KR102588034B1 - Polymerizable resin composition and cured product thereof - Google Patents

Abstract

(Problem) To provide a polymerizable resin composition that enables the cured product to have excellent adhesion to metal and also excellent heat and moisture resistance.
(Solution) Contains a compound obtained by reaction with at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and its hydrogenated product, and a polyisocyanate, and the compound It is a polymerizable resin composition in which the amount of acryloyl group and methacryloyl group is 12.5 to 50 mol% relative to the total amount of isocyanate group, acryloyl group, and methacryloyl group contained in .

Description

Polymerizable resin composition and cured product thereof {POLYMERIZABLE RESIN COMPOSITION AND CURED PRODUCT THEREOF}

The present invention relates to polymerizable resin compositions and their cured products.

Conventionally, for example, in electrical wiring, circuit boards, etc., polymerizable resin compositions have been used to cover the surfaces of electrical wiring, circuit boards, etc. for the purposes of moisture proof insulation, rust prevention, protection from gases and foreign substances, etc. In such a polymerizable resin composition, in addition to excellent adhesion to metal, electrical insulation of the cured product under heating and humidification conditions, that is, heat-and-moisture resistance, is required.

For example, terminal metal fittings are connected to terminal wires of coated wires that are colored in vehicles such as automobiles. In order to improve the fuel efficiency of vehicles, weight reduction is in progress, and to achieve this weight reduction, aluminum or aluminum alloy is used as the material for electric wires. In such a coated electric wire, rust prevention of the connection part between the terminal of the wire and the terminal metal fitting is attempted by covering the connection part with a photocurable resin composition (polymerizable resin composition) (see Patent Documents 1 to 3).

However, in the techniques of Patent Documents 1 to 3, it is difficult to say that the adhesion of the cured product obtained by polymerizing the polymerizable resin composition to the connection part made of the metal is sufficient, and it is difficult to say that the heat-and-moisture resistance is also sufficient. In addition, in the technology of Patent Document 2, in order to improve adhesion, it is necessary to interpose a coupling agent between the polymerizable resin composition and the connection portion, and also in this respect, it is difficult to say that the adhesion of the polymerizable resin composition itself is sufficient. .

Meanwhile, conventionally, there are products equipped with a large number of control electronic circuits, such as home appliances such as refrigerators and washing machines, electric hot water heaters, and home fuel cells. The circuit boards mounted on these products are sealed with a curable resin for the purposes of moisture-proof insulation, prevention of adhesion of foreign substances such as dust, and protection against vibration and heat. As these resins, two-component curing urethane resins, epoxy resins, silicone resins, or their solvent dilutions are used, and since they involve heat drying or a crosslinking reaction using a curing agent, a long curing time is required, reducing productivity. There were challenges in improving.

Therefore, as a method to replace the conventional two-liquid curing thick film potting using urethane resin, epoxy resin, or silicone resin, processing using a thin film insulating coating called conformal coating is being implemented. This method's sealing performance is inferior to that of conventional potting, but it does not require a case for pouring liquid, and the amount of resin used is small (about 100 ㎛ for potting with a resin thickness of several centimeters), making it possible to reduce the overall weight of the device. So, it is spreading. Currently, inventions related to resins used in conformal coating are also being actively implemented (see Patent Documents 4 to 6), and urethane acrylate resin compositions are prepared by reacting various polyol components with isocyanate and capping the ends with an acrylate compound containing a hydroxyl group. Photocurable resin compositions using are being developed. However, it is difficult to say that these conventional polymerizable resin compositions have sufficient adhesion to a circuit board that is a composite of metal and resin, and it is difficult to say that they have sufficient heat-and-moisture resistance.

Japanese Patent Publication No. 2014-116195 Japanese Patent Publication No. 2015-151617 Japanese Patent Publication No. 2015-106516 Japanese Patent Publication No. 2014-201593 Japanese Patent Publication No. 2017-125120 Japanese Patent Publication No. 2011-032405

An embodiment of the present invention aims to provide a polymerizable resin composition and a cured product thereof that enable the cured product to have excellent adhesion to metals and also have excellent heat-and-moisture resistance.

