TWI710583B - Hydroxyl-containing polyurethane resins, polyurethane resins using them as raw materials, and urethane (meth)acrylate resins, manufacturing methods for these resins, and compositions for protective films And UV curable resin composition - Google Patents

Abstract

Provide a protective film resin with excellent environmental resistance and scratch resistance, which can be cured by radiation such as UV, as a protective film for metal nanowires.

It is provided with a polyurethane skeleton (A) having a carboxyl group and at least a part of the aforementioned carboxyl group, which contains an alkenyl oxide ring-opening addition portion represented by the following formula (b1) or formula (b2) The aliphatic oxide ring-opening addition part (B) of the cycloalkenyl oxide ring-opening addition part represented is the aliphatic oxide ring-opening addition part of the hydroxyl-containing polyurethane resin (B) A protective film resin in which at least a part of the polyisocyanate compound (Q) or the compound (R) having a (meth)acryloyl group and an isocyanate group is bonded.

(In formula (b1), n ₁ is an integer from 1 to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 16 carbon atoms, or a phenyl group.)

(In formula (b2), n ₂ is an integer from 1 to 10, and Z is an atomic group forming an alicyclic hydrocarbon group with 4 to 14 carbon atoms including the two carbon atoms bonded by Z.)

Description

Hydroxyl-containing polyurethane resins, polyurethane resins using them as raw materials, and urethane (meth)acrylate resins, manufacturing methods of these resins, and compositions for protective films And UV curable resin composition

The present invention relates to hydroxyl-containing polyurethane resins, polyurethane resins and urethane (meth)acrylate resins using them as raw materials, and methods for manufacturing these resins, And a composition for a protective film and a UV curable resin composition.

Transparent conductive films are used in liquid crystal displays (LCD), plasma display panels (PDP), organic electroluminescent displays, transparent electrodes of solar cells (PV) and touch panels (TP), anti-static (ESD) films and electromagnetic waves Various fields such as EMI film. As such transparent conductive films, those using ITO (Indium Tin Oxide) have been used in the past, but there are problems with low supply stability of indium, high manufacturing costs, lack of flexibility, and the need for high temperatures for film formation. Therefore, the search for a transparent conductive film to replace ITO is booming. Among them, the transparent conductive film containing metal nanowires has excellent conductivity, optical properties, and flexibility, and can be formed into a film by a wet process. In terms of low temperature and no need for high temperature during film formation, it is best as ITO instead of transparent conductive film. For example, a transparent conductive film containing silver nanowires and having high conductivity, optical properties, and flexibility is known (Patent Document 1 is used as a reference).

However, the transparent conductive film containing silver nanowires has a large surface area per unit weight of silver, easily reacts with various compounds, and therefore has the problem of lack of environmental resistance. It is also affected by the various chemicals or detergents used in the steps. The nanostructure is prone to corrosion and the conductivity is easily reduced due to the effects of long-term storage of oxygen or moisture exposed to the air. In addition, especially in electronic materials and other applications, in order to prevent particulate impurities, dust, dust, etc. from adhering or mixing into the surface of the substrate, there are many cases where physical cleaning steps such as brushes are used, but there is a problem of surface damage after this step .

In order to solve this problem, many attempts have been made to laminate a protective film on the surface of a transparent conductive film containing silver nanowires to provide the transparent conductive film with environmental resistance and scratch resistance. As protective films used for transparent conductive films containing silver nanowires, there are known protective films for transparent conductive films using urethane resins, etc., and various optical materials containing polyester polyamides and epoxy resins. A protective film for a material, a protective film using inorganic silicon oxide, etc. (Patent Documents 1 to 5 are referenced).

[Prior technical literature] 〔Patent Literature〕

[Patent Document 1] JP 2010-507199 A

[Patent Document 2] JP 2008-156546 A

[Patent Document 3] JP 2009-205924 A

[Patent Document 4] Japanese Patent Application Publication No. 2011-204649

[Patent Document 5] JP 2011-102003 A

However, these protective films do not satisfy all the above-mentioned characteristics. In addition, when using as a protective film, if productivity is considered, it is better not to be cured by heating but quickly cured by radiation such as UV. If considering the style of the transparent conductive film, the surface hardness is preferably hard.

The present invention was made in view of this problem, and its purpose is to provide a protective film for metal nanowires that is excellent in environmental resistance, scratch resistance, and can be cured by electronic rays such as UV as a protective film for metal nanowires. Resin synthesis Suitable raw materials (polyurethane resins containing hydroxyl groups) and resins for protective films (polyurethane resins and urethane (meth)acrylate resins) using them as raw materials.

One embodiment of the present invention is a hydroxyl-containing polyurethane resin, which is characterized by having a polyurethane skeleton (A) having a carboxyl group, and at least a part bonded to the aforementioned carboxyl group containing the following The aliphatic oxide ring-opening addition part (B) of the alkenyl oxide ring-opening addition part represented by the formula (b1) or the cycloalkenyl oxide ring-opening addition part represented by the formula (b2).

(In formula (b1), n ₁ is an integer from 1 to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 16 carbon atoms, or a phenyl group.)

(In formula (b2), n ₂ is an integer from 1 to 10, and Z is an atomic group forming an alicyclic hydrocarbon group with 4 to 14 carbon atoms including the two carbon atoms bonded by Z.)

The polyurethane skeleton (A) is a polyurethane skeleton based on the reaction product of (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group Appropriate.

In addition, the aforementioned (a1) polyisocyanate compound is an alicyclic ring having 6 to 30 carbon atoms other than the carbon atoms in the isocyanate group (-NCO group) The compound of formula is suitable.

In addition, the polyol compound (a2) is preferably polycarbonate polyol, polyether polyol, or polybutadiene polyol.

In addition, the above-mentioned (a3) dihydroxy compound having a carboxyl group is preferably one having two carboxylic acids or amino carboxylic acids having a molecular weight of 200 or less selected from hydroxyl groups and hydroxyalkyl groups having 1 or 2 carbon atoms.

In addition, the above-mentioned (a3) dihydroxy compound having a carboxyl group is 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine, N, One type or two or more types of the group consisting of N-bishydroxyethylalanine are suitable.

In addition, n ₁ in the above formula (b1) is 1-10, and R ¹ and R ² are each independently a hydrogen atom or a methyl group, or at least one of R ¹ and R ² is a hydrogen atom and the other is a carbon An alkyl group or phenyl group having 1 to 10 atoms is preferable.

In addition, n ₂ in the above formula (b2) is an integer of 1 to 3, and Z is preferably an atomic group that forms an alicyclic hydrocarbon group with 6 to 12 carbon atoms including two carbon atoms bonded by Z.

In addition, another embodiment of the present invention is a polyurethane resin characterized by at least a part of the aliphatic oxide ring-opening addition part (B) of any of the above-mentioned hydroxyl-containing polyurethane resins Reaction product with polyisocyanate compound (Q).

The above-mentioned polyisocyanate compound (Q) is preferably an aliphatic polyisocyanate compound or a blocked isocyanate derived therefrom.

In addition, the above-mentioned polyisocyanate compound (Q) may contain The isocyanate group blocked by the compound having active hydrogen selected from the group consisting of endoamide, ketoxime, phenol, and secondary amine is preferable.

In addition, still another embodiment of the present invention is a composition for a protective film, which is characterized by containing any one of the above-mentioned polyurethane resins and a solvent.

Furthermore, still another embodiment of the present invention is a urethane (meth)acrylate resin characterized by the aliphatic oxide ring-opening addition portion (B) of any of the above-mentioned hydroxyl-containing polyurethane resins ) A reaction product with a compound (R) having a (meth)acryloyl group and an isocyanate group.

The above-mentioned compound (R) preferably contains one or more (meth)acrylic acid groups in one molecule and one isocyanate group, or one whose isocyanate group is protected.

In addition, the above-mentioned compound (R) is composed of 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacryloxymethyl)ethyl isocyanate, and methacrylic acid as a blocked body. 2-(0-[1'-Methylpropyleneamino]carboxyamino)ethyl ester, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate The person selected from the group is appropriate.

In addition, still another embodiment of the present invention is a UV curable resin composition characterized by containing any one of the above-mentioned urethane (meth)acrylate resins and a photoinitiator.

Furthermore, still another embodiment of the present invention is a composition for a protective film characterized by containing any one of the above-mentioned urethane (meth)acrylate resins or the above-mentioned UV curable resin composition.

Furthermore, still another embodiment of the present invention is a method for producing a hydroxyl-containing polyurethane resin, characterized in that the carboxyl group of the carboxyl-containing polyurethane is combined with the alkenyl oxide represented by formula (x1) And at least one of the cycloalkenyl oxides represented by formula (x2) reacts.

(In formula (x1), 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 formula (x2), Z represents an atomic group that forms an alicyclic hydrocarbon group with 4 to 14 carbon atoms together with the two carbon atoms bonded to Z.)

The alkenyl oxide represented by the above formula (x1) is ethylene oxide, propylene oxide, or phenyloxirane, and the cycloalkenyl oxide represented by the above formula (x2) is cyclohexane oxide should.

Furthermore, still another embodiment of the present invention is a method for producing a polyurethane resin, which is characterized by having a hydroxyl-containing polyurethane formic acid obtained by the above-mentioned method for producing a hydroxyl-containing polyurethane resin Ester tree The step of reacting fat with polyisocyanate compound (Q).

Furthermore, still another embodiment of the present invention is a method for producing a urethane (meth)acrylate resin, which is characterized by having a hydroxyl group-containing compound obtained by the method for producing a hydroxyl group-containing polyurethane resin. A step of reacting a polyurethane resin with a compound (R) having a (meth)acryloyl group and an isocyanate group.

In addition, the suitable combination of the above elements also covers the scope of the invention that the patent in this application seeks to protect.

According to the present invention, polyurethane resin and urethane (meth)acrylate resin using hydroxyl-containing polyurethane resin as raw materials are used as wiring or electrodes printed with metallic ink, etc. In the case of the conductive pattern protective film, the conductive characteristics are reduced and the conductive pattern with high reliability can be made, and it is especially useful for the conductive pattern with low reliability like silver nanowire.

[Figure 1] ¹ H-NMR spectrum of the resin composition of Synthesis Example 5.

[Figure 2] IR spectrum of the resin composition of Synthesis Example 5.

[Figure 3] A diagram showing the bending test method.

[Figure 4] ¹ H-NMR spectrum of the urethane acrylate resin of Example 1.

[Figure 5] IR spectrum of the urethane acrylate resin of Example 1.

Hereinafter, embodiments of the present invention will be described.

The hydroxyl-containing polyurethane resin of the first embodiment has a polyurethane skeleton (A) containing a carboxyl group and at least a part of the carboxyl group bonded to the above-mentioned carboxyl group and contains the following formula (b1) The aliphatic oxide ring-opening addition part (B) of the alkenyl oxide ring-opening addition part or the cycloalkenyl oxide ring-opening addition part represented by formula (b2).

In formula (b1), n ₁ is an integer from 1 to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 16 carbon atoms, or a phenyl group.

In formula (b2), n ₂ is an integer from 1 to 10, and Z is an atomic group forming an alicyclic hydrocarbon group with 4 to 14 carbon atoms including 2 carbon atoms bonded by Z.

<Polyurethane skeleton (A) with carboxyl group>

The number average molecular weight of the polyurethane skeleton (A) having a carboxyl group is preferably 1,000 to 100,000, more preferably 3,000 to 50,000. Here, the molecular weight is a polystyrene conversion value measured by colloid permeation chromatography (hereinafter referred to as GPC). If the molecular weight is less than 1,000, the elongation, flexibility, and strength of the coating film after printing with polyurethane resin or urethane (meth)acrylate resin described later may be impaired. If it exceeds 100,000 In addition to the low solubility of the hydroxyl-containing polyurethane resin or the polyurethane resin or urethane (meth)acrylate resin described later in the solvent, the viscosity becomes too high even if it is dissolved , So the use surface has become greatly restricted.

