groups in its skeleton. The use of the copolymer 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 the end 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, oxetane compound or tetrahydrofuran compound having 2 to 12 carbon atoms. Yes, for example, represented by the following 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 said C2-C12 diol can also be used individually by making a single polymer, and can also make it a copolymer by using 2 or more types together.

  Specific examples of the polyether polyol represented by the above formula (2) include polyethylene glycol, polypropylene glycol, poly-1,2-butylene glycol, polytetramethylene glycol ( Poly (1,4-butanediol), poly-3-methyltetramethylene glycol, polyneopentyl glycol and the like. For the purpose of improving the compatibility of (polyetherpolyol) and the hydrophobicity of (polyetherpolyol), these copolymers, such as 1,4-butanediol-neopentyl glycol, etc. Can also be used.

The polyester polyol is obtained by dehydration condensation of dicarboxylic acid and diol or ester exchange reaction of diol with lower alcohol ester of dicarboxylic acid, for example, the following structure: It is represented by Formula (3).
In the formula (3), R ⁵ is a residue obtained by removing a hydroxyl group from a corresponding diol (HO—R ⁵ —OH), and R ⁶ is a residue of two corresponding dicarboxylic acids (HOCO—R ⁶ —COOH). It is a residue excluding a carboxyl group, and n ₅ is a positive integer, preferably 2-50.

Specific examples of the diol (HO—R ⁵ —OH) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol -L, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethyleneglycol -L or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, 1,3-cyclohexanedimethanol, 3-xylylene glycol 1,4-xy Renguriko - le, diethylene glycol - Le, triethylene glycol - le, dipropylene glyco - le, and the like.

Specific examples of the dicarboxylic acid (HOCO-R ⁶ -COOH) include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, brassic acid, 1,4-cyclohexanedicarboxylic acid, hexa Hydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4- Naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid are mentioned.

The polylactone polyol is obtained by a condensation reaction between a ring-opening polymer of a lactone and a diol, or a condensation reaction between a diol and a hydroxyalkanoic acid. For example, the following structural formula (4) It is represented by
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 corresponding diol (HO—R ⁸ —OH). ) Is a residue obtained by removing a hydroxyl group, and n ₆ is a positive integer, preferably 2-50.

Specific examples of the hydroxyalkanoic acid (HO—R ⁷ —COOH) include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, and 5-hydroxyhexanoic acid (ε-caprolactone).

  The polybutadiene polyol is, for example, a diol obtained by polymerizing butadiene or isoprene by anionic polymerization and introducing hydroxyl groups at both ends by terminal treatment, and a diol obtained by hydrogen reduction of these double bonds. -

  Specific examples of the polybutadiene polyol include hydroxylated polybutadiene mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)), hydroxylation. Hydrogenated polybutadiene (for example, Polyter H, Polyter HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene having mainly 1,2-repeating units (for example, G-1000, G-2000, G-) 3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxylated hydrogenated polybutadiene (for example, GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxylated polyisoprene (for example, Poly IP (Idemitsu Kosan) ), Hydroxylated hydrogenated polyisoprene (for example, Epole (Idemitsu Kosan Co., Ltd.) Company, Ltd.)), and the like.

The said both terminal hydroxylated poly silicone is represented, for example by following Structural formula (5).
In the formula (5), R ⁹ is independently an aliphatic hydrocarbon divalent residue or an aromatic hydrocarbon divalent residue having 2 to 50 carbon atoms, and n ₇ is a positive integer, preferably 2 to 50 is there. These may contain 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.

  As a commercial item of the said both terminal hydroxylated poly silicone, Shin-Etsu Chemical Co., Ltd. "X-22-160AS, KF6001, KF6002, KF-6003" etc. are mentioned, for example. Specific examples of the above-mentioned “polyol compound having an oxygen atom only in the hydroxyl group and having 18 to 72 carbon atoms” include a diol compound having a skeleton obtained by hydrogenating dimer acid. Examples of the product include “Sovermol (registered trademark) 908” manufactured by Cognis.

  In addition, as long as the effects of the present invention are not impaired, a polyol having a molecular weight of 300 or less and having no repeating unit can be used as the (a2) polyol compound. Specific examples of such low molecular weight diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3. -Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, , 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 Co - le, diethylene glycol - Le, triethylene glycol - le or di propylene glycol, - le, and the like.

(A3) Dihydroxy compound containing a carboxyl group (a3) The dihydroxy compound containing a carboxyl group has a molecular weight of 200 or less having either one selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms. Of these, carboxylic acid or aminocarboxylic acid is preferable 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. 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred. These (a3) dihydroxy compounds containing a carboxyl group can be used singly or in combination of two or more.

  The above-mentioned polyurethane resin having a polyurethane skeleton (A) containing a carboxyl group can be synthesized only from the above three components ((a1), (a2) and (a3)). (A4) a monohydroxy compound and / or (a5) a monoisocyanate compound is reacted for the purpose of imparting the property of cationic property or cationic polymerization, or for the purpose of suppressing the influence of the isocyanate group or hydroxyl group 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 (meta) ) Acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Compounds having radically polymerizable double bonds such as dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxyethanol, glycolic acid, hydroxy Compounds with carboxylic acids such as pivalic acid are listed. It is.

  (A4) Monohydroxy compounds can be used alone or in combination of two or more. Among these compounds, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, glycolic acid, hydroxypivalic acid 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are more preferable.

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

(A5) Monoisocyanate compound (a5) Monoisocyanate compound includes (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) to diisocyanate compound Acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, Trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxyethanol -Radiation of mono adducts 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, dodecyl isocyanate and the like.

  The above-mentioned polyurethane resin having a polyurethane skeleton (A) containing a carboxyl group is described above using a suitable organic solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate. By reacting (a1) 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. Although synthesis is possible, it is preferable that the reaction is carried out without a catalyst because it is not necessary to finally consider mixing of tin or the like.