The polymerizable resin composition according to an embodiment of the present invention is obtained by reaction of at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and a hydrogenated product thereof, and a polyisocyanate. The obtained compound is contained, and the amount of acryloyl group and methacryloyl group relative to the total amount of isocyanate group, acryloyl group, and methacryloyl group contained in the compound is 12.5 to 50 mol%.

The cured product according to the embodiment of the present invention is obtained by polymerizing and curing the polymerizable resin composition.

According to an embodiment of the present invention, a polymerizable resin composition and a cured product thereof that enable the cured product to have excellent adhesion to metal and also have excellent heat-and-moisture resistance are provided.

Hereinafter, the polymerizable resin composition and its cured product according to an embodiment of the present invention will be described in detail.

The polymerizable resin composition of the present embodiment is a compound obtained by reaction of at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group, at least one of a conjugated diene polymer polyol and its hydrogenated product, and a polyisocyanate. and the amount of acryloyl group and methacryloyl group relative to the total amount of isocyanate group, acryloyl group, and methacryloyl group contained in the above compound is 12.5 to 50 mol%.

Hereinafter, “at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group” may be referred to as “acrylate having a hydroxyl group, etc.”

“Conjugated diene polymer polyol and at least one of its hydrogenated products” may be referred to as “conjugated diene polymer polyol, etc.”

“At least either an acryloyl group or a methacryloyl group” may hereinafter be referred to as a “(meth)acryloyl group.”

In addition, the compound obtained by the above reaction may be referred to as a “urethane acrylate compound.”

The compound contained in the polymerizable resin composition of the present embodiment is, for example, a urethane having an isocyanate group at both ends, which is formed by polymerizing at least one of a conjugated diene polymer polyol and its hydrogenated product and a polyisocyanate through a urethane bond. It is a urethane acrylate compound in which a (meth)acryloyl group is introduced into one of the isocyanate groups at both terminals of the compound by reacting at least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group.

The urethane acrylate compound has a urethane bond due to at least one of the conjugated diene polymer polyol and its hydrogenated product and polyisocyanate.

Originating from at least one of the acrylate having a hydroxyl group and the methacrylate having a hydroxyl group, the compound has a (meth)acryloyl group at one terminal.

Originating from the polyisocyanate, the urethane acrylate compound has an isocyanate group at the other terminal.

The urethane acrylate compound according to one embodiment has a (meth)acryloyl group and/or an isocyanate group at both terminals, a group originating from a conjugated diene polymer polyol, etc. between both terminals, and the conjugated diene polymer polyol. It has a group originating from polyisocyanate through a urethane bond at both ends of the group originating from a polyisocyanate.

Regarding the (meth)acryloyl group and/or isocyanate group present at both terminals of the urethane acrylate compound, the isocyanate group is an isocyanate group possessed by a group originating from the polyisocyanate, and the (meth)acryloyl group is the polyisocyanate group. It is a (meth)acryloyl group possessed by acrylates and the like, which has a hydroxyl group bonded to a group originating from isocyanate through a urethane bond.

And, it satisfies that the amount of the isocyanate group relative to the total amount of the isocyanate group and (meth)acryloyl group at both terminals is 50 to 87.5 mol%, and the amount of the (meth)acryloyl group is 12.5 to 50 mol%.

The urethane acrylate compound is composed of an isocyanate group at one terminal and a (meth)acryloyl group at the other terminal, but also has an isocyanate group at both terminals, and/or (meth)acryloyl group at both terminals. ) You may include those having an acryloyl group.

At least one of the acrylate having a hydroxyl group and the methacrylate having a hydroxyl group is a starting material for introducing a (meth)acryloyl group into the terminal of the compound. Acrylates etc. having this hydroxyl group may have one hydroxyl group in the molecule.

Examples of the acrylates having the hydroxyl group include derivatives of acrylic acid. Derivatives of acrylic acid include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutylacrylate, caprolactone adducts thereof, and alkyl derivatives thereof. A rene oxide adduct, etc. can be mentioned.

Examples of the methacrylate having the hydroxyl group include derivatives of methacrylic acid. Derivatives of methacrylic acid include, for example, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate, and their capro Lactone adducts, their alkylene oxide adducts, etc. can be mentioned.

Hereinafter, at least one of acrylic acid and methacrylic acid may be referred to as “(meth)acrylic acid.” Additionally, at least one of acrylate and methacrylate may be referred to as “(meth)acrylate.”