In this specification, without particular limitation, the measurement conditions of GPC are as follows.

Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

String: Shodex string LF-804

Mobile phase: Tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus manufactured by JASCO Corporation

Temperature: 40.0℃

Sample volume: 100μL sample loop tube

Sample concentration: Prepared to about 0.1% by mass

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

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

In a 100ml Erlenmeyer flask, approximately 0.2g of the sample was accurately weighed with a precision balance, and 10ml of a mixed solvent of ethanol/toluene = 1/2 (mass ratio) was added to it to dissolve. Furthermore, 1 to 3 drops of a phenolphthalein ethanol solution as an indicator are added to the container, and the mixture is sufficiently stirred until the sample is uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the neutralization end point is when the reddish color of the indicator is maintained for 30 seconds. From this result, the value obtained by the following calculation formula was used as the acid value of the resin.

Acid value (mgKOH/g)=〔B×f×5.611〕/S

B: Usage amount of 0.1N potassium hydroxide-ethanol solution (ml)

f: Factor of 0.1N potassium hydroxide-ethanol solution

S: The amount of sample taken (g)

The polyurethane skeleton (A) having a carboxyl group is more specifically synthesized by using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group as monomers. A skeleton based on the reaction product of (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxyl group. In other words, it is a polyamine having a reaction production unit of (a1) a polyisocyanate compound and (a3) a dihydroxy compound having a carboxyl group, and a reaction production unit of a (a2) polyol compound and (a3) a dihydroxy compound having a carboxyl group The skeleton of the carbamate resin. Each monomer will be described in more detail below.

(a1) Polyisocyanate compound

(a1) As the polyisocyanate compound, a diisocyanate having two isocyanate groups per molecule is usually used. As the polyisocyanate compound, for example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, and the like. In the range where the carboxyl group-containing polyurethane skeleton (A) is not colloidal, a small amount of polyisocyanate having 3 or more isocyanate groups like triphenylmethane triisocyanate can also be used.

As the aliphatic polyisocyanate, for example, 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-trimethyl Hexamethylene diisocyanate, lysine diisocyanate, 2,2'-diethyl ether diisocyanate, dimer acid diisocyanate, etc.

Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 3- Isocyanate methyl-3,3,5-trimethylcyclohexane (IPDI, isophorone diisocyanate), bis-(4-isocyanatecyclohexyl)methane (hydrogenated MDI), hydrogenated (1,3- or 1 ,4-) Xylylene diisocyanate, norbornane diisocyanate, etc.

Examples of aromatic polyisocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, and 2,4-toluene diisocyanate , 2,6-toluene diisocyanate, (1,2,1,3, or 1,4)-xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl ester, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate Wait.

Examples of araliphatic polyisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate Isocyanate, 3,3'-Tolylene-4,4'-diisocyanate, etc. These diisocyanates can be used alone or in combination of two or more.

As the (a1) polyisocyanate compound, by using an alicyclic compound having 6 to 30 carbon atoms other than the carbon atoms in the isocyanate group (-NCO group), the following embodiment is made of polyurethane The protective film formed by resin has high reliability especially at high temperature and humidity, and is suitable for electronic equipment The component of the part.

In the (a1) polyisocyanate compound, the alicyclic compound contains 10 mol% or more, preferably 20 mol%, and more preferably 30 mol% or more relative to the total amount (100 mol%) of the (a1) polyisocyanate compound.

Examples of the alicyclic compound include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylidene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanate methyl) ring Hexane, 1,4-bis(isocyanatemethyl)cyclohexane.

(a2) Polyol compound

(a2) Polyol compound (However, (a2) polyol compound does not include the (a3) dihydroxy compound having a carboxyl group described later.) The number average molecular weight is usually 250 to 50,000, preferably 400 to 10,000, more preferably 500~5,000. This molecular weight is a polystyrene conversion value measured by GPC under the aforementioned conditions.

(a2) Polyol compounds are, for example, polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polybutadiene polyols, two-terminal hydroxylated polysiloxanes, and only containing hydroxyl groups Polyol compounds with oxygen atoms and carbon atoms ranging from 18 to 72. Among these considerations, as a balance of water resistance, insulation reliability, and adhesion to the substrate, polycarbonate polyols and polybutadiene polyols are preferred.

The above polycarbonate polyols can be determined by the number of carbon atoms Diols of 3-18 are raw materials and are obtained by reacting with carbonate or phosgene, as represented by the following structural formula (1), for example.

In the formula (1), R ^{3 is} a residue obtained by removing the hydroxyl group from the corresponding diol (HO-R ³ -OH), and n ₃ is a positive integer, preferably 2-50.

The polycarbonate polyol represented by the formula (1) can be specifically used by 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanedi Alcohol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonane Alkanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 1,2-tetradecanediol, etc. are produced as raw materials.

The above-mentioned polycarbonate polyol may be a polycarbonate polyol having a plurality of alkylene groups in its skeleton (copolymerized polycarbonate polyol). The use of the copolymerized polycarbonate polyol is advantageous in many cases from the viewpoint of preventing the crystallization of the polyurethane skeleton (A) having a carboxyl group. In addition, considering the solubility to the solvent, it is better to use a polycarbonate polyol having a branched skeleton and a hydroxyl group at the end of the branch chain in combination.

The above-mentioned polyether polyol is obtained by dehydration condensation of a diol having 2 to 12 carbon atoms, or ring-opening polymerization of an ethylene oxide compound, oxetane compound, or tetrahydrofuran compound having 2 to 12 carbon atoms This is represented by the following structural formula (2), for example.

In the formula (2), R ^{4 is} a residue obtained by removing the hydroxyl group from the corresponding diol (HO-R ⁴ -OH), and n ₄ is a positive integer, preferably 4-50. The above-mentioned diols having 2 to 12 carbon atoms may be used alone as a single polymer, or two or more of them may be used as a copolymer.

The polyether polyol represented by the above formula (2) specifically includes polyethylene glycol, polypropylene glycol, poly-1,2-butanediol, polytetramethylene glycol (poly1,4-butane Diol), poly-3-methyltetramethylene glycol, polyneopentyl glycol and other polyalkylene glycols. In addition, for the purpose of improving the compatibility of (polyether polyol) and the hydrophobicity of (polyether polyol), these copolymers can also use, for example, 1,4-butanediol-neopentyl glycol.

The polyester polyol is one obtained by dehydration condensation of dicarboxylic acid and diol, or transesterification reaction between an esterification product of a lower alcohol of dicarboxylic acid and diol, and is represented by the following structural formula (3), for example.

In formula (3), R ^{5 is} the residue obtained by removing the hydroxyl group from the corresponding diol (HO-R ⁵ -OH), and R ^{6 is} the residue obtained by removing 2 carboxyl groups from the corresponding dicarboxylic acid (HOCO-R ⁶ -COOH) , N ₅ is a positive integer, preferably 2-50.

The above diols (HO-R ⁵ -OH), specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol Alcohol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol Or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, 1,3-cyclohexanedimethanol, 3-benzenedi Methyl glycol, 1,4-benzenedimethyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, etc.

The above-mentioned dicarboxylic acid (HOCO-R ⁶ -COOH), specifically, for example succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, palacelic acid, 1, 4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, bridged methyl tetrahydrophthalic acid, methyl bridged methyl tetrahydrophthalic acid, chlorosonic acid, rich Maleic acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid.

The above-mentioned polylactone polyol is obtained by a condensation reaction of a ring-opening polymer of lactone and a diol, or a condensation reaction of a diol and a hydroxyalkane acid, and is represented by the following structural formula (4), for example.

In formula (4), R ^{7 is} the residue obtained by removing the hydroxyl group and carboxyl group from the corresponding hydroxyalkane acid (HO-R ⁷ -COOH), and R ^{8 is} the residue obtained by removing the hydroxyl group from the corresponding diol (HO-R ⁸ -OH). Base, n ₆ is a positive integer, preferably 2-50.

Specific examples of the hydroxyalkane acid (HO-R ⁷ -COOH) include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, 5-hydroxyhexane acid (ε-caprolactone), and the like.

The above-mentioned polybutadiene polyol is, for example, a diol obtained by subjecting butadiene or isoprene to anionic polymerization and polymerization, terminal treatment to introduce hydroxyl groups at both ends, and hydrogen reduction of their double bonds Diol.

Specific examples of polybutadiene polyols include hydroxylated polybutadienes mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)), Hydroxylated hydrogenated polybutadiene (for example, POLYTAIL (registered trademark) H, POLYTAIL (registered trademark) HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene (for example, G- 1000, G-2000, G-3000 (manufactured by Soda Co., Ltd.), hydroxylated hydrogenated polybutadiene (such as GI-1000, GI-2000, GI-3000 (made by Soda Co., Ltd.) )), hydroxylated polyisoprene (for example, Poly IP (manufactured by Idemitsu Kosan Co., Ltd.), and hydroxylated hydrogenated polyisoprene (for example, EPOL (registered trademark, manufactured by Idemitsu Kosan Co., Ltd.)).

The above-mentioned two-terminal hydroxylated silicone is represented by the following structural formula (5), for example.

In the formula (5), R ^{9 is} independently an aliphatic hydrocarbon divalent residue or aromatic hydrocarbon divalent residue having 2-50 carbon atoms, and n ₇ is a positive integer, preferably 2-50. These may contain ether groups, and a plurality of R ¹⁰ , independently of each other, are aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1 to 12 carbon atoms.

Examples of commercially available products of the above-mentioned two-terminal hydroxylated silicone include "X-22-160AS, KF6001, KF6002, KF-6003" manufactured by Shin-Etsu Chemical Co., Ltd. and the like. The above-mentioned "polyol compound containing oxygen atoms only in the hydroxyl group and having carbon atoms of 18 to 72" specifically includes, for example, a diol compound having a skeleton hydrogenated by a dimer acid, and its commercially available products include, for example, Cognis "SOVERMOL (registered trademark) 908" etc.

In addition, as long as the effect of the present invention is not impaired, as the (a2) polyol compound, a diol having a molecular weight of 300 or less that does not have a repeating unit can also be used. Such low molecular weight diols specifically 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, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,10-decanediol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butyl ethyl Propanediol, 1,3-cyclohexanedimethanol, 1,3-benzenedimethylene glycol, 1,4-benzenedimethylene glycol, diethylene glycol, triethylene glycol, or dipropylene glycol Wait.

(a3) Dihydroxy compound with carboxyl group

(A3) A dihydroxy compound having a carboxyl group is a carboxylic acid or an amino carboxylic acid having a molecular weight of 200 or less selected from a hydroxyl group and a hydroxyalkyl group having 1 or 2 carbon atoms, and is capable of controlling crosslinking Point is better. Specific examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine, N,N-bishydroxyethylalanine, etc. Among them, from the standpoint of solubility in solvents, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred. These (a3) carboxyl group-containing dihydroxy compounds can be used alone or in combination of two or more.

The aforementioned polyurethane resin having a polyurethane skeleton (A) having a carboxyl group can be synthesized using only the above three components ((a1), (a2), and (a3)), but it is Urethane is for the purpose of imparting radical polymerizability or cationic polymerizability, or for the purpose of suppressing the influence of the isocyanate group or the residue of the hydroxyl group at the end of the polyurethane, and can be combined with (a4) monohydroxyl Compound and/or (a5) monoisocyanate compound are reacted to synthesize.

(a4) Monohydroxy compound

(a4) Monohydroxy compound, for example 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate Base) acrylate, caprolactone or alkylene oxide adducts of the aforementioned (meth)acrylates, glycerol di(meth)acrylate, trimethylol di(meth)acrylate, pentaerythritol tri( Meth) acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, allyl alcohol, allyloxyethanol, etc. have radically polymerizable double bonds Compounds, glycolic acid, hydroxypivalic acid, and other compounds having carboxylic acids.