  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. The solvent which is the above is preferable. Examples of such solvents 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. Propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, acetic acid Ethyl, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexane Non, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, can be mentioned chloroform and methylene chloride.

  In view of the fact that the organic solvent having low solubility of the resulting polyurethane resin is not preferable, and considering that polyurethane is used as the raw material of the ink in the electronic material application, among these, in particular, propylene glycol monomethyl ether monoacetate, Propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, γ-butyrolactone and the like are preferable.

  Although there is no restriction | limiting in particular about the order which charges a raw material, Usually, after preparing (a2) a polyol compound and (a3) the dihydroxy compound which has a carboxyl group first, and making it melt | dissolve in a solvent, 20-150 degreeC, The polyisocyanate compound (a1) is preferably added dropwise at 60 to 120 ° C, and then reacted at 30 to 160 ° C, more preferably 50 to 130 ° C.

  The starting molar ratio of the raw material is adjusted according to the molecular weight and acid value of the target polyurethane resin, but when the (a4) monohydroxy compound is introduced into the polyurethane resin, the end of the polyurethane molecule becomes an isocyanato group. In addition, it is necessary to use (a1) polyisocyanate compound in excess of (a2) polyol compound and (a3) carboxyl group-containing dihydroxy compound (so that the isocyanate group is in excess of the total of hydroxyl groups). .

  Specifically, these charged molar ratios are: (a1) isocyanato group of polyisocyanate compound: ((a2) hydroxyl group of polyol compound + (a3) hydroxyl group of dihydroxy compound having carboxyl group). 5 to 1.5: 1, preferably 0.8 to 1.2: 1, more preferably 0.95 to 1.05: 1.

  Further, (a2) 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 (a4) a monohydroxy compound is used, the number of moles of (a1) polyisocyanate compound is made larger than the number of moles of ((a2) polyol compound + (a3) dihydroxy compound having a carboxyl group), (A4) It is preferable to use the monohydroxy compound in an amount of 0.5 to 1.5 times, preferably 0.8 to 1.2 times the molar amount of the excess moles of the isocyanato group.

  (A5) In the case of using a monoisocyanate compound, the number of moles of ((a2) polyol compound + (a3) dihydroxy compound having a carboxyl group) is set to be larger than the number of moles of (a1) polyisocyanate compound. The molar amount of the hydroxyl group is 0.5 to 1.5 times, preferably 0.8 to 1.2 times.

  (A4) In order to introduce a monohydroxy compound into the polyurethane skeleton (A) containing a carboxyl group, (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group and (a1) a polyisocyanate compound, When the reaction of is almost completed, in order to react the isocyanate group remaining at both ends of the polyurethane skeleton (A) containing a carboxyl group with the (a4) monohydroxy compound, (a4) The monohydroxy compound is added dropwise at 20 to 150 ° C., more preferably 70 to 120 ° C., and then the reaction is completed by maintaining the same temperature.

  (A5) In order to introduce a monoisocyanate compound into a polyurethane skeleton (A) containing a carboxyl group, (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group and (a1) a polyisocyanate compound (A5) monoisocyanate compound in the reaction solution in order to react (A) the hydroxyl groups remaining at both ends of the polyurethane skeleton with (a5) monoisocyanate compound. Is dropped at 20 to 150 ° C., more preferably at 50 to 120 ° C., and then the reaction is completed by holding at the same temperature.

<Aliphatic oxide ring-opening addition part (B1), (B2) constituting the hydroxy-containing resin (P)>
The aliphatic oxide ring-opening addition moieties (B1) and (B2) are represented by the following formula (x1) in the carboxyl group (—COOH) contained in the polyurethane resin having the polyurethane skeleton (A) containing the carboxyl group. Or an aliphatic oxide containing a cycloalkene oxide represented by the formula (x2). A mixture of both in a predetermined ratio can also be reacted. In this case, a hydroxy-containing resin (P) in which the unit represented by the above formula (p1) and the unit represented by the above 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 undergo addition polymerization 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 or a phenyl group, having 1 to 16 carbon atoms Represent. In terms of easy availability, 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 has 1 to 10 carbon atoms. An alkyl group or a phenyl group is preferred. Specifically, examples of the alkene oxide represented by the above formula (x1) include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.
In the formula (x2), Z is the same as Z in the formula (p2), that is, a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group having 2 to 12 carbon atoms, and the carbon number is 4 to 14 alicyclic structures are formed. What is a C6-C12 alicyclic structure is preferable at the point which is easy to acquire. Specific examples of the cycloalkene oxide represented by the above formula (x2) include cycloalkene oxides such as cyclohexene oxide, cyclooctene oxide, cyclodocene oxide, and dicyclopentadiene monooxide.

  As a condition for reacting the above-described polyurethane skeleton (A) containing a carboxyl group with the aliphatic oxide, a catalyst for promoting the reaction of an epoxy group and a carboxylic acid in a solution obtained by synthesizing a polyurethane skeleton (A) containing a carboxyl group And is reacted by heating to 50 to 160 ° C, more preferably 80 to 140 ° C. If the reaction temperature is too low, the speed is 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.

  As the use amount of the polyurethane skeleton (A) containing a carboxyl group and the aliphatic oxide, the epoxy group of the aliphatic oxide is 0.5 equivalent to the carboxyl group in the polyurethane skeleton (A) containing a carboxyl group. The amount is preferably 50 equivalents. When the above equivalent is lower than 0.5, the concentration of the generated hydroxyl group is lowered, and the reaction point with the isocyanate group is lowered, which is not preferable. If the equivalent exceeds 50 equivalents, adverse effects such as a decrease in the moisture absorption rate of the resin itself will occur.