An acryloyl group is a group represented by CH ₂ =CHCO-.

A methacryloyl group is a group represented by CH ₂ =CCH ₃ CO-.

Since these (meth)acryloyl groups have a double bond, they can polymerize with each other when irradiated with active energy rays such as ultraviolet rays (UV), electron beams, and microwaves due to this double bond. In addition to irradiation with active energy rays, (meth)acryloyl groups can be polymerized with each other by thermal polymerization using a thermal polymerization initiator, moisture polymerization using a moisture curing agent, anaerobic polymerization under oxygen blocking, etc.

At least one of the conjugated diene polymer polyol and its hydrogenated substance reacts with polyisocyanate to generate a urethane bond, thereby introducing a urethane bond into the urethane acrylate compound. Examples of the polyol include diols having two hydroxyl groups, that is, conjugated diene polymers having hydroxyl groups at both terminals, and hydrogenated products thereof.

Examples of the conjugated diene polymer polyol include hydroxylated polybutadiene at both ends, hydroxylated polyisoprene at both ends, and the like.

Examples of the hydrogenated agent of the conjugated diene polymer polyol include terminally hydroxylated polybutadiene obtained by hydrogenating the terminal hydroxylated polybutadiene, and terminally hydroxylated polyisoprene obtained by hydrogenating the terminal hydroxylated polyisoprene.

Conjugated diene-based polymer polyols and the like have a diene-based monomer group or a hydride group thereof (hereinafter, these may be referred to as “diene-based monomer groups, etc.”). Examples of such a diene monomer group or its hydride group include at least one of the groups represented by the following general formulas (1) and (2).

[Formula 1]

Here, R ₁ is CH=CH ₂ or CH ₂ CH ₃ , and R ₂ is CH=CH or CH ₂ CH ₂ .

In the general formula (1), x is preferably an integer of 1 to 100.

In the general formula (2), y is preferably an integer of 1 to 100.

The amount of diene-based monomer group, etc. in the molecule of the conjugated diene-based polymer polyol, etc. is not particularly limited and can be set appropriately. For example, this amount may be 10 to 100 mol%, 50 to 100 mol%, or 80 to 100 mol%, based on 100 mol% of all monomers constituting the conjugated diene polymer polyol.

In addition, the conjugated diene polymer polyol and the like may have groups other than these.

Conjugated diene polymer polyols having groups exemplified by the above general formulas (1) and (2) have lower hydrophilicity than diol compounds such as polytetramethylene glycol and polyethylene glycol. Therefore, as the hydrophilicity is low, the group originating from the conjugated diene polymer polyol or the like is introduced into the urethane acrylate compound, so that the polymerizable resin composition and the cured product obtained by polymerizing the same have excellent water resistance.

As for the conjugated diene polymer polyol, etc., the larger the molecular weight, the lower the density of urethane bonds contained in the urethane acrylate compound, thereby lowering the viscosity of the polymerizable resin composition. Therefore, for example, when it is intended to obtain a low-viscosity polymerizable resin composition, the number average molecular weight Mn of the conjugated diene polymer polyol or the like may be 2000 to 5000.

On the other hand, when it is desired to obtain a high viscosity polymerizable resin composition, the number average molecular weight Mn of the conjugated diene polymer polyol or the like may be set to 800 to 1800, for example.

Here, the number average molecular weight Mn can be measured by GPC measurement using a Shimadzu RID-6A as a differential refractive index detector and tetrahydrofuran as the solvent.

The polyisocyanate is a starting material for introducing a urethane bond into the urethane acrylate compound and introducing an isocyanate group at the terminal of the urethane acrylate compound.

Examples of such polyisocyanate include aliphatic polyisocyanate, cycloaliphatic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate. Among these, alicyclic polyisocyanates are preferred.

Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, etc. are mentioned.

Alicyclic polyisocyanates include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1 , 3-bis(isocyanate methyl)cyclohexane, etc.

Aromatic polyisocyanates include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and 4,4' -Dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc. are mentioned.

Examples of aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

Moreover, examples of polyisocyanate include dimers, trimers, and modified forms of these organic isocyanates, such as biuretized isocyanate. Additionally, these may be used individually or in combination of two or more types.