(a4) The monohydroxy compound can be used alone or in combination of two or more. In addition, among these compounds, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl alcohol, glycolic acid, hydroxy Valeric acid is preferred, and 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are more preferred.

In addition, (a4) monohydroxy compounds include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, amyl alcohol, and hexyl alcohol , Octyl alcohol, etc.

(a5) Monoisocyanate compound

(a5) Monoisocyanate compound, for example (meth)acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth)acrylate of diisocyanate compound, hydroxypropyl (meth)acrylate, hydroxyl Ding Alkyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, caprolactone or alkylene oxide adducts of the aforementioned (meth)acrylates, glycerol di(meth)acrylate , Trimethylol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, allyl alcohol , Radical carbon-carbon double bond compounds such as monoadducts of allyloxyethanol.

In addition, the monoisocyanate hydroxy compound used for the purpose of suppressing the influence of the terminal hydroxy residue includes, for example, phenyl isocyanate, hexyl isocyanate, and dodecyl isocyanate.

The aforementioned polyurethane resin having a polyurethane skeleton (A) having a carboxyl group can be used in the presence or absence of a conventional urethane catalyst like dibutyltin dilaurate Next, use an appropriate organic solvent to make the above (a1) polyisocyanate compound, (a2) polyol compound, (a3) dihydroxy compound having a carboxyl group, and (a4) monohydroxy compound or (a5) monoisocyanate as necessary The compound is synthesized by reaction, but if the reaction is carried out without a catalyst, it is better not to consider the final tin etc. mixing.

The above organic solvent is not particularly limited if its reactivity with isocyanate compounds is low, but it does not contain basic functional groups such as amines and has a boiling point of 110°C or higher, preferably 150°C or higher, and more preferably 200°C or higher Better. Such solvents include, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono Methyl ether monoacetate, propylene glycol monomethyl ether monoethyl Ester, propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, methoxypropane Acetic acid ethyl ester, ethoxy propionic acid methyl ester, ethoxy propionic acid ethyl ester, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl Ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, Chloroform and dichloromethane etc.

In addition, considering the poor solubility of organic solvents to the resulting polyurethane resin, and the use of polyurethane as a raw material for inks in electronic material applications, propylene glycol monomethyl is particularly preferred. Ether monoacetate, propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, γ-butyrolactone, etc. are preferred.

The order of adding raw materials is not particularly limited. Usually, (a2) polyol compound and (a3) dihydroxy compound with carboxyl group are added first, dissolved in a solvent, and then added dropwise at 20~150℃, more preferably 60~120℃ (a1) The polyisocyanate compound is then reacted at 30 to 160°C, more preferably 50 to 130°C.

The molar ratio of the raw materials is adjusted according to the molecular weight and acid value of the polyurethane resin. However, when the (a4) monohydroxy compound is introduced into the polyurethane resin, The molecular terminal becomes an isocyanate group, and it is necessary to use (a1) a polyisocyanate compound in a larger amount than (a2) a polyol compound and (a3) a dihydroxy compound having a carboxyl group (to make the isocyanate group exceed the total amount of hydroxyl groups).

Specifically, these molar ratios are added, (a1) polyisocyanate The isocyanate group of the compound: ((a2) the hydroxyl group of the polyol compound + (a3) the hydroxyl group of the dihydroxy compound having a carboxyl group) is 0.5~1.5:1, preferably 0.8~1.2:1, more preferably 0.95~ 1.05.

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

When using (a4) a monohydroxy compound, the molar number of (a1) polyisocyanate compound is excessive compared to the molar number of ((a2) polyol compound + (a3) dihydroxy compound having a carboxyl group), and Relative to the excess molar number of isocyanate groups, it is better to use (a4) monohydroxy compound 0.5 to 1.5 times molar amount, preferably 0.8 to 1.2 times molar amount.

When (a5) a monoisocyanate compound is used, the number of moles of ((a2) polyol compound + (a3) dihydroxy compound having a carboxyl group) is excessive compared to the number of moles of (a1) polyisocyanate compound, so that Relative to the excess molar number of the hydroxyl group, 0.5 to 1.5 times the molar amount, preferably 0.8 to 1.2 times the molar amount is preferably used.

In order to introduce (a4) the monohydroxy compound into the carboxyl-containing polyurethane skeleton (A), (a2) the polyol compound and (a3) the dihydroxy compound having the carboxyl group react quickly with (a1) the polyisocyanate compound At the end, in order to react the remaining isocyanate groups at both ends of the polyurethane skeleton (A) having carboxyl groups with the (a4) monohydroxy compound, the reaction solution should be at 20 to 150°C, more preferably 70 The (a4) monohydroxy compound is dropped at ~120°C, and then the reaction is completed after maintaining the same temperature.

In order to introduce (a5) monoisocyanate compound with carboxyl group The polyurethane skeleton (A) of (a2) polyol compound and (a3) the reaction of the dihydroxy compound with carboxyl group and (a1) polyisocyanate compound is about to end, in order to make (A) polyamine The hydroxyl groups remaining at both ends of the carbamic acid ester skeleton react with the (a5) monoisocyanate compound, and the (a5) monoisocyanate compound is dropped in the reaction solution at 20 to 150°C, more preferably 50 to 120°C, and then maintained at the same temperature End the reaction.

(B) Aliphatic oxide ring-opening addition part

(B) The aliphatic oxide ring-opening addition part can be obtained by combining the carboxyl group (-COOH) contained in the polyurethane resin having the polyurethane skeleton (A) having a carboxyl group with the following It is obtained by reacting the alkenyl oxide represented by the formula (x1) or the aliphatic oxide of the cycloalkenyl oxide represented by the formula (x2).

In formula (x1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group. From the viewpoint of easy acquisition, 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 a carbon atom number of 1-10 The alkyl group or phenyl group is preferred. Specifically, the alkenyl oxide represented by the above formula (x1) includes, for example, ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.

In formula (x2), Z is a monocyclic aliphatic hydrocarbon group with 2-12 carbon atoms or a bicyclic aliphatic hydrocarbon group, and the formation of 2 carbon atoms including the Z bond has 4-14 carbon atoms的alicyclic structure. In terms of easy accessibility, an alicyclic structure with 6 to 12 carbon atoms is preferred. Specifically, the cycloalkenyl oxide represented by the above formula (x2) includes, for example, epoxycyclohexane, cyclooctene oxide, cyclododecene oxide, and dicyclopentadiene monooxide. Cycloalkenyl oxide.

Regarding the conditions for the reaction of the polyurethane skeleton (A) having a carboxyl group with the aliphatic oxide, the solution for synthesizing the polyurethane skeleton (A) having a carboxyl group is added to promote epoxy The catalyst for the reaction between the radical and the carboxylic acid is heated at 50°C to 160°C, more preferably 80 to 140°C for the reaction. When the reaction temperature is too low, the speed may become too slow, and when the reaction temperature is too high, there is a risk of colloidization. The reaction time is 2 to 48 hours, preferably 3 to 24 hours, more preferably 4 to 12 hours.

Regarding the usage amount of the polyurethane skeleton (A) having a carboxyl group and the above-mentioned aliphatic oxide, relative to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group, the aliphatic oxide is The epoxy group becomes 0.5 equivalent to 50 equivalents, preferably 0.7 equivalents to 20 equivalents, 1 equivalent The amount is better than 10 equivalents. If the above equivalent is lower than 0.5, the concentration of generated hydroxyl groups will be lower, and the reaction point with isocyanate groups will be lower and unfavorable. If the above equivalent exceeds 50 equivalents, there will be negative effects such as a decrease in the moisture absorption rate of the resin itself.

The aforementioned polyurethane skeleton (A) having a carboxyl group and an aliphatic oxide containing at least one of the alkenyl oxide represented by the above formula (x1) or the cycloalkenyl oxide represented by the formula (x2) The hydroxyl-containing polyurethane resin obtained by the reaction may also contain a part of unreacted carboxyl groups. By having an unreacted carboxyl group, the adhesion to the substrate or metal wiring may be improved. The amount of unreacted carboxyl groups is 50% or less, preferably 20% or less, and more preferably 10% or less with respect to the original carboxyl groups, and the acid value is 0-50mg-KOH/g. , Preferably 0~30mg-KOH/g, more preferably 0~10mg-KOH/g hydroxyl-containing polyurethane resin. The obtained hydroxyl-containing polyurethane resin has a structure represented by formula (p1) or formula (p2).

In the formula, R ¹ , R ² , Z, n ₁ , and n ₂ have the same symbols as in the aforementioned formula (b1) or formula (b2). More preferably n ₁ is an integer from 1 to 10, and more preferably n ₂ is an integer from 1 to 3. In addition, the hydroxyl-containing polyurethane resin is as represented by formula (p1) or formula (p2), although the carboxyl group in the polyurethane skeleton (A) is bonded with an integer number of parentheses. The structure of the unit, but it is not necessary that all the carboxyl groups are bonded with the units shown in parentheses. That is, the number of units shown in parentheses bonded to each carboxyl group does not need to be the same, and may have an unreacted carboxyl group that is not bonded as described above. Since the number of units shown in parentheses bonded to each carboxyl group could not be confirmed, the average value was calculated in the examples described later. The epoxy group of the aliphatic oxide is reacted in an amount of 0.5 to 50 equivalents relative to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group, the average value of n ₁ and n ₂ Theoretically, it can be 0.5-50, but it is actually a value smaller than the theoretical value. The preferable average value of n ₁ is 0.4-10, more preferably 0.5-5. The preferred average value of n ₂ is 0.4-10, more preferably 0.5-5.

Since the hydroxyl-containing polyurethane resin thus obtained has a hydroxyl group, the number of functional groups can be measured by measuring the concentration of the hydroxyl group as the hydroxyl value. In terms of the preferred range of hydroxyl valence, the original urethane resin has It is also included when the terminal hydroxyl group is 10~140mg-KOH/g, more preferably 20~140mg-KOH/g, still more preferably 30~140mg-KOH/g.

In addition, the above reaction can be carried out in an inert gas or air environment, but in the case of a compound with high flammability like ethylene oxide, it needs to be carried out in an inert gas environment. Moreover, because the boiling point is also very low, it needs to be under pressure. Under the reaction.

Regarding the reaction catalyst, although the carboxyl group contained in the polyurethane skeleton (A) having a carboxyl group can also be used as a catalyst, a basic compound may be added for the purpose of further increasing the reaction rate or the degree of polymerization. Examples of basic compounds include tertiary amines, phosphine compounds, and tertiary ammonium hydroxide. More specifically, the tertiary amine includes, for example, 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-dimethylaminomethylphenol, etc. The phosphine compound includes, for example, triphenylphosphine, triphenylphosphite, trimethylphosphine, and trimethylphosphite. The quaternary ammonium hydroxide includes, for example, tetramethylammonium hydroxide. Too little of these usage amounts will have no effect, and too much will reduce the electrical insulation of the resulting polyurethane resin. Therefore, it has a carboxyl group-containing polyurethane skeleton (A) and aliphatic oxide. The total mass of the product is 0.1~5 mass%, more preferably 0.5~3 mass%.