  Obtained by reacting the polyurethane skeleton (A) containing the carboxyl group with an aliphatic oxide containing at least one of the alkene oxide represented by the above formula (x1) and the cycloalkene oxide represented by the formula (x2). The resulting hydroxy-containing resin (P) can also contain some unreacted carboxyl groups. By having an unreacted carboxyl group, the adhesiveness with a base material or metal wiring may improve. The reaction is carried out so that the amount of unreacted carboxyl groups is 50% or less, preferably 20% or less, more preferably 10%, based on the amount of the original carboxyl groups, and the acid value is 0 to 50 mg-KOH / g. A polyurethane resin of preferably 0 to 30 mg-KOH / g, more preferably 0 to 10 mg-KOH / g can be obtained.

  Since the hydroxy-containing resin (P) thus obtained has a hydroxyl group, the number of functional groups can be measured by measuring the hydroxyl group concentration as the 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 when the original urethane resin has a terminal hydroxyl group. 30-140 mg-KOH / g.

  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 must be performed in an inert gas atmosphere, and the boiling point is very high. Since it is low, it is necessary to carry out the reaction under pressure.

  As the reaction catalyst, the carboxyl group contained in the polyurethane skeleton (A) containing a carboxyl group also acts as a catalyst, but a basic compound can be added for the purpose of further increasing the reaction rate and the degree of polymerization. Examples of basic compounds include tertiary amines, phosphine compounds, and quaternary ammonium hydroxides. More specifically, as the 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), 2,4,6-trisdimethylaminomethylphenol and the like. Examples of the phosphine compound include triphenylphosphine, triphenylphosphite, trimethylphosphine, and trimethylphosphite. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide. If the amount used is too small, the added effect will not be obtained, and if it is too large, the electrical insulation of the resulting polyurethane resin will be reduced, so the total amount of the polyurethane skeleton containing carboxyl groups (A) and aliphatic oxides will be reduced. 0.1 to 5 mass%, more preferably 0.5 to 3 mass%.

<Compound (Q) having (meth) acryloyl group and isocyanato group>
Next, the fat containing the alkene oxide ring-opening addition portion bonded to at least a part of the carboxyl group-containing polyurethane skeleton (A) represented by the formula (p1) and the carboxyl group, obtained as described above. Hydroxy-containing resin (P) having a group oxide ring-opening addition part (B1), and a polyurethane skeleton containing a carboxyl group represented by formula (p2) and a cycloalkene bonded to at least a part of the carboxyl group The compound (Q) having a (meth) acryloyl group and an isocyanato group is reacted with at least one of the hydroxy group-containing resin (P) having an aliphatic oxide ring-opening addition part (B2) including an oxide ring-opening addition part. The compound (Q) preferably contains at least one (meth) acryloyl group in one molecule and has one isocyanate group, or a compound in which the isocyanate group is protected.

  Specific examples of the compound (Q) include 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and block bodies having a protecting group for the isocyanato group. There are 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and the like. These compounds may be used alone or in combination of two or more.

  Since the reaction between the hydroxy-containing resin (P) and the compound (Q) is a reaction between a hydroxy group and an isocyanato group, that is, a urethanization reaction, the solvent used so far can be used as it is, It can also be made to react by substituting with a solvent.

  Moreover, it is preferable to put a catalyst for promoting the urethanization reaction if necessary, and if it has been added in advance, it can be used as it is.

  In addition, since it is better that the unreacted content of the compound (Q) in the product is low, it is preferable that the isocyanato group and the hydroxyl group are equivalent or the hydroxyl group is somewhat excessive.

(UV curable resin composition)
By adding a photoinitiator and, if necessary, monomers having other radical polymerizable groups, more preferably monofunctional and polyfunctional acrylates, to the urethane (meth) acrylate resin described above. A UV curable resin composition is obtained. The added amount of the monomers is 50 to 300 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the urethane (meth) acrylate resin. When a solvent-free UV curable resin composition is used, another (poly) acrylate compound that is liquid at room temperature is added, the solvent used so far is distilled off, and then the compound (Q ) May be reacted.

  The amount of photoinitiator to be blended in the UV curable resin composition is not particularly specified, but urethane (meth) acrylate resin (urethane (meth) in the case of containing monomers having other radical polymerizable groups) The total of the acrylate resin and the monomers having other radically polymerizable groups) is 100 to 15 parts by mass, preferably 1 to 10 parts by mass. If the amount exceeds 15 parts by mass, a large amount of photoinitiator remains after UV curing, causing contamination. On the other hand, when the amount is less than 0.5 parts by mass, sufficient reaction does not proceed with UV irradiation, and there is a possibility that a pick-up failure or the like may occur without insufficient adhesion due to insufficient curing.

  The photoinitiator is not particularly limited, but a photoradical initiator is preferably used from the viewpoint of high reactivity with ultraviolet rays. Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentyl. Acetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoinmethi Ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxyketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1- ON (IRGACURE (registered trademark) 651, manufactured by BASF Japan), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE (registered trademark) 184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl-propane- 1-one (DAROCUR (registered trademark) 1173, manufactured by BASF Japan), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE (registered) Trademark) 2959, manufactured by BASF Japan), 2-methyl-1- [4- (methyl) Thio) phenyl] -2-morpholinopropan-1-one (IRGACURE® 907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ( IRGACURE (registered trademark) 369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (IRGACURE (registered) Trademark) 379, manufactured by BASF Japan), dibenzoyl and the like.

  Among these, α-hydroxyketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenylketone derivatives (for example, acetophenone, propiophenone, Benzophenone, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred.