The isocyanate group is represented by NCO. These isocyanate groups can polymerize with each other by reacting with an active hydrogen group to form a urethane bond. In this embodiment, isocyanate groups can polymerize with each other through water in the air. As the isocyanate group remains in the cured product, high adhesion to a base material such as metal can be achieved.

In this embodiment, for example, when the polymerizable resin composition is cured, not only can the (meth)acryloyl groups at one terminal in the urethane acrylate compound polymerize, but also the isocyanate at the other terminal. Elements can polymerize through water in the air. At this time, when the isocyanate group is equal to or more than the (meth)acryloyl group, the resulting cured product tends to have better adhesion to the metal.

Therefore, for example, taking this viewpoint into consideration, the ratio of the amounts of (meth)acryloyl group and isocyanate group can be appropriately set.

For example, the amount of (meth)acryloyl group relative to the total amount (100 mol%) of (meth)acryloyl group and isocyanate group in the molecule of the urethane acrylate compound is 12.5 to 50 mol%, and 25 to 50 mol%. % is more preferable. When the ratio is 12.5 to 50 mol%, the adhesion to metal becomes more excellent.

Moreover, the amount of the isocyanate group relative to the total amount of the (meth)acryloyl group and the isocyanate group in the molecule of the urethane acrylate compound is 50 to 87.5 mol%, and is more preferably 50 to 75 mol%.

The urethane acrylate compound is obtained, for example, by reacting the conjugated diene polyols exemplified above, the polyisocyanate exemplified above, the acrylate having a hydroxyl group exemplified above, etc. as starting materials. .

More specifically, for example, the conjugated diene polyols exemplified above and the polyisocyanate exemplified above are reacted in the presence of a diluent and a polymerization inhibitor (reaction in the first step) to form isocyanate groups at both ends. The urethane acrylate compound can be obtained by producing a urethane compound as an intermediate and reacting the intermediate with an acrylate having a hydroxyl group as exemplified above (second stage reaction). That is, by linking the hydroxyl group (active hydrogen group) of the conjugated diene polyol or the like with the isocyanate group of the polyisocyanate through a urethane bond, an intermediate having this linkage as the main skeleton and isocyanate groups at both ends is once produced, The above-mentioned urethane acrylate compound can be obtained by connecting the hydroxyl group (active hydrogen group) of an acrylate, such as an acrylate having a hydroxyl group on one side of the isocyanate group at both terminals of the intermediate, with a urethane bond.

As starting materials, the blending amount of acrylate having a hydroxyl group, polyisocyanate, and conjugated diene polymer polyol is, for example, the amount of the terminal (meth)acryloyl group and the terminal isocyanate group in the urethane acrylate compound. The content can be appropriately set so that it is within the above range. For example, the compounding quantity of polyisocyanate may be 1.1 to 2.0 times the molar ratio with respect to the compounding quantity of conjugated diene polymer polyol or the like. Moreover, the compounding amount of acrylate having a hydroxyl group or the like may be 0.125 to 0.5 times the molar ratio with respect to the amount of isocyanate groups at both terminals of the intermediate.

The urethane acrylate compound may have other groups in addition to the above groups.

In addition to the urethane acrylate compound, the polymerizable resin composition may contain additives such as a diluent, a polymerization inhibitor, a polymerization initiator, a polymerization accelerator, and a catalyst. The amount of the urethane acrylate compound contained in the polymerizable resin composition is not particularly limited, and may be, for example, 1 to 99% by mass, and preferably 10 to 90% by mass.

Polymerization inhibitors include, for example, hydroquinones such as hydroquinone monomethyl ether, p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, and 2,5-diphenylparabenzoquinone, and tetramethylpiperidinyl- N-oxy radicals such as N-oxy radical (TEMPO), substituted catechols such as t-butylcatechol, amines such as phenothiazine, diphenylamine, phenyl-β-naphthylamine, cuperone, nitroso Benzene, picric acid, molecular oxygen, sulfur, copper (II) chloride, etc. are mentioned.

When the polymerizable resin composition contains a polymerization inhibitor, it is possible to prevent the urethane acrylate compound from suddenly polymerizing.