The hydroxyl-containing polyurethane resin having a polyurethane skeleton (A) having a carboxyl group according to the first embodiment can be used as an element containing selected elements from the group consisting of gold, silver, copper, and aluminum Metal particles and/or metal oxide particles containing the above-mentioned elements (hereinafter, these It is collectively referred to as a metal component) as a binder for the composition (for example, ink). The volume average particle diameter of the metal particles or metal oxide particles is, for example, in the range of 0.01 μm to 100 μm, more preferably 0.02 to 50 μm, more preferably 0.1 to 10 μm. Various particle shapes such as spherical, flat, and needle shapes can be used. Although linear ones can also be used, the average wire diameter in this case is preferably 1 nm or more and 500 nm or less, more preferably 5 nm or more and 200 nm or less, more preferably 5 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 100 nm or less. In addition, the average length of the long axis of the metal nanowire is preferably 1 μm or more and 100 μm or less, more preferably 1 μm or more and 50 μm or less, more preferably 2 μm or more and 50 μm or less, and particularly preferably 5 μm or more and 30 μm or less. The average diameter of the wire and the average length of the major axis conform to the above range, and the average aspect ratio is preferably 10 or more, preferably 100 or more, and even more preferably 200 or more. Here, the aspect ratio is a value calculated as a/b when the average thickness of the metal nanowire diameter is approximately b and the average long axis length is approximately a. A and b can be measured by scanning electron microscope. The composition containing the metal component and the adhesive is formed on a substrate with a printing method such as screen printing, gravure printing, inkjet method, etc., and the printed pattern is subjected to heat treatment, light irradiation or microwave Heating produces a metal sintered body, thereby forming a conductive pattern.

The substrate on which the composition containing the metal component and the adhesive is printed includes, for example, a polyimide film and a polyester film. In particular, polyimide film has excellent electrical insulation or heat resistance, and the printability itself has the advantage that it can be improved by surface treatment such as corona treatment and plasma treatment on the substrate, but it is generally dense with resin It is difficult to improve the adhesion if no adhesive layer is provided. Moreover, by providing the adhesive layer, the heat resistance and insulation are damaged Yu. Since the hydroxyl-containing polyurethane resin of this embodiment also has good adhesion to the polyimide film, a polyimide film without an adhesion layer on the surface can be used as a substrate.

When the hydroxyl-containing polyurethane resin of the first embodiment is used as a binder for the above composition, even when a resin such as ethylene terephthalate or polycarbonate is used as a base material, Heat treatment at a relatively low temperature than general adhesives can still exhibit high conductivity and have excellent adhesion to the above-mentioned substrate.

<Polyurethane resin bonded with polyisocyanate compound (Q)>

The polyurethane resin of the second embodiment is obtained as described above by having a polyurethane skeleton (A) having a carboxyl group and at least a part of the carboxyl group bonded to the above-mentioned formula The aliphatic oxide ring-opening addition part (B) of the alkenyl oxide ring-opening addition part represented by the formula (b2) or the cycloalkenyl oxide ring-opening addition part represented by the formula (b2) The polyisocyanate compound (Q) obtained by reacting at least a part of the aliphatic oxide ring-opening addition part (B) of the polyurethane resin with the polyisocyanate compound (Q) and the hydroxyl-containing polyurethane The reaction product of acid ester resin. Here, at least a part of the aliphatic oxide ring-opening addition part (B) refers to at least the alkenyl oxide ring-opening addition part (b1) and the cycloalkenyl oxide ring-opening addition part (b2) One part of the open-loop bonus (B). As a result of the above reaction, at least a part of the aliphatic oxide ring-opening addition part (B) of the hydroxyl-containing polyurethane resin and the reaction product of the polyisocyanate compound (Q) are produced. Acid ester resin (hereinafter referred to as Polyurethane resin. ).

In addition, the isocyanate group in the polyisocyanate compound (Q) is preferably reacted in an equivalent amount relative to the hydroxyl group in the hydroxy-containing polyurethane resin, but the isocyanate group in the polyisocyanate compound (Q) is It can be used within the equivalent deviation of -20%~+20%.

Such polyisocyanate compounds (Q) include, for example, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and aromatic aliphatic polyisocyanate compounds.

As the aliphatic polyisocyanate compound, for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2, 4,4-Trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.

Examples of the alicyclic polyisocyanate compound include 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, and 3-isocyanatemethyl-3,3,5 -Trimethylcyclohexane (IPDI, isophorone diisocyanate), bis-(4-isocyanate cyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, etc.

Examples of aromatic polyisocyanate compounds include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate Isocyanate, 2,6-toluene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane , 1,5-naphthylene diisocyanate, etc.

As the aromatic aliphatic polyisocyanate compound, for example Such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc.

Moreover, as the polyisocyanate compound (Q) other than the above, for example, an isocyanate group terminal compound formed by the reaction of an isocyanate compound and an active hydrogen group-containing compound, and a reactant of these compounds (for example, an adduct type poly Isocyanate, or allophanate reaction, carbodiimide reaction, uretdionization reaction, isocyanuration reaction, ketimination reaction, biuretization reaction, etc. Sex body, etc.), or these mixtures, etc.

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

In addition, these polyisocyanate compounds (Q) may be prepolymers obtained by reacting excess isocyanate remaining in the raw polyisocyanate compound with respect to the hydroxyl group of the raw polyol compound.

The polyol compound used to obtain the prepolymer is a compound containing two or more hydroxyl groups reactive to isocyanate groups, specifically, for example, acrylic polyol, polyester polyol, polyether polyol, epoxy polyol Wait.

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

A polymerizable monomer having one or more active hydrogens in one molecule, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc. Methacrylic 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate and other hydroxy methacrylates, glycerol monoacrylate or methacrylate monoester , Monoacrylate or methacrylate of trimethylolpropane, or monomers obtained by ring-opening polymerization of ε-caprolactone of these hydroxyl groups.

The monomers that can be copolymerized with the above polymerizable monomers include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-butyl acrylate, 2-ethylhexyl acrylate, etc. Acrylic esters, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n- methacrylate Methacrylates such as hexyl ester, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, etc., unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid , Unsaturated amides such as acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, vinyl toluene, vinyl acetate, acrylonitrile, etc.

Examples of polyester polyols include condensation polyester polyols, polycarbonate polyols, and polylactone polyols.

Condensed polyester polyols, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Alkyl glycol, 1,6-hexanediol, neopentyl glycol, butyl ethyl propane glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, three Diols such as propylene glycol, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, anhydrous maleic acid, fumaric acid, 1,3- Cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid and other dicarboxylic acid reactants.

Specifically, such as polyethylene adipate diol, polybutene adipate diol, polyhexamethylene adipate diol, polyneopentenyl adipate diol, polyethylene propylene diol Diester diol, polyethylene butene adipate diol, polybutene hexamethylene adipate diol, poly(polytetramethylene ether) adipate diol, etc. Azelaate-based condensed polyester diol, such as ester-based condensed polyester diol, polyethylene azelate diol, polybutene azelate diol, etc.

Polycarbonate polyols, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Alkyl glycol, 1,6-hexanediol, neopentyl glycol, butyl ethyl propane glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, three Diols such as propylene glycol, reactants with dialkyl carbonates such as dimethyl carbonate, etc. Specifically, such as polytetramethylene carbonate diol, poly 3-methyl pentamethylene carbonate diol, polyhexamethylene carbonate diol and the like.

The polylactone polyol includes, for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone, and ring-opening polymers of a mixture of two or more of these. Specifically, such as polycaprolactone diol and the like.

Polyether polyols include, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, Catechol, hydroquinone, bisphenol A and other compounds containing more than 2 active hydrogen atoms are used as initiators to make ethylene oxide, propylene oxide, butylene oxide, phenylethylene oxide, and Monomers of chlorohydrin, tetrahydrofuran, cyclohexene, etc. The reactant for addition polymerization. When it is a reactant for addition polymerization of two or more monomers, it may be an end-capping addition, a random addition, or a mixed system of the two. Specifically, such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like.

Examples of epoxy polyols include novolac type, β-methylepichlorohydrin type, cyclic ethylene oxide type, glycidyl ether type, glycol ether type, and epoxy type of aliphatic unsaturated compound. , Epoxidized fatty acid ester type, polycarboxylic acid ester type, aminoglycidyl type, halogenated type, resorcinol type and other epoxy polyols.

The polyisocyanate compound (Q) may have a plurality of isocyanate groups, but at least one of these isocyanate groups may be blocked by a compound having active hydrogen.

Examples of compounds that block isocyanate groups include alcohols using conventional blocking agents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, etc. Phenols, phenols, cresols, nitrophenols, chlorophenols, resorcinols and other phenols, mercaptans such as benzene mercaptan, caprolactams such as ε-caprolactam, ethylaminomethyl Carbamates such as esters, ketone-enols such as acetylacetone, ketoximes such as methyl ethyl ketoxime, diisopropylamine, triazole, 3,5-dimethylpyridine Secondary amines such as azoles, sodium bisulfite, and other compounds that block the aforementioned polyisocyanate compounds or their modified products and prepolymers. Among these, a compound with active hydrogen selected from the group consisting of caprolactam, ketoxime, phenol, and secondary amine is a balance between the stability at room temperature and the rate of hardening after the high temperature protective group is released Better.

Also, in order to promote these polyisocyanate compounds (Q) and For the urethane reaction of hydroxyl-containing polyurethane resins, dibutyltin laurate-like hardening accelerators can also be used.

As such a hardening accelerator, in addition to tin compounds, salts of strong basic amines like DBU and phenol, carboxylic acid compounds or special amine compounds, acetone acetone metal complexes or bismuth, aluminum or zirconium complexes can be used And other non-tin compounds.

Examples of tin compounds for hardening accelerating catalysts include, for example, NEOSTANN U-100, NEOSTANN U-130, NEOSTANN U-200 manufactured by Nitto Chemical Co., Ltd., and Dabco (registered trademark) T-12, Dabco T manufactured by Air Products. -120, Dabco T-125, etc.

Examples of non-tin compounds used as hardening accelerators include U-CAT SA 1, U-CAT SA 102, U-CAT SA 102-50 manufactured by San-Apro Co., Ltd., and K-CAT SA 102-50 manufactured by Kusei Kasei Co., Ltd. KAT (registered trademark) 348, K-KATXC-C227, K-KATXK-628, etc., Nasemu aluminum manufactured by Nippon Kasei Sangyo Co., Ltd., Nasemu chromium, Nasemu second cobalt, etc.

The polyurethane resin of this embodiment is dissolved in an appropriate solvent, and if necessary, a hardening acceleration catalyst and additives for printing or coating can be used to form a protective film ink (composition for protective film). The polyurethane resin may be at least a part of the aliphatic oxide ring-opening addition part (B) of the hydroxyl-containing polyurethane resin, that is, the aliphatic oxide ring-opening addition part (B) At least one of the alkenyl oxide ring-opening addition part (b1) and the cycloalkenyl oxide ring-opening addition part (b2) of ), which is obtained by reacting with the polyisocyanate compound (Q), or 2 A mixture of more than species. Rear In this case, it may be the ring-opening addition of the aforementioned polyurethane skeleton (A) having a carboxyl group and an alkenyl oxide represented by formula (b1) containing at least a part of the aforementioned carboxyl group. The reaction product of the hydroxyl-containing polyurethane resin of the aliphatic oxide ring-opening addition part (B1) and the polyisocyanate compound (Q), which has at least a part that is bonded to the aforementioned carboxyl group Between the aliphatic oxide ring-opening addition part (B2) of the cycloalkenyl oxide ring-opening addition part represented by formula (b2) and the polyisocyanate compound (Q) A mixture of reaction products.

The solvent that can be used for the protective film ink can be directly used for the synthesis of hydroxyl-containing polyurethane resin, or other solvents for adjusting viscosity or printability can be added. In addition, other solvents can also be used. When using other solvents, the reaction solvent can be distilled off before and after adding a new solvent to replace the solvent.

However, considering the complexity of the operation or the energy cost, it is better to directly use the solvent used in the synthesis of the hydroxyl-containing polyurethane resin.

Solvents that can be used to adjust viscosity or printability vary depending on the printing style, but are not particularly limited if they have low reactivity with isocyanate compounds. They do not contain basic functional groups such as amines and have a boiling point of 60°C or higher. A solvent above 110°C is preferred. Such solvents include, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono Methyl ether monoacetate, propylene glycol monomethyl ether monoacetate, propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetic acid Ester, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate Ester, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N- Dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, chloroform and dichloromethane, etc.