  Furthermore, as an initiator species that can suppress oxygen inhibition on the surface of the cured product, a photoradical initiator having two or more photodegradable groups in the molecule and a hydrogen abstraction type photoradical initiation having three or more aromatic rings in the molecule An agent may be used. As a photo radical initiator having two or more photodegradable groups in the molecule, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2- Methyl-propan-1-one (IRGACURE® 127, manufactured by BASF Japan), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) ) Propan-1-one (trade name ESURE1001M), Methylbenzoylformate (SPEEDCURE (registered trademark) manufactured by MBF LAMBSON) O-Ethoxyimino-1-phenylpropan-1-one (SPEEDCURE (registered trademark) PDO LAMBSON) Manufactured), oligo [2-hydroxy-2-methyl- [4- (1-methylvinyl) phenol Sulfonyl] propanone (trade name ESCURE KIP150 LAMBERTI), and the like. 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [as a hydrogen abstraction type photo radical initiator having three or more aromatic rings in the molecule 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 4-benzoyl-4′methyldiphenyl sulfide, 4-phenylbenzophenone, 4, 4 ′, 4 ″-(hexamethyltriamino) triphenylmethane and the like.

  Moreover, you may use the photoradical initiator characterized by deep part sclerosis | hardenability improvement. Photoradical initiators characterized by improved deep curability include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR® TPO, manufactured by BASF Japan), bis (2,4,6- Acylphosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide A photo radical initiator is mentioned.

  As a photo radical initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE (registered trademark) 184, manufactured by BASF Japan), 2 in terms of the balance between curability and storage stability of the curable composition of the present invention, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR (registered trademark) 1173, manufactured by BASF Japan), bis (4-dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4 -(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (IRGACURE (registered trademark) 127, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1 (IRGACURE® 369, BASF di) Bread), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (IRGACURE (registered trademark) 379, manufactured by BASF Japan) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR (registered trademark) TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE (registered trademark)) 819, manufactured by BASF Japan) and bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide are more preferable.

  These photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  Specific examples of combinations with other compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, diethylethanolamine, dimethylethanolamine, triethanolamine, Combinations with amines such as ethyl-4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, and further combinations with iodonium salts such as diphenyliodonium chloride, methylene blue -And the like in combination with a dye and an amine.

  In addition, when using the said photoradical initiator, polymerization inhibitors, such as a hydroquinone, hydroquinone monomethyl ether, a benzoquinone, a para-tert- butyl techol, can also be added as needed.

  Moreover, you may mix | blend a photosensitizer with UV curable resin composition. Examples of the photosensitizer include triethylamine and tri-n-butylphosphine.

  In addition, you may mix a thermosetting initiator with UV curable resin composition. As the thermosetting initiator, conventionally known ones such as azo type and peroxide type can be used.

  In addition, when polymerizing a resin layer by UV, generally an appropriate amount of a photopolymerization initiator may be added, and an appropriate amount of a photosensitizer may be added if necessary. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoyl benzoate, and thioxanthone. Examples of the photosensitizer include triethylamine and tri-n-butylphosphine.

  The solvent that can be used for adjusting the viscosity and printability of the UV curable resin composition varies depending on the printing mode, but is not particularly limited as long as it has low reactivity with the compound (Q). A solvent having a basic functional group and a boiling point of 50 ° C. or higher, preferably 110 ° C. or higher is preferable. Examples of such solvents 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. Propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, acetic acid Ethyl, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexane Non, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, and chloroform.

  For the purpose of improving workability by reducing the viscosity, improving the physical properties of the molded article, etc., monomers having other radical polymerizable groups can be used in combination with the UV curable resin composition.

  Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryloyl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the ultraviolet crosslinkable group used in the vinyl polymer used in the present invention are preferable.

  Specific examples of the monomers include (meth) acrylate monomers, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone types. Monomers, vinyl halide / vinylidene halide monomers, polyfunctional monomers and the like can be mentioned.

Examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate , N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Isodecyl acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, tridecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) Propyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate Ethyl, (meth) acrylic acid 2-perfluoroethyl- 2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Etc.
Examples of the styrene monomer include styrene and α-methylstyrene.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate and vinyl butyrate.

  Examples of acrylamide monomers include acrylamide and N, N-dimethylacrylamide.

  Examples of the conjugated diene monomer include butadiene and isoprene. Examples of the vinyl ketone monomer include methyl vinyl ketone.

  Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

  Examples of the polyfunctional monomer include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, neopentyl glycol diacrylate, trimethylolpropane polyethoxytriacrylate, Bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexa Noridotriacrylate, tricyclodecanedimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetrabromo Bisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl ester Fide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexane diacrylate, dimethylol tricyclodecane diacrylate, ditrimethylolpropane Tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipenta Erythritol hexaacrylate, 1,4-butylene glycol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, aromatic and aliphatic urethane acrylates (oligomers) -) Etc. are mentioned.

  A so-called epoxy (meth) acrylate resin obtained by reacting an epoxy resin with (meth) acrylic acid can also be used.

(Protective film ink (overcoat composition))
A polyurethane skeleton (A) containing a carboxyl group represented by the formula (p1) and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part bonded to at least a part of the carboxyl group A hydroxy-containing resin (P) and a polyurethane skeleton containing a carboxyl group represented by the formula (p2) and a cycloalkene oxide ring-opening addition moiety bonded to at least a part of the carboxyl group. A reaction product (urethane (meth) acrylate resin) of at least one of the hydroxyl group-containing resin (P) having a ring addition part (B2) and the compound (Q) or the above-described UV curable resin is appropriately used. Dissolved in solvent and added for printing or coating with other (poly) (meth) acrylate compounds and light or thermosetting agents as needed By blending, protective film ink to (e - preparative composition Ba - - co).