The amount of the polymerization inhibitor contained in the polymerizable resin composition is not particularly limited, and may be, for example, 0.0001 to 5% by mass, and preferably 0.01 to 1% by mass.

Diluents include, for example, acrylates such as isoboronyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, isostearyl acrylate, and phenoxyethanol acrylate, and isoboronyl methacrylate. , methacrylates such as tetrahydrofurfuryl methacrylate, lauryl methacrylate, isostearyl methacrylate, and phenoxyethanol methacrylate.

Here, when the polymerizable resin composition further contains a component having such a (meth)acryloyl group as a diluent, when the polymerizable resin composition is cured, the (meth)acrylate of the urethane acrylate compound In addition to the polymerization of the groups, the (meth)acryloyl group of the urethane acrylate and the (meth)acryloyl group of the diluent polymerize, resulting in a polymerizable resin composition with more excellent polymerization properties.

As a diluent, at least one of acyclic acrylamide and acyclic methacrylamide (hereinafter sometimes referred to as acyclic (meth)acrylamide) may be used. For example, N,N-dimethylacrylamide, N,N-dialkylacrylamide such as N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, etc. N,N-dialkyl methacrylamide, dialkylaminopropyl (meth)acrylamide such as dimethylaminopropylacrylamide, and monoalkyl (meth)acrylamide such as isopropylacrylamide.

Any one of these may be used, or two or more types may be used in combination. Acyclic (meth)acrylamide can also be polymerized with the (meth)acryloyl group of the urethane acrylate compound in the same way as the component having a (meth)acryloyl group as a diluent.

The amount of diluent (preferably acyclic (meth)acrylamide) contained in the polymerizable resin composition is not particularly limited, and may be, for example, 1 to 90% by mass, preferably 10 to 70% by mass. do.

Examples of the polymerization initiator include conventionally known polymerization initiators, for example, aromatic ketones such as 1-hydroxycyclohexylphenyl ketone and benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and diphenyl sulfur. Sulfur compounds such as phide and thiocarbamate, acetophenone, acetophenone benzyl ketal, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone , triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, Benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2 -Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1-( 4-(1-methylvinyl)phenyl)propanone) and the like.

In addition, commercially available polymerization initiators include, for example, Chiba Specialty Chemicals Co., Ltd. brand names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850. , CG24-61, Darocure 1116, 1173, BASF brand name: Lucirin TPO, UCB brand name: Eubecryl P36, Fratelli-Lamberti brand name: Ezacure KIP150, KIP65LT, KIP100F, KT37, Examples include KT55, KTO46, KIP75/B, etc.

When the polymerizable resin composition contains a polymerization initiator, it becomes easy to polymerize when irradiated with active energy rays, especially ultraviolet rays.

The amount of the polymerization initiator contained in the polymerizable resin composition is not particularly limited, and may be, for example, 0.0001 to 10 mass%, and preferably 0.1 to 5 mass%.

Catalysts that promote curing (moisture curing) by water in the air include dimorpholinodiethyl ether, N-ethylmorpholine, and the like.

Uses of the polymerizable resin composition include uses for adhesion to metal. For example, use for covering metal in electric wiring, use as an insulating thin film (conformal coat) on circuit boards, optical adhesive for displays, etc., moisture-proof insulating paint, rust-prevention paint, It can be used as a heat-resistant coating material, etc.

In one embodiment, the polymerizable resin composition may be used for covering the connection portion of the wire and the connection terminal in a wire harness provided with an electric wire and a metal connection terminal connected to an end of the wire. . That is, the polymerizable resin composition may be used, for example, for end treatment of wire harness.

Here, since the wire harness is usually formed by connecting the end of an electric wire covered with a vinyl chloride film and a connection terminal (connector), the cured product formed by curing the polymerizable resin composition so that it covers the connection portion is , comes into contact with a film made of vinyl chloride. Even in such a case, the cured product is difficult to embrittle the film made of vinyl chloride, and thus the wire harness has excellent heat and moisture resistance. In this way, when the polymerizable resin composition is used to cover the connection portion of the wire harness, the polymerizable resin composition becomes more useful.

In one embodiment, the polymerizable resin composition may be used for covering and protecting circuit boards, and more specifically, for conformal coating. Conformal coating is a thin insulating film that follows the