When the aforementioned isocyanate-terminated compound is used as the polyisocyanate compound (Q), methanol, ethanol, isopropanol, cyclohexanol, benzyl alcohol, etc. that react with isocyanate can also be used as a solvent.

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

The blended protective film ink is used to form a printed pattern on a substrate with a conductive pattern by printing methods such as screen printing, gravure printing, and inkjet printing. The printed pattern is necessary after the solvent is distilled off. Carry out heat treatment, light irradiation or microwave heating to harden to form a conductive pattern protective film.

The substrate on which the above-mentioned conductive pattern is formed includes, for example, a polyimide film, a polyester film, a ZEONOR (registered trademark) film, and a polycarbonate film.

In terms of conductive patterns, for example, the particles of metals such as silver or copper and/or metal oxides, nanowires, nanotubes, etc. are formed into ink, and then a printed pattern is formed on the substrate to form the printed pattern. Conductor. Especially when silver nanoparticle ink or silver nanowire ink is used to make transparent conductive patterns, because the surface area per unit mass of silver is large and the insulation reliability of fine wiring is low at high temperature and humidity, the above embodiment can be used. Protective film resin protection.

<Urethane (meth)acrylate resin to which a compound (R) having a (meth)acryloyl group and an isocyanate group is bonded>

The urethane (meth)acrylate resin of the third embodiment has the polyurethane skeleton (A) having the carboxyl group, and at least a part bonded to the carboxyl group contains the The aliphatic oxide ring-opening addition part (B) of the alkenyl oxide ring-opening addition part represented by formula (b1) or the cycloalkenyl oxide ring-opening addition part represented by formula (b2) It is obtained by reacting at least a part of the aliphatic oxide ring-opening addition part (B) of a hydroxyl-based polyurethane resin with a compound (R) having a (meth)acryloyl group and an isocyanate group A reaction product of a hydroxyl-containing polyurethane resin and a compound (R) having a (meth)acryloyl group and an isocyanate group. The compound (R) preferably contains one or more (meth)acrylic acid groups in one molecule and one isocyanate group, or a protected isocyanate group. Here, at least a part of the aliphatic oxide ring-opening addition part (B) refers to at least the alkenyl oxide ring-opening addition part (b1) and the cycloalkenyl oxide ring-opening addition part (b2) One. As a result of the above reaction, at least a part of the aliphatic oxide ring-opening addition part (B) formed in the hydroxyl-containing polyurethane resin is bonded with a (meth)acrylic acid group and an isocyanic acid The urethane (meth)acrylate resin of the compound (R) (hereinafter, referred to as urethane (meth)acrylate resin).

In addition, in this specification, (meth)acrylate means acrylate or methacrylate, and (meth)acryloyl means acryloyl Or methacrylic acid group, (meth)acrylic acid means acrylic acid or methacrylic acid.

Specific examples of the compound (R) include 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacryloxymethyl)ethyl isocyanate, and those having the isocyanate group The blocking form of the protecting group 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonyl Amino] ethyl methacrylate and the like. These compounds can be used alone or in combination of two or more kinds.

The reaction between the hydroxyl-containing polyurethane resin and the compound (R) is the reaction between the hydroxyl group and the isocyanate group, that is, the urethane reaction, so the solvent used so far can be used directly, or it can be substituted with Other solvents perform the reaction.

Furthermore, if necessary, it is better to add a catalyst for promoting the urethane reaction in advance, and it can be used as it is if it is added beforehand.

In addition, since the unreacted component of the compound (R) in the product is better, the isocyanate group and the hydroxyl group are the same amount or the hydroxyl group is slightly excessive.

(UV curable resin composition)

In the above-mentioned urethane (meth)acrylate resin, by adding a photoinitiator, and if necessary, monomers having other radical polymerizable groups, more preferably monofunctional and polyfunctional acrylates, A UV curable resin composition can be obtained. The addition amount of the monomers is 50~300 parts by mass relative to 100 parts by mass of the urethane (meth)acrylate resin, preferably It is 80 to 200 parts by mass. In addition, when preparing a solvent-free UV curable resin composition, another (poly)acrylate compound that is liquid at room temperature may be added, and the solvent used so far may be distilled off, and the compound (R) may be reacted.

Although the amount of the photoinitiator used in the UV curable resin composition is not particularly limited, it is relative to the case of a urethane (meth)acrylate resin (containing monomers with other radical polymerizable groups) , Is the sum of urethane (meth)acrylate resin and monomers having other radical polymerizable groups) 100 parts by mass, 0.5-15 parts by mass, preferably 1-10 parts by mass. If it is more than 15 parts by mass, a large amount of photoinitiator remains after UV curing, which causes contamination. In addition, if it is less than 0.5 parts by mass, it may not be able to react sufficiently by UV irradiation, the curing may be insufficient, and the adhesive force may not decrease, which may cause pick-up problems.

The photoinitiator is not particularly limited, but it is preferable to use a photoradical initiator from the viewpoint of high reactivity to ultraviolet rays. Examples of photo-radical initiators include acetophenone, phenylacetone, benzophenone, xanthone, fluorene, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylbenzene Ethyl ketone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone Ketones, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl Ether, benzoin butyl ether, bis(4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy -1,2-Diphenylethane-1-one (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, made by BASF Japan), 1-[4-(2-hydroxyethoxy)-phenyl ]-2-Hydroxy-2-methyl-1-propane-1-one (IRGACURE (registered trademark) 2959, manufactured by BASF Japan), 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropane-1-one (IRGACURE (registered trademark) 907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanol Ketone-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), dibenzyl and the like.

Among these, α-hydroxy ketone compounds (such as benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (such as acetophenone, benzene Acetone, benzophenone, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone Ketone, 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 a kind of initiator that can suppress oxygen inhibition on the surface of the hardened product, a photoradical initiator having 2 or more photodegradable groups in the molecule or a hydrogen abstraction type light having 3 or more aromatic rings in the molecule can be used. free Base initiator. As the photoradical initiator having two or more photodegradable groups in the molecule, for example, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propanyl)-benzyl Yl)phenyl)-2-methyl-propan-1-one (IRGACURE (registered trademark) 127, manufactured by BASF Japan), 1-[4-(4-benzylphenylthio)phenyl]-2 -Methyl-2-(4-methylphenylsulfonyl)propan-1-one (trade name ESURE1001M), methylbenzyl formate (manufactured by SPEEDCURE (registered trademark) MBF LAMBSON) O-B Oxyimino-1-phenylpropan-1-one (manufactured by SPEEDCURE (registered trademark) PDO LAMBSON), oligo[2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl ] Acetone (trade name Escure KIP150 LAMBERTI), etc. Examples of hydrogen abstraction type photoradical initiators having 3 or more aromatic rings in the molecule include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O- Benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(0-acetyl Oxime), 4-benzyl-4'methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4',4"-(hexamethyltriamino)triphenylmethane, etc. .

In addition, photo-radical initiators characterized by improved deep-part hardenability can also be used. Examples of photo-radical initiators characterized by improved deep hardening properties include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (DAROCUR (registered trademark) TPO, BASF Japan Made), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (IRGACURE (registered trademark) 819, BASF Japan make), bis(2,6-dimethylbenzyl) Yl)-2,4,4-trimethyl-pentylphosphine oxide and other phosphine oxide-based photo-radical initiators.

Regarding the photo-radical initiator, the balance between the curability and storage stability of the curable composition of the present invention is based on 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE (registered trademark) 184, BASF Japan ), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (DAROCUR (registered trademark) 1173, made by BASF Japan), bis(4-dimethylaminophenyl) ketone, 2- Hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propanyl)-benzyl]phenyl]-2-methyl-propane-1-one (IRGACURE (registered trademark) 127, BASF Japan made), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (IRGACURE (registered trademark) 369, BASF Japan made), 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-trimethylbenzyl-diphenyl-phosphine oxide (DAROCUR (registered trademark) TPO, made by BASF Japan), bis(2,4,6-trimethylbenzyl) )-Phenylphosphine oxide (IRGACURE (registered trademark) 819, made by BASF Japan), bis(2,6-dimethylbenzyl)-2,4,4-trimethyl-pentylphosphine oxide Better.

These photo-radical initiators can be used alone or in a mixture of two or more, and can also be used in combination with other compounds.

In combination with other compounds, specific examples include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, diethanol Combinations of amines such as methylamine, dimethylethanolamine, triethanolamine, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, etc., Furthermore, it is combined with iodonium salts such as diphenyl iodonium chloride, and those combined with dyes and amines such as methylene blue.

In addition, when using the aforementioned photoradical initiator, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and p-tert-butylcatechol may be added as necessary.

In addition, a photosensitizer can also be combined with the UV curable resin composition. As for the photosensitizer, for example, triethylamine, tri-n-butylphosphine and the like can be mentioned.

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

In addition, when the resin layer is polymerized by UV, a photopolymerization initiator is generally added in an appropriate amount, and a photosensitizer can be added in an appropriate amount as necessary. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoyl benzoate, and thioxanthones. As for the photosensitizer, for example, triethylamine, tri-n-butylphosphine and the like can be mentioned.

Solvents that can be used to adjust the viscosity or printability of the UV curable resin composition vary depending on the printing style, but are not particularly limited if they have low reactivity with the compound (R), and do not contain basic functional groups such as amines. , And a solvent with a boiling point above 50°C, preferably above 110°C is preferred. Such solvents include, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono Methyl ether monoacetate, propylene glycol monomethyl ether monoacetate, propylene glycol monoethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetic acid Ester, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate Ester, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethyl Acetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide and chloroform, etc.

For the purpose of improving the workability due to the decrease in viscosity and improving the physical properties of the molded body, the UV curable resin composition can also be used in combination with monomers having other radical polymerizable groups.

With respect to the aforementioned radically polymerizable group, for example, a (meth)acryloyl group and a vinyl group can be mentioned. Among them, those having the same (meth)acrylic acid group as the ultraviolet crosslinkable group used in the present invention are preferred.

Specific examples of the aforementioned monomers include (meth)acrylate-based monomers, styrene-based monomers, (meth)acrylonitrile, vinyl ester-based monomers, N-vinylpyrrolidone, ( Meth)acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, halogenated vinyl groups. Halogenated vinylidene monomers, (meth)allyl ester monomers, polyfunctional monomers, etc. (Meth)allyl means allyl or methallyl.

In terms of (meth)acrylate monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Base ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, (meth) N-hexyl acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth) )2-ethylhexyl acrylate Ester, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, Lauryl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, (meth)acrylate Base) benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(methacrylic acid) (Oxypropyl) trimethoxysilane, (meth)acrylic acid ethylene oxide adduct, (meth)acrylic acid trifluoromethyl methyl ester, (meth)acrylic acid 2-trifluoromethyl ethyl Ester, 2-perfluoroethyl ethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate Ester, perfluoromethyl (meth)acrylate, diperfluoromethyl methyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth)acrylate, ( 2-perfluorohexylethyl meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc.

As for the styrene-based monomer, for example, styrene, α-methylstyrene, and the like can be mentioned.

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

For (meth)acrylamide-based monomers, for example (Meth)acrylamide, N,N-dimethylacrylamide, etc.

With regard to conjugated diene-based monomers, for example, butadiene, isoprene, etc. may be mentioned. With regard to vinyl ketone monomers, for example, methyl vinyl ketone and the like can be mentioned.

Halogenated ethylene. The vinylidene halide monomers include, for example, vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

In terms of multifunctional monomers, for example, trimethylolpropane triacrylate, neopentyl glycol polypropoxy diacrylate, neopentyl glycol diacrylate, trimethylol propane polyethoxy triacrylate Ester, bisphenol F polyethoxy diacrylate, bisphenol A polyethoxy diacrylate, dipentaerythritol polycaprolactone hexaacrylate, ginseng (hydroxyethyl) isocyanurate polycaprolactone three Acrylate, tricyclodecane dimethylol diacrylate 2-(2-propenyloxy-1,1-dimethyl)-5-ethyl-5-propenyloxymethyl-1 ,3-Dioxane, tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercapto diphenyl sulfide dimethacrylate, polyethylene glycol diacrylate, 1,9- Nonanediol diacrylate, 1,6-hexane diacrylate, dimethylol tricyclodecane diacrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tetraacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate or Aromatic and aliphatic urethane acrylate (oligomer), etc.