  The solvent used in the protective film ink is an aliphatic group including a polyurethane skeleton (A) containing a carboxyl group represented by the formula (p1) and an alkene oxide ring-opening addition moiety bonded to at least a part of the carboxyl group. A hydroxy-containing resin (P) having an oxide ring-opening addition part (B1) or a polyurethane skeleton containing a carboxyl group represented by the formula (p2) and a cycloalkene oxide bonded to at least a part of the carboxyl group The solvent used in the synthesis of the hydroxy-containing resin (P) having the aliphatic oxide ring-opening addition part (B2) including the ring-opening addition part can be used as it is, or other solvents can be used for adjusting the viscosity and printability. A solvent can also be used. Other solvents can also be used. When another solvent is used, the reaction solvent may be distilled off before and after the addition of a new solvent to replace the solvent. However, in view of the complexity of operation and energy cost, it is preferable to use the solvent used for the synthesis of the hydroxy-containing resin as it is.

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

  The protective film ink prepared by mixing the urethane (meth) acrylate resin or the UV curable resin described above is a base material having a conductive pattern by a printing method such as a screen printing method, a gravure printing method, or an ink jet method. A printed pattern is formed on the protective film, and after the solvent is distilled off as necessary, the printed pattern is cured by heat treatment, light irradiation or microwave heating to be cured. And

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

  As the conductive pattern, particles of metal such as silver and copper and / or metal oxide particles, nanowires, nanotubes, etc. are formed into inks to form a print pattern on the substrate, and this print pattern is used. It is a conductor. In particular, when a transparent conductive pattern is produced 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 by the protective film resin according to the above-described embodiment is effective.

  Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

The hydroxyl value was measured as follows.
About 2.0 g of a sample is precisely weighed with a precision balance in a 200 ml eggplant-shaped flask, and 5 ml of an acetylating reagent is added thereto using a pipette. Heat for 1 hour in an oil bath fitted with a Dimroth condenser and adjusted to 95 ° C to 100 ° C. After standing to cool, the liquid on the flask wall is washed with 1 ml of pure water, the flask is shaken well, and further heated in an oil bath with a gym roast and adjusted to 5 to 100 ° C. for 10 minutes. After cooling, the flask wall is washed with 5 ml of ethanol. A few drops of phenolphthalein solution is added as an indicator, and titrated with a 0.5 mol / L potassium hydroxide ethanol solution. The end point is when the light red color of the indicator lasts for about 30 seconds. In addition, the above test is carried out without putting a sample to make a blank test. The value obtained from the result using the following formula is defined as the hydroxyl value of the resin.
Hydroxyl value (mg-KOH / g) = [(BC) × f × 28.05] / S + D
B: Amount of 0.5 mol / L potassium hydroxide-ethanol solution used for the blank test (ml)
C: Amount of 0.5 mol / L potassium hydroxide-ethanol solution used for titration (ml)
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 is put into a 100 ml brown volumetric flask and pyridine is added to make 100 ml.

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 (produced by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol) 2 / 2-methyl-1,8-octanediol = 15/85, molecular weight 964) 211 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 40.0 g as a dihydroxyl compound having a carboxyl group, In addition, 379 g of γ-butyrolactone (Mitsubishi Chemical Corporation) was charged as a solvent, and the 2,2-dimethylolbutanoic acid was dissolved at 90 ° C.

  The temperature of the reaction solution was lowered to 70 ° C., and desmod (registered trademark) -W (methylene bis (4-cyclohexyl isocyanate), manufactured by Sumika Bayer Urethane Co., Ltd.) 128 g as a polyisocyanate by a dropping funnel. Was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was carried out at 80 ° C. for 1 hour, then at 100 ° C. for 1 hour, then at 120 ° C. for 2 hours. After confirming that the isocyanate had almost disappeared by IR, further at 120 ° C. for 1.5 hours. Time reaction was performed. 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 mg-KOH / g.

<Identification of product>
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 by decantation. 10 g of methanol was added again, and the standing and removal of the supernatant were repeated three times. Finally, the residue was concentrated under reduced pressure to obtain a solid resin. The identification of the obtained resin was carried out using ¹ H-NMR measurement (measured by dissolving in JEOL JNM-EX270, deuterated chloroform) and IR measurement (measured by applying to Nicolet 6700, AgCl plate). It was confirmed to be a polyurethane skeleton (A) containing a carboxyl group.

[Synthesis Example 2]
Using the same apparatus as in Synthesis Example 1, 212 g of GI-1000 (manufactured by Nippon Soda Co., Ltd., hydrogenated both-end hydroxylated polybutadiene (1,2-skeleton 90%), molecular weight 1729) as a polyol compound, carboxyl group 2,3-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxyl compound having a hydrogen content, 398 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel Corporation) as a solvent, and desmodulate as a polyisocyanate The reaction was performed in the same manner as in Synthesis Example 1 using 122 g of (registered trademark) -I (isophorone diisocyanate), manufactured by Sumika Bayer Urethane Co., Ltd.). The number average molecular weight of the obtained carboxyl group-containing polyurethane was 10600, and the acid value of the solid content was 59.8 mg-KOH / g.

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

[Synthesis Example 4]
Using the same apparatus as in Synthesis Example 1, 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, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 63.4 g as a dihydroxyl compound having a carboxyl group, diethyleneglycol as a solvent Reaction was carried out in the same manner as in Synthesis Example 1 using 400 g of rumonoethyl ether acetate (manufactured by Daicel Corporation) and 131 g of NBDI (norbornane diisocyanate, Mitsui Chemicals Fine Co., Ltd.) as the 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 mg-KOH / g.

  A polyurethane skeleton (A) containing a carboxyl group represented by the formula (p1) and an aliphatic oxide ring-opening addition part (B1) including an alkene oxide ring-opening addition part bonded to at least a part of the carboxyl group Hydroxyl-containing resin (P) or a polyurethane skeleton containing a carboxyl group represented by formula (p2) and a cycloalkene oxide ring-opening addition part (B2) bonded to at least a part of the carboxyl group Synthesis example of hydroxy-containing resin (P) having aliphatic oxide ring-opening addition part (B)

[Synthesis Example 5]
After 100 g of the carboxyl group-containing polyurethane solution (solid content concentration 50 mass%, acid value 40.2 mg-KOH / g) obtained in Synthesis Example 1 was transferred to a 300 ml autoclave and replaced with nitrogen gas, nitrogen gas was replaced. The temperature was raised to 80 ° C. under a pressure of 0.5 MPa, and 4.73 g of ethylene oxide (manufactured by Mitsubishi Chemical Corporation) was introduced into the autoclave via the mass flow controller, and the temperature was raised to 120 ° C. Warmed and allowed to react for 6 hours. The charged molar ratio ((Epoxy) / (Acid)) of ethylene oxide (epoxy group) to the carboxyl group in the urethane resin in this reaction is 3. The obtained resin composition (hereinafter referred to as “resin composition 1”) has a solid number average molecular weight of 22700, an acid value of 0.2 mg-KOH / g, a hydroxyl value of 37.1 mg-KOH / g, and a solid content concentration. Was 52 mass%.

<Identification of product>
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, standing and removing the supernatant were repeated three times, and 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, and a proton peak having an epoxy ring opened in the vicinity of 2.4 ppm in NMR measurement was confirmed. From IR measurement, CH near 1040 cm ⁻¹ was confirmed. From the increase in peak strength based on —OH stretching and peak strength based on OH stretching vibration in the vicinity of 3300 cm ⁻¹ , it was confirmed that the obtained resin was a polyurethane resin grafted with ethylene oxide. 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} formula (p1)) The average value of was 2.5. 1 and 2 show the ¹ H-NMR spectrum and IR spectrum of the resin composition 1 obtained in Synthesis Example 5, respectively.

[Synthesis Example 6]
After 100 g of the carboxyl group-containing polyurethane solution obtained in Synthesis Example 1 (solid content concentration 50% by mass, acid value 40.2 mg-KOH / g) was transferred to a 300 ml autoclave and replaced with nitrogen gas, propylene oxide (Purchased from Tokyo Chemical Industry Co., Ltd.) 8.32 g was introduced into the autoclave by a pump, and the temperature was raised to 120 ° C. with a nitrogen gas pressure of 0.5 MPa and reacted for 6 hours. In this reaction, the charged molar ratio of propylene oxide (epoxy group) to the carboxyl group in the urethane resin ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter referred to as “resin composition 2”) has a solid number average molecular weight of 28000, an acid value of almost zero, a hydroxyl value of 38.4 mg-KOH / g, and a solid content concentration of 54 mass%. there were.

<Identification of product>
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 having an epoxy ring opened in the vicinity of 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} formula (p1)) reacted with a carboxyl group in a 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]
After 100 g of the carboxyl group-containing polyurethane solution obtained in Synthesis Example 2 (solid content concentration 50 mass%, acid value 59.8 mg-KOH / g) was transferred to a 300 ml autoclave and replaced with nitrogen gas, nitrogen gas was replaced. The temperature was raised to 80 ° C. at a pressure of 0.5 MPa, and 9.52 g of ethylene oxide was introduced into the autoclave via the mass flow controller, and the temperature was raised to 120 ° C. and reacted for 6 hours. In this reaction, the charged molar ratio of ethylene oxide (epoxy group) to the carboxyl group in the urethane resin ((Epoxy) / (Acid)) is 4. The obtained resin composition (hereinafter referred to as “resin composition 3”) has a solid number average molecular weight of 11400, an acid value of 0.2 mg-KOH / g, a hydroxyl value of 57.2 mg-KOH / g, and a solid content concentration. Was 53 mass%.

<Identification of product>
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 in the vicinity of 2.4 ppm in the 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, it confirmed that ethylene oxide is a polyurethane resin grafted It 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} formula (p1)) The average value of was confirmed to be 3.4.

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

<Identification of product>
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 in the vicinity of 2.4 ppm in the 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, it confirmed that ethylene oxide is a polyurethane resin grafted It 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} formula (p1)) The average value of was confirmed to be 3.7.

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

<Identification of product>
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 in the vicinity of 2.4 ppm in the 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, it confirmed that ethylene oxide is a polyurethane resin grafted It 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} formula (p1)) The average value of was confirmed to be 3.6.

[Synthesis Example 10]
Carboxy group-containing polyurethane solution obtained in Synthesis Example 1 (solid content concentration 50 mass%, acid value 40.2 mg-KOH / g) 100 g cyclohexene oxide (purchased from Wako Pure Chemical Industries, Ltd.) 3.52 g tri Add 0.05 g of phenylphosphine (made by Hokuko Chemical Co., Ltd.), transfer to a 300 ml autoclave and replace with nitrogen gas. Then, raise the nitrogen gas pressure to 120 ° C over 0.5 MPa and react for 6 hours. I let you. In this reaction, the charged molar ratio ((Epoxy) / (Acid)) of cyclohexene oxide (epoxy group) to carboxyl group in the urethane resin is 1. The obtained resin composition (hereinafter referred to as “resin composition 6”) has a solid content number average molecular weight of 30,100, an acid value of 4.5 mg-KOH / g, a hydroxyl value of 32.3 mg-KOH / g, and a solid content concentration. Was 52 mass%.

<Identification of product>
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 in the vicinity of 3.1 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, it confirmed that ethylene oxide is a polyurethane resin grafted It was done. Further, cyclohexene 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 in NMR measurement and a proton ratio of 2.5 ppm to 5.0 ppm. The average value of was confirmed to be 0.6.