It is also possible to use a so-called epoxy (meth)acrylate resin in which an epoxy resin and (meth)acrylic acid are reacted.

(Protective film ink (composition for protective film))

Dissolve the above-mentioned urethane (meth)acrylate resin or the above-mentioned UV curable resin composition in an appropriate solvent, and mix with other (poly)(meth)acrylate compounds and light or thermal hardeners as necessary. Additives for printing or coating to make protective film ink (composition for protective film).

The solvent that can be used in the protective film ink can be the solvent used in the synthesis of the above-mentioned hydroxyl-containing polyurethane resin, or other solvents for adjusting the viscosity or printability can also be added. In addition, other solvents can also be used. When other solvents are used, the reaction solvent can be distilled off before and after adding a new solvent to replace the solvent. However, considering the complexity of the operation or the energy cost, it is better to directly use the solvent used in the synthesis of the hydroxyl-containing polyurethane resin.

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

The protective film ink blended with the above-mentioned urethane (meth)acrylate resin or UV curable resin composition is electrically conductive by printing methods such as screen printing, gravure printing, and inkjet printing. A printed pattern is formed on the patterned base material, and the printed pattern is subjected to heat treatment, light irradiation or microwave heating after the solvent is distilled off as necessary to harden it to form a conductive pattern protective film.

The above-mentioned conductive patterned substrates include, for example, polyimide film, polyester film, ZEONOR (registered trademark) film, polycarbonate film.

In terms of conductive pattern, it is used to form a printed pattern on a substrate by converting silver or copper and other metals and/or metal oxide particles, nanowires, nanotubes, etc. into ink, and then making the printed pattern conductive . Especially when silver nanoparticle ink or silver nanowire ink is used to make transparent conductive patterns, the surface area per unit mass of silver is large, and the insulation reliability of fine wiring at high temperature and high humidity is low, so it can be protected by the above embodiment The membrane resin effectively protects.

[Example]

Hereinafter, embodiments of the present invention will be described. These embodiments are only preferred examples for describing the present invention and do not limit the present invention.

In addition, the hydroxyl value measurement is performed as follows.

In a 200ml eggplant type flask, a precision balance is used to accurately weigh about 2.0g of the sample, and 5ml of the acetylated reagent is added to it using a pipette. It is heated for 1 hour in an oil bath adjusted to 95°C~100°C with Dai's cooling tube. After leaving to cool, use 1ml of pure water to make the liquid contact the wall of the flask for cleaning, shake the flask sufficiently, and then heat it for 10 minutes in an oil bath adjusted to 5°C~100°C with a Dai's cooling tube. After allowing to cool, wash the walls of the flask with 5 ml of ethanol. Add a few drops of phenolphthalein solution as an indicator, titrate with 0.5mol/L potassium hydroxide ethanol solution, and take the light red of the indicator lasting for about 30 seconds as the end point. In addition, the above test was performed without adding a sample as a blank test. The value obtained from the result using the following calculation formula is the hydroxyl value of the resin.

Hydroxyl value (mg-KOH/g)=[(B-C)×f×28.05]/S+D

B: The amount of 0.5mol/L potassium hydroxide-ethanol solution used in the blank test (ml)

C: The amount of 0.5mol/L potassium hydroxide-ethanol solution used in titration (ml)

f: Factor of 0.5mol/L potassium hydroxide-ethanol solution

S: The amount of sample taken (g)

D: acid value

In addition, the acetylation reagent system used a brown measuring flask in which 25 g of anhydrous acetic acid was added to a 100 ml, and pyridine was added to obtain 100 ml.

. Synthesis example of polyurethane skeleton (A) with carboxyl group [Synthesis Example 1]

In a 2L three-necked flask equipped with a stirring device, a thermometer, and a capacitor, add C-1015N (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol: 1,9-nonane diol) as a polyol compound /2-Methyl-1,8-octanediol = 15/85, molecular weight 964) 211 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxy compound having a carboxyl group 40.0 g and 379 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and the aforementioned 2,2-dimethylolbutanoic acid was dissolved at 90°C.

The temperature of the reaction solution was lowered to 70°C, and 128 g of Desmodur (registered trademark)-W (Methylene bis(4-cyclohexyl isocyanate), manufactured by Sumika Bayer Polyurethane Co., Ltd.), which is a polyisocyanate compound, was poured in a dropping funnel for 30 minutes dropping. After dripping, proceed to 80℃ for 1 hour When the reaction was performed at 100°C for 1 hour, and then at 120°C for 2 hours, it was confirmed by IR that the isocyanate had almost disappeared, and then the reaction was carried out at 120°C for 1.5 hours. The number average molecular weight of the obtained carboxyl group-containing polyurethane was 34,100, and the acid value of its solid content was 40.2 mg-KOH/g.

<Identification of products>

1 g of the reaction liquid after the above synthesis was dropped into 10 g of methanol, and after standing still, the supernatant was removed in a decantation tank. Repeat 3 times to add 10g of methanol and let it stand. The supernatant is removed, and finally the remaining part is concentrated under reduced pressure to obtain a solid resin. The identification of the obtained resin was carried out using ¹ H-NMR measurement (JNM-EX270 manufactured by JEOL, dissolved in deuterated chloroform for measurement) and IR measurement (Nicolet 6700, coated on AgCl plate for measurement), and the obtained resin was confirmed to contain carboxyl groups Polyurethane skeleton (A).

[Synthesis Example 2]

Using the same apparatus as in Synthesis Example 1, 212 g of GI-1000 (manufactured by Soda Co., Ltd., hydrogenated two-terminal hydroxylated polybutadiene (1,2-skeleton 90%), molecular weight 1729) as a polyol compound was used as 63.3 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) of a dihydroxy compound having a carboxyl group, 398 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel Co., Ltd.) as a solvent, And 122 g of Desmodur (registered trademark)-I (isophorone diisocyanate), manufactured by Sumika Bayer Polyurethane Co., Ltd., which is a polyisocyanate compound, was reacted in the same manner as in Synthesis Example 1. The number average molecular weight of the obtained carboxyl-containing polyurethane is 10600. The acid value of its solid content is 59.8mg-KOH/g.

[Synthesis Example 3]

Using the same device as in Synthesis Example 1, 117 g of PTXG-1000 (1,4-butanediol-neopentyl glycol polyether copolymer (manufactured by Asahi Kasei Fiber Co., Ltd.) as a polyol compound with a molecular weight of 1000 was used as 64.1 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) of a dihydroxy compound having a carboxyl group, 304 g of diethylene glycol monoethyl ether monoacetate (manufactured by Daicel Co., Ltd.) as a solvent And 122 g of Dcsmodur (registered trademark)-I (isophorone diisocyanate, manufactured by Sumika Bayer Polyurethane Co., Ltd.) as a polyisocyanate compound, and reacted in the same manner as in Synthesis Example 1. The obtained carboxyl-containing polyurethane The number average molecular weight of the acid ester is 6120, and the acid value of its solid content is 79.8 mg-KOH/g.

[Synthesis Example 4]

The same device as in Synthesis Example 1 was used, and Kuraray polyol C-1090 (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 3-methyl-1,5-pentane) was used as a polyol compound Alkanediol+1,6-hexanediol raw material 90:10, molecular weight 992) 206g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 63.4g as a dihydroxy compound having a carboxyl group, 400 g of diethylene glycol monoethyl ether acetate (manufactured by Daiccl Co., Ltd.) as a solvent and 131 g of NBDI (norbornane diisocyanate, manufactured by Mitsui Chemicals, Fine Co., Ltd.) as a polyisocyanate compound, and In Synthesis Example 1, the reaction was carried out in the same manner. Carboxyl-containing polyamine The number average molecular weight of the carbamate is 6570, and the acid value of its solid content is 60.6 mg-KOH/g.

. Possess a polyurethane skeleton (A) having a carboxyl group, and an alkenyl oxide ring-opening addition portion (b1) or cycloalkenyl oxide that contains at least a part of the aforementioned carboxyl group. Synthesis example of hydroxyl-containing polyurethane resin of part (b2) of aliphatic oxide ring-opening addition part (B)

[Synthesis Example 5]

Transfer 100 g of the solution (solid content 50% by mass, acid value 40.2 mg-KOH/g) of the polyurethane skeleton (A) having carboxyl groups obtained in Synthesis Example 1 to a 300 ml autoclave, nitrogen gas After replacement, the temperature was raised to 80°C under a nitrogen gas pressure of 0.5 MPa, 4.73 g of ethylene oxide (manufactured by Mitsubishi Chemical Corporation) was introduced into the autoclave through a mass flow controller, and the temperature was raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of ethylene oxide (epoxy) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 3. The obtained resin composition (hereinafter referred to as resin composition 1) has a 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 of 52 mass. %.

<Identification of products>

1 g of the reaction solution after the above synthesis was dropped into 10 g of methanol, and after standing still, the supernatant was removed. Repeat 3 times to add methanol and let stand. The supernatant was removed, and finally the remaining part was concentrated under reduced pressure to obtain a liquid resin. The identification of the obtained resin was carried out using ¹ H-NMR measurement and IR measurement. In the NMR measurement, the proton peak of epoxy ring opening was confirmed near 2.4 ppm, and the peak of CH-OH stretching near 1040 cm ^-1 was confirmed by IR measurement. The increase in the strength and the peak strength of the OH stretching vibration near 3300 cm ^-1 confirmed that the obtained resin is a polyurethane resin grafted with ethylene oxide. Also, confirm that the ethylene oxide reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm in the NMR measurement and the proton ratio of 2.5 ppm to 5.0 ppm (in formula (b1) The average value of n ₁ ) is 2.5. FIGS. 1 and 2 are the ¹ H-NMR spectrum and IR spectrum of the resin composition 1 obtained in Synthesis Example 5, respectively.

[Synthesis Example 6]

Transfer 100 g of the solution (solid content 50% by mass, acid value 40.2 mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 1 to a 300 ml autoclave, and perform nitrogen After the gas substitution, 8.32 g of propylene oxide (purchased from Tokyo Chemical Industry Co., Ltd.) was pumped into the autoclave, and the pressure was 0.5 MPa with nitrogen gas, and the temperature was raised to 120° C. for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of propylene oxide (epoxy group) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 4. The obtained resin composition (hereinafter, referred to as resin composition 2) had a number average molecular weight of solid content of 28,000, an acid value of almost zero, a hydroxyl value of 38.4 mg-KOH/g, and a solid content concentration of 54% by mass.

<Identification of products>

The identification of the solid resin obtained in the same manner as in Synthesis Example 5 was carried out by ¹ H-NMR measurement and IR measurement. In the NMR measurement, the proton peak of epoxy ring opening was confirmed near 2.4 ppm. 1040cm ^-1 peak intensity increases the peak intensity of the CH-OH stretching and close to the OH stretching vibration near 3300cm ^-1, confirming propylene oxide-grafted polyurethane resin. Confirm that the propylene oxide reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm and the proton ratio of 2.5 ppm to 5.0 ppm in the NMR measurement (n ₁ in formula (b1) The average value of) is 1.6.

[Synthesis Example 7]

Transfer 100 g of the solution (solid content 50% by mass, acid value 59.8 mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 2 to a 300 ml autoclave, and perform nitrogen After the gas is replaced, the temperature is raised to 80°C with a nitrogen gas pressure of 0.5 MPa, 9.52 g of ethylene oxide is introduced into the autoclave through the mass flow controller, and the temperature is raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of ethylene oxide (epoxy group) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 4. The number average molecular weight of the solid content of the obtained resin composition (hereinafter referred to as resin composition 3) is 11400, the acid value is 0.2mg-KOH/g, the hydroxyl value is 57.2mg-KOH/g, and the solid content concentration is 53 mass. %.