[Synthesis Example 11]
100 g of carboxyl group-containing polyurethane solution obtained in Synthesis Example 1 (solid content concentration 50 mass%, acid value 40.2 mg-KOH / g) 4.30 g of styrene oxide (purchased from Tokyo Chemical Industry Co., Ltd.), triphenyl as catalyst Add 0.05g of phosphine (made by Hokuko Chemical Co., Ltd.), transfer to 300ml autoclave and replace with nitrogen gas, then raise the nitrogen gas pressure to 120 ° C over 0.5MPa and react for 6 hours. It was. The molar ratio ((Epoxy) / (Acid)) of styrene oxide (epoxy group) to carboxyl group in the urethane resin in this reaction is 1. The obtained resin composition (hereinafter referred to as “resin composition 7”) has a solids number average molecular weight of 28100, an acid value of 1.6 mg-KOH / g, a hydroxyl value of 35.3 mg-KOH / g, and a solid content concentration. Was 53 mass%.

<Identification of product>
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 in the vicinity of 7.3 ppm in the 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 a urethane resin calculated from a proton ratio of 7.0 ppm to 7.5 ppm (excluding peaks derived from heavy chloroform) and a proton ratio of 0.8 ppm to 5.0 ppm in NMR measurement. The average value of oxide (n ₁ in formula (p1)) was confirmed to be 0.8.

Example 1
To 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 5 (solid content concentration 52 mass%, hydroxyl value 37.1 mg-KOH / g), Karenz (registered trademark) MOI (2-methacryloyloxyethyl produced by Showa Denko KK) (Isocyanate) 2.67 g and 0.20 g of triphenylphosphine were charged into a 200 ml flask equipped with a Dimroth condenser and allowed to react at 90 ° C. for 6 hours without performing nitrogen gas replacement. IR was confirmed by IR. The obtained resin was identified by ¹ H-NMR measurement and IR measurement, and was found to be 6.1 ppm and 5.8 ppm, which were not found in the ¹ H-NMR spectrum (FIG. 1) of the resin composition 1 by NMR measurement. The peak derived from methacryloyl group was confirmed, and the peak of 3400 cm ⁻¹ derived from the NH stretching of urethane bond was increased from the IR spectrum of resin composition 1 (FIG. 2) by IR measurement. It was confirmed. A novel urethane acrylate resin having a solid content of 54% by mass was obtained. 3 and 4 show the ¹ H-NMR spectrum and IR spectrum of the urethane acrylate resin according to Example 1, respectively.

(Example 2)
In the same manner as in Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 6 (solid content concentration 54 mass%, hydroxyl value 38.4 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 2.87 g (manufactured 2-methacryloyloxyethyl isocyanate) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 56% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

(Example 3)
In the same manner as in Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 7 (solid content concentration 53 mass%, hydroxyl value 57.2 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 4.19 g (manufactured 2-methacryloyloxyethyl isocyanate) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 56% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

Example 4
In the same manner as in Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 8 (solid content concentration 56 mass%, hydroxyl value 73.6 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 5.70 g of 2-methacryloyloxyethyl isocyanate manufactured) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 60% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

(Example 5)
Similarly to Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 9 (solid content concentration 54 mass%, hydroxyl value 60.1 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 4.49 g of 2-methacryloyloxyethyl isocyanate manufactured) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 58% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

(Example 6)
Similarly to Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 10 (solid content concentration 52 mass%, hydroxyl value 32.3 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 2.32 g (manufactured 2-methacryloyloxyethyl isocyanate) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 54% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

(Example 7)
As in Example 1, 50 g of the hydroxy-containing resin solution obtained in Synthesis Example 11 (solid content concentration 53 mass%, hydroxyl value 35.3 mg-KOH / g) was added to Karenz (registered trademark) MOI (Showa Denko KK). 2.59 g (manufactured 2-methacryloyloxyethyl isocyanate) was reacted to obtain a novel urethane acrylate resin having a solid concentration of 55% by mass. From the NMR measurement, methacryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From the IR measurement, the peak of 3400 cm ⁻¹ derived from the NH stretching of the urethane bond increased, so the introduction of the methacryloyl group was introduced. confirmed.

(Example 8)
Similarly to Example 1, 30 g of the hydroxy-containing resin solution obtained in Synthesis Example 8 (solid content concentration 56 mass%, hydroxyl value 73.6 mg-KOH / g) was added to Karenz (registered trademark) AOI (Showa Denko Co., Ltd.). 2.10 g of 2-acryloyloxyethyl isocyanate manufactured) was reacted to obtain a novel urethane acrylate resin having a solid content concentration of 60% by mass. From NNMR measurement, acryloyl-derived peaks were confirmed at 6.1 ppm and 5.8 ppm. From IR measurement, peak of 3400 cm ^-1 derived from NH stretching of urethane bond was increased. confirmed.

<Preparation of silver nanowire coating film>
Disperse 0.125 g of silver nanowires (average diameter of wire about 40 nm, average length of about 10 μm, all of which is the number average value of 100 silver nanowires arbitrarily observed by SEM) in 50 g of ethanol (0.25% by mass) ), 0.05 g of this solution was applied to Lumila-125U98 Co., Ltd. (manufactured by Toray Industries, Inc.) with a drop coat, and air-dried for 6 hours to deposit the silver nanowires.

  Next, a xenon irradiation device Pulse Forge 3300 manufactured by NovaCentrix was used, and a transparent conductive pattern was produced by irradiating the pulsed light once with a pulsed light irradiation condition of a drive voltage of 600 V and an irradiation time of 60 μsec. The surface resistance of the obtained transparent conductive pattern was about 100Ω / □. In addition, the surface resistance was measured using a non-contact type resistance measuring device (EC-80P manufactured by Napson Corporation).

<Evaluation as protective film resin>
A rotation / revolution vacuum mixer ARV-310 ARV-310 (manufactured by Shinki Co., Ltd.), using the urethane acrylate resin, polyacrylate and photoinitiator shown in Examples 9 to 18 of Table 1. ) Were mixed well (5 rotations at 500 rotations and 1500 rotations for 5 minutes) to prepare a coating ink (overcoat composition).

  The obtained ink was applied onto a silver nanowire coating film coated on the above-mentioned Lumila-125U98 Co., Ltd. manufactured by Toray with a bar coater so that the surface resistance was about 100Ω / □, and after air drying, Using a xenon irradiation device Pulse Forge (registered trademark) 3300 manufactured by NovaCentrix, the irradiation conditions of the pulsed light are as follows: the driving voltage of the light source is 150 V, the irradiation time is 500 μsec, and the pulse light is irradiated 10 times at 1 Hz to cure the resin. It was. Comparative Example 1 has no overcoat (protective film), and Comparative Example 2 is a commercial product (JELCON IN-10.C: Jujo Chemical Co., Ltd.) instead of the composition for overcoat of the present invention. Overcoat resin (manufactured by company) was overcoated. The thicknesses of the cured films in Examples 9 to 18 and Comparative Example 2 measured using Mitutoyo high-precision Digimatic Micrometer MDH-25M 293-100 were about 20 μm.

<Adhesion evaluation>
Using a cutter knife with a new blade, 11 cuts were made in the thin film insulation pattern at intervals of 1 mm, and then changed to 90 ° and another 11 were drawn to form 100 1 mm square cells. did. The cellophane adhesive tape was attached so as to adhere to the cut printed 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 attached, the tape was held at a right angle to the printing surface with the edge of the tape, peeled off instantaneously, and judged according to the old JIS K5400. The results are shown in Table 2.

<Reliability test>
Table 1 shows the results of measuring the surface resistance before and after the elapse of 500 hours by putting the coating film of Table 2 in a high temperature bath at 100 ° C. and a constant temperature and humidity chamber adjusted at 85 ° C.-85% relative humidity. In addition, the surface resistance was measured using a non-contact type resistance measuring device (EC-80P manufactured by Napson Corporation).

  From Table 1, it can be seen that although Examples 9-18 and Comparative Example 2 have good adhesion results, the reliability of Examples 9-18 is better than Comparative Examples 1 and 2.

Claims (14)

An aliphatic oxide ring-opening addition part (B1) including a polyurethane skeleton (A) containing a carboxyl group and an alkene oxide ring-opening addition part bonded to at least a part of the carboxyl group represented by the following formula (p1): A fat containing a hydroxy-containing resin (P) and a polyurethane skeleton (A) containing a carboxyl group represented by the following formula (p2) and a cycloalkene oxide ring-opening addition moiety bonded to at least a part of the carboxyl group (Meth) acrylate resin obtained by reacting compound (Q) having (meth) acryloyl group and isocyanato group with at least one of hydroxy-containing resin (P) having group oxide ring-opening addition part (B2) Because
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.
(A2) A urethane (meth) acrylate resin in which the polyol compound is any one of a polycarbonate polyol, a polyester polyol, a polylactone polyol, a polybutadiene polyol, and a both-end hydroxylated polysilicone .
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 Z is an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which Z is bonded. . 2. The urethane (meth) acrylate according to claim 1, 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). Resin. The urethane (meth) acrylate resin according to claim 1 or 2 , wherein the (a2) polyol compound is a polycarbonate diol or a polybutadiene polyol. The (a3) dihydroxy compound having a carboxyl group is a carboxylic acid or aminocarboxylic acid having a molecular weight of 200 or less and having any two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms. urethane according to any one of 1 to 3 (meth) acrylate - DOO resin. The group (a3) wherein the dihydroxy compound having a carboxyl group is 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine The urethane (meth) acrylate resin according to claim 4 , which is one or more of the following. N ₁ in the formula (p1) is 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 The urethane (meth) acrylate resin according to any one of claims 1 to 5 , wherein is an alkyl group having 1 to 10 carbon atoms or a phenyl group. In the formula (p2), n ₂ is an integer of 1 to 3, and Z is an atomic group forming an alicyclic hydrocarbon group having 6 to 12 carbon atoms including two carbon atoms to which the Z is bonded. The urethane (meth) acrylate resin according to any one of claims 1 to 6 . Wherein the compound (Q) is (meth) one or more acryloyl groups in one molecule, those having one isocyanate group, or any one of claims 1 to 7 that the isocyanato groups are those that are protected Urethane (meth) acrylate resin described in 1. Compound (Q) is 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2- (0- [1′- The urethane according to any one of claims 1 to 7 , which is selected from the group consisting of methylpropylideneamino] carboxyamino) ethyl and 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate. (Meth) acrylate resin. The urethane (meth) acrylate resin according to any one of claims 1 to 9 ,
A photoinitiator;
A UV curable resin composition comprising: An overcoat composition comprising the urethane (meth) acrylate resin according to any one of claims 1 to 9 or the UV curable resin composition according to claim 10 . A step of reacting a carboxyl group contained in a polyurethane resin having a polyurethane skeleton (A) containing a carboxyl group with at least one of an alkene oxide represented by formula (x1) and a cycloalkene oxide represented by formula (x2) When,
A step of reacting the hydroxy group-containing resin (P) obtained in the above step with a compound (Q) having a (meth) acryloyl group and an isocyanato group;
Bei to give 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, urethane (meth) acrylate, wherein either Der Rukoto polybutadiene polyol and polysilicone having hydroxyl groups at both ends, - DOO resin Production method.
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), Z represents an atomic group forming an alicyclic hydrocarbon group having 4 to 14 carbon atoms including two carbon atoms to which the Z is bonded.) The method for producing a urethane (meth) acrylate resin according to claim 12 , wherein the alkene oxide represented by the formula (x1) is ethylene oxide, propylene oxide, or styrene oxide. The method for producing a urethane (meth) acrylate resin according to claim 12 or 13 , wherein the cycloalkene oxide represented by the formula (x2) is cyclohexene oxide.