<Identification of products>

The identification of the liquid resin refined in the same manner as in Synthesis Example 5 was carried out by ¹ H-NMR measurement and IR measurement. In the NMR measurement, the proton peak of epoxy ring opening was confirmed near 2.4 ppm. The measurement was performed by IR. 1040cm ^-1 peak intensity increases the peak intensity of the CH-OH stretching vibration of OH stretching and close to the vicinity of 3300cm ^-1, as confirmed grafted ethylene oxide polyurethane resin. Also, confirm that the ethylene oxide reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm in the NMR measurement and the proton ratio of 2.5 ppm to 5.0 ppm (in formula (b1) The average value of n ₁ ) is 3.4.

[Synthesis Example 8]

Transfer 100 g of the solution (solid content 50% by mass, acid value 79.8 mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 3 to a 300 ml autoclave, and perform nitrogen After the gas is replaced, the temperature is raised to 80°C with a nitrogen gas pressure of 0.5 MPa, 12.8 g of ethylene oxide is introduced into the autoclave through the mass flow controller, and the temperature is raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of ethylene oxide (epoxy group) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 4. The number average molecular weight of the solid content of the obtained resin composition (hereinafter referred to as resin composition 4) is 7400, the acid value is 0.5 mg-KOH/g, the hydroxyl value is 73.6 mg-KOH/g, and the solid content concentration is 56 mass. %.

<Identification of products>

The identification of the liquid resin obtained in the same manner as in Synthesis Example 5 was carried out using ¹ H-NMR measurement and IR measurement. The proton peak of epoxy ring opening was confirmed in the vicinity of 2.4 ppm in the NMR measurement. It was measured by IR from 1040 cm and increase the peak intensity of the CH-OH stretching ^{cm -1} peak intensity of the OH stretching vibration near 3300 cm ^-1, it was confirmed for the ethylene oxide-grafted polyurethane resin. Also, confirm that the ethylene oxide reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm in the NMR measurement and the proton ratio of 2.5 ppm to 5.0 ppm (in formula (b1) The average value of n ₁ ) is 3.7.

[Synthesis Example 9]

Transfer 100 g of the solution (solid content 50% by mass, acid value 60.6 mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 4 to a 300 ml autoclave, and perform nitrogen After the gas is replaced, the temperature is raised to 80°C with a nitrogen gas pressure of 0.5 MPa, 9.73 g of ethylene oxide is introduced into the autoclave through the mass flow controller, and the temperature is raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of ethylene oxide (epoxy group) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 4. The number average molecular weight of the solid content of the obtained resin composition (hereinafter referred to as resin composition 5) is 8900, the acid value is 0.1 mg-KOH/g, the hydroxyl value is 60.1 mg-KOH/g, and the solid content concentration is 54 mass. %.

<Identification of products>

The identification of the liquid resin obtained in the same manner as in Synthesis Example 5 was carried out using ¹ H-NMR measurement and IR measurement. In the NMR measurement, the proton peak of the epoxy ring opening was confirmed at around 2.4 ppm. The measurement by IR was 1040 cm and increase the peak intensity of the CH-OH stretching ^{cm -1} peak intensity of the OH stretching vibration near 3300 cm ^-1, it was confirmed for the ethylene oxide-grafted polyurethane resin. Also, confirm that the ethylene oxide reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm in the NMR measurement and the proton ratio of 2.5 ppm to 5.0 ppm (in formula (b1) The average value of n ₁ ) is 3.6.

[Synthesis Example 10]

To 100 g of the solution (solid content 50% by mass, acid value 40.2 mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 1, was added cyclohexane epoxy (purchased From Wako Pure Chemicals Co., Ltd.) 3.52g, as a catalyst, triphenylphosphine (made by Beixing Chemical Industry Co., Ltd.) 0.05g, transferred to a 300ml autoclave, replaced with nitrogen gas, and pressure 0.5MPa with nitrogen gas , The temperature was raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of epoxycyclohexane (epoxy group) to the carboxyl group in the polyurethane skeleton (A) having a carboxyl group in this reaction is 1. The obtained resin composition (hereinafter referred to as resin composition 6) has a number average molecular weight of 30,100, an acid value of 4.5 mg-KOH/g, and a hydroxyl value of 32.3 mg-KOH/g, The solid content concentration was 52% by mass.

<Identification of products>

The identification of the liquid resin obtained in the same manner as in Synthesis Example 5 was carried out using ¹ H-NMR measurement and IR measurement. In the NMR measurement, the proton peak of the epoxy ring opening was confirmed near 3.1 ppm, and it was measured by IR. increase in the peak intensity of the peak intensity of the CH-OH stretching vibration of OH stretching and close to the vicinity of 3300cm ^-1 1040cm ^-1, as confirmed polyurethane resin graft-epoxycyclohexane. Also, it was confirmed that the epoxy cyclohexane reacted with the carboxyl group in the urethane resin calculated from the proton ratio of 0.8 ppm to 2.5 ppm and the proton ratio of 2.5 ppm to 5.0 ppm in the NMR measurement (formula (b2) The average value of n ₂ ) is 0.6.

[Synthesis Example 11]

To 100 g of the solution (solid content 50% by mass, acid value 40.2mg-KOH/g) of the polyurethane skeleton (A) having a carboxyl group obtained in Synthesis Example 1, phenyloxirane (purchased From Tokyo Kasei Co., Ltd.) 4.30g, as a catalyst of triphenylphosphine (made by Beixing Chemical Industry Co., Ltd.) 0.05g, transferred to a 300ml autoclave, replaced with nitrogen gas, and then pressurized with nitrogen gas at 0.5MPa, The temperature was raised to 120°C for 6 hours of reaction. The molar ratio ((Epoxy)/(Acid)) of the phenyloxirane (epoxy group) to the carboxyl group in the carboxyl-containing polyurethane skeleton (A) in the reaction is 1. The obtained resin composition (hereinafter referred to as resin composition 7) has a number average molecular weight of 28,100 and an acid value of 1.6 mg-KOH/g, a hydroxyl value of 35.3 mg-KOH/g, and a solid content concentration of 53% by mass.

<Identification of products>

The identification of the liquid resin obtained in the same manner as in Synthesis Example 5 was carried out using ¹ H-NMR measurement and IR measurement. The proton peak derived from the benzene ring was confirmed in the vicinity of 7.3 ppm in the NMR measurement. It was measured by IR and measured from 1040 cm and increase the peak intensity of the CH-OH stretching ^{cm -1} peak intensity of the OH stretching vibration near 3300 cm ^-1, it was confirmed benzene ethylene oxide-grafted polyurethane resin. Also, confirm the benzene ring that reacts with the carboxyl group in the urethane resin calculated from the proton ratio of 7.0 ppm to 7.5 ppm (excluding the peak derived from deuterated chloroform) and the proton ratio of 0.8 ppm to 5.0 ppm in the NMR measurement The average value of oxyethane (n ₁ in formula (b1)) is 0.8.

<Production of Coated Film of Silver Nanowire>

0.125g of silver nanowires (the average wire diameter is about 40nm, the average length is about 10μm, and the average value of 100 silver nanowires randomly observed by SEM) is dispersed in 50g (0.25% by mass) of ethanol to make the solution A drop-coat of 0.05 g was applied to Lumirror 125U98 (shares) (manufactured by Toray Co., Ltd.) and air-dried for 6 hours to deposit the silver nanowire.

Next, a xenon irradiation device Pulse Forge 3300 manufactured by NovaCentrix was used. The pulsed light irradiation conditions were as follows: a pulsed light was irradiated with a light source drive voltage of 600V and an irradiation time of 60 μs to produce an evaluation Transparent conductive pattern. The surface resistance of the obtained transparent conductive pattern was about 100Ω/□. In addition, the surface resistance was measured using a non-contact resistance measuring device (EC-80P manufactured by Napuson Co., Ltd.).

. Synthesis and evaluation of a polyurethane resin in which at least a part of the aliphatic oxide ring-opening addition part (B) of a hydroxyl-containing polyurethane resin is bonded with a polyisocyanate compound (Q)

. Examples 1 to 10, Comparative Examples 1 to 2 <Evaluation of protective film resin>

As shown in Table 1, using polyisocyanate compound (Q) (Desmodur (registered trademark) BL4265SN, DURANATE (registered trademark) SBB-70P, DURANATE (registered trademark) 17B-60P), blocked isocyanate (Desmodur (registered trademark)-I) , Dabco T-12 catalyst (Dibutyltin dilaurate, DBTDL), after mixing with the collocation in Table 2, use rotation. Revolving Vacuum Mixer Defoaming Nintaro ARV-310 (manufactured by THINKY Co., Ltd.) thoroughly mixed (500 rotations and 1,500 rotations for 5 minutes) to prepare coating inks (Examples 1-10).

The obtained ink was applied to Lumirror (registered trademark) 125U98 (manufactured by Toray Co., Ltd.) with a bar coater. A silver nanowire coating film with a surface resistance of approximately 100Ω was applied. After air drying, it was dried at 120°C, 1 Hours to harden the resin. Comparative example 1 is not coated with ink, and comparative example 2 is to use a commercially available protective film resin (JELCON IN-10C: protective film resin made by Jujo Chemical Co., Ltd., cured by UV irradiation (using a halogen lamp, 200mj/cm at room temperature) ² )).

<Assessment of bending>

After depositing the silver nanowires on the substrate, cut the film before curing after applying the inks of Examples 1 to 10 (to form a protective film) into 10cm×5cm, with the coated side facing up, and perform it at 120°C for 1 hour Hardening (Comparative Example 2 is UV irradiation at room temperature). The cured film was placed on the surface (reference surface) of the base, and as shown in Fig. 3, the bending of the film end was measured.

<Adhesion Evaluation>

Using a utility knife with a new blade, cut 11 strips on the cured film at 1 mm intervals, change the direction of 90°, and cut 11 more strips to form 100 squares of 1 mm square. Paste cellophane tape to adhere to the cut printing surface, rub the cellophane tape with an eraser to make the tape adhere to the coating film. After 1 to 2 minutes have passed after the tape is attached, grab the end of the tape to maintain a right angle to the printed surface and peel off instantly, and it is judged according to the old JIS K5400. The results are shown in Table 2.

<Reliability Test>

In a high temperature tank at 100°C, a constant temperature and humidity tank adjusted to 85°C and a relative humidity of 85%, the coating film with the ingredients in Table 2 was placed, and the surface resistance before and after 500 hours was measured. The results obtained are shown in Table 2. In addition, the surface resistance was measured using a non-contact resistance measuring device (EC-80P manufactured by Napuson Co., Ltd.).

. A urethane formic acid obtained by reacting the aliphatic oxide ring-opening addition part (B) of a hydroxyl-containing polyurethane resin with a compound (R) having a (meth)acryloyl group and an isocyanate group Synthesis and evaluation of ester (meth)acrylate resin

(Example 11)

In 50 g of the hydroxyl-containing polyurethane resin solution (resin composition 1) obtained in Synthesis Example 5 (solid content 52% by mass, hydroxyl value 37.1 mg-KOH/g), Karenz (registered trademark) 2.67 g of MOI (2-methacryloxyethyl isocyanate manufactured by Showa Denko Co., Ltd.) and 0.20 g of triphenylphosphine were added to a 200-ml flask equipped with a Dai's cooling tube, and nitrogen gas substitution was not performed. The reaction was carried out at 90°C for 6 hours, and it was confirmed by IR that almost all the isocyanate had disappeared. The identification of the obtained resin was carried out using ¹ H-NMR measurement and IR measurement, and it was confirmed that the 6.1 ppm and 5.8 ppm of the ¹ H-NMR spectrum of the resin composition 1 (Figure 1) that were not seen in the NMR measurement were derived from the The peak of the acryloyl group was measured by IR. The IR spectrum of the resin composition 1 (Figure 2) The peak of 3400 cm ^-1 derived from the NH stretching of the urethane bond increased, confirming the introduction of the methacryloyl group . A novel urethane acrylate resin with a solid content concentration of 54% by mass was obtained. 4 and 5 each show the ¹ H-NMR spectrum and the IR spectrum of the urethane acrylate resin of Example 11.

(Example 12)

As in Example 11, 50 g of the hydroxyl-containing resin solution (resin composition 2) obtained in Synthesis Example 6 (solid content 54% by mass, hydroxyl value 38.4 mg-KOH/g) and Karenz (registered trademark) MOI (Showa Denko Corporation 2-methacryloxyethyl isocyanate) 2.87 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 56% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks at 3400 cm ^-1 derived from the NH stretch of the urethane bond measured by IR increased. Import of base.

(Example 13)

As in Example 1, 50 g of the hydroxyl-containing resin solution (resin composition 3) obtained in Synthesis Example 7 (solid content 53% by mass, hydroxyl value 57.2 mg-KOH/g) and Karenz (registered trademark) MOI (Showa Denko Corporation 2-methacryloxyethyl isocyanate) 4.19 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 56% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks of 3400 cm ^-1 derived from the NH stretching of the urethane bond by IR measurement increased. Import of base.

(Example 14)

As in Example 11, 50 g of the hydroxyl-containing resin solution (resin composition 4) obtained in Synthesis Example 8 (solid content 56% by mass, hydroxyl value 73.6 mg-KOH/g) and Karenz (registered trademark) MOI (Showa Denko Co., Ltd. 2-methacryloxyethyl isocyanate) 5.70 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 60% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks of 3400 cm ^-1 derived from the NH stretching of the urethane bond by IR measurement increased. Import of base.

(Example 15)

As in Example 11, 50 g of the hydroxyl-containing resin solution (resin composition 5) obtained in Synthesis Example 9 (solid content 54% by mass, hydroxyl value 60.1 mg-KOH/g) and Karenz (registered trademark) MOI (Showa Denko Corporation 2-methacryloxyethyl isocyanate) 4.49 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 58% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks of 3400 cm ^-1 derived from the NH stretching of the urethane bond by IR measurement increased. Import of base.

(Example 16)

As in Example 11, 50 g of the hydroxyl-containing resin solution (resin composition 6) obtained in Synthesis Example 10 (solid content 52% by mass, hydroxyl value 32.3 mg-KOH/g) and Karenz (registered trademark) MOI (Showa Denko Corporation 2-methacryloxyethyl isocyanate) 2.32 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 54% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks of 3400 cm ^-1 derived from the NH stretching of the urethane bond by IR measurement increased. Import of base.

(Example 17)

As in Example 11, 50 g of the hydroxyl-containing resin solution (resin composition 7) obtained in Synthesis Example 11 (solid content 53% by mass, hydroxyl value 35.3 mg-KOH/g) and Karenz (registered trademark) MOI (2-Methacryloxyethyl isocyanate manufactured by Showa Denko Co., Ltd.) 2.59 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 55% by mass. The peaks derived from the methacrylic acid group were confirmed by NMR measurement at 6.1 ppm and 5.8 ppm, and the peaks of 3400 cm ^-1 derived from the NH stretching of the urethane bond by IR measurement increased. Import of base.

(Example 18)

In the same manner as in Example 11, 30 g of the hydroxyl-containing resin solution (resin composition 4) obtained in Synthesis Example 8 (solid content 56% by mass, hydroxyl value 73.6 mg-KOH/g) and Karenz (registered trademark) AOI (2-acryloxyethyl isocyanate manufactured by Showa Denko Co., Ltd.) 3.10 g was reacted to obtain a novel urethane acrylate resin with a solid content concentration of 60% by mass. The peaks derived from the acrylic group were confirmed at 6.1 ppm and 5.8 ppm by NNMR measurement, and the introduction of the acrylic group was confirmed that the peak at 3400 cm ^-1 derived from the NH stretch of the urethane bond increased by the IR measurement.

<Evaluation of protective film resin>

Use the combination of urethane acrylate resin, polyacrylic acid, and photoinitiator shown in Examples 19-28 in Table 3, and use rotation. Revolution Vacuum Mixer Go to Soak Nintaro ARV-310 (THINKY Co., Ltd. (Preparation) Fully mixing (rotation 500 rotation, revolution 1500 rotation for 5 minutes), the ink for coating (protective film composition) is produced.

The obtained ink was coated with a bar coater on the aforementioned silver nanowire coated film made by Lumirror 125U98 (stock) Toray, the surface resistance of which was about 100Ω/□, and after air-dried, it was made by NovaCentrix. Xenon irradiation device Pulse Forge (registered trademark) 3300, pulsed light irradiation conditions are the driving voltage of the light source 150V, irradiation time 500μsec, 1Hz pulse light irradiation 10 times to harden the resin. Comparative Example 3 is without a protective film (protective film), and Comparative Example 4 uses a commercially available product (JELCON IN-10.C: protective film resin manufactured by Jujo Chemical Co., Ltd.) as a protective film instead of the protective film composition of the present invention . The thickness of the cured film in Examples 19 to 28 and Comparative Example 4 measured using Mitutoyo's high-precision digital micrometer MDH-25M 293-100 was about 20 μm.

<Adhesion Evaluation>

Using a utility knife with a new blade, cut 11 pieces of the above-mentioned film insulation pattern at 1mm intervals, change the direction of 90°, and then cut 11 pieces to form 100 1mm squares. The cellophane tape is attached to the cut printing surface and pasted, and the cellophane tape is rubbed with an eraser to attach the tape to the coating film. After 1 to 2 minutes after the tape is attached, grab the end of the tape and maintain it at a right angle to the printed surface, and then peel off instantly. The judgment is based on the old JIS K5400. The results are shown in Table 4.

<Reliability Test>

The coating film of Table 3 was placed in a high temperature tank of 100°C and a constant temperature and humidity chamber adjusted to 85°C-85% relative humidity, and the results of measuring the surface resistance before and after 500 hours are shown in Table 4. In addition, the surface resistance was measured using a non-carboxy contact resistance measuring device (EC-80P manufactured by Napuson Co., Ltd.).

It can be seen from Table 4 that although Examples 19 to 28 and Comparative Example 4 have good results in adhesion, compared with Comparative Examples 3 and 4, Examples 19 to 28 have good reliability.

Claims (19)

A hydroxyl-containing polyurethane resin characterized by a polyurethane skeleton (A) having a carboxyl group, and at least a part of the carboxyl group bonded to at least a part selected from the following formula (b1) The alkene oxide (alkene oxides) ring-opening addition part or the cycloalkene oxide (Cycloalkene oxide) represented by the formula (b2) ring-opening addition part of the aliphatic oxide ring-opening addition part (B ),

(In formula (b1), n ₁ is an integer from 1 to 50, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 16 carbon atoms, or a phenyl group)

(In formula (b2), n ₂ is an integer from 1 to 10, and Z is an atomic group forming an alicyclic hydrocarbon group with 4 to 14 carbon atoms including the two carbon atoms bonded by Z) and the aforementioned having a carboxyl group Polyurethane skeleton (A) is based on (a1) polyisocyanate compound, (a2) polycarbonate polyol or polybutadiene polyol, and (a3) a reaction product of a dihydroxy compound having a carboxyl group Polyurethane skeleton. The hydroxyl-containing polyurethane resin according to claim 1, wherein the (a1) polyisocyanate compound is the number of carbon atoms other than the carbon atoms in the isocyanato group (-NCO group) of 6 ~30 alicyclic compounds. The hydroxyl-containing polyurethane resin according to claim 2, wherein the aforementioned (a3) dihydroxy compound having a carboxyl group is any one having two hydroxyalkyl groups selected from hydroxyl groups and having 1 or 2 carbon atoms A carboxylic acid or amino carboxylic acid with a molecular weight of 200 or less. The hydroxyl-containing polyurethane resin according to claim 3, wherein the (a3) dihydroxy compound having a carboxyl group is 2,2-dimethylolpropionic acid, 2,2-dimethylolbutane One or more of the group consisting of alkanoic acid, N,N-bishydroxyethylglycine, and N,N-bishydroxyethylalanine. The hydroxyl-containing polyurethane resin according to claim 1, wherein n ₁ in the aforementioned formula (b1) is 1 to 10, and R ¹ and R ² are independent of each other and are a hydrogen atom, a methyl group, or R ^1. At least one of R ² is a hydrogen atom and the other is an alkyl group with 1 to 10 carbon atoms or a phenyl group. The hydroxyl-containing polyurethane resin according to claim 1, wherein n ₂ in the aforementioned formula (b2) is an integer of 1 to 3, and Z is a carbon forming two carbon atoms including the Z bond The atomic group of an alicyclic hydrocarbon group with 6 to 12 atoms. A polyurethane resin, which is any 1 of claims 1 to 6 The reaction product of at least a part of the aliphatic oxide ring-opening addition part (B) of the hydroxyl-containing polyurethane resin described in the item and the polyisocyanate compound (Q). The polyurethane resin according to claim 7, wherein the polyisocyanate compound (Q) is an aliphatic polyisocyanate compound or a blocked isocyanate derived therefrom. The polyurethane resin according to claim 7, wherein the polyisocyanate compound (Q) contains a compound having active hydrogen selected from the group consisting of caprolactam, ketoxime, phenol, and secondary amine Blocked isocyanate groups. A composition for a protective film characterized by containing the polyurethane resin described in any one of claims 7 to 9 and a solvent. A urethane (meth)acrylate resin, which is an aliphatic oxide ring-opening addition part (B) of a hydroxyl-containing polyurethane resin described in any one of claims 1 to 6 The reaction product with a compound (R) having a (meth)acryloyl group and an isocyanate group. The urethane (meth)acrylate resin according to claim 11, wherein the compound (R) contains one or more (meth)acrylic groups in one molecule and one isocyanate group, Or its isocyanate group is protected. The urethane (meth)acrylate resin according to claim 11, wherein the compound (R) is selected from 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacrylic acid) 2-(0-[1'-methylpropyleneamino]carboxy Group amino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate group. A UV curable resin composition characterized by containing the urethane (meth)acrylate resin described in any one of Claims 11 to 13, and a photoinitiator. A composition for a protective film characterized by containing the urethane (meth)acrylate resin described in any one of claims 11 to 13 or the UV curable resin composition described in claim 14. A method for producing a hydroxyl-containing polyurethane resin described in claim 1, characterized by combining the carboxyl group of the carboxyl-containing polyurethane with the alkenyl oxide represented by the formula (x1) and the formula ( x2) reaction of at least one of the cycloalkenyl oxides represented,

(In formula (x1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group with 1 to 16 carbon atoms, or a phenyl group)

(In formula (x2), Z represents an atomic group that forms an alicyclic hydrocarbon group with 4 to 14 carbon atoms together with the two carbon atoms bonded to Z). The method for producing a hydroxyl-containing polyurethane resin as described in claim 16, wherein the alkenyl oxide represented by the aforementioned formula (x1) is ethylene oxide, propylene oxide, or styrene oxide ( styrene oxide), and the cycloalkenyl oxide represented by the aforementioned formula (x2) is cyclohexene oxide. A method for producing a polyurethane resin, characterized by comprising a hydroxyl-containing polyurethane obtained by the method for producing a hydroxyl-containing polyurethane resin described in claim 16 or 17 The step of reacting the resin with the polyisocyanate compound (Q). A method for producing a urethane (meth)acrylate resin, which is characterized by having a hydroxyl-containing polycarbonate obtained by the method for producing a hydroxyl-containing polyurethane resin described in claim 16 or 17. The step of reacting a urethane resin with a compound (R) having a (meth)acryloyl group and an isocyanate group.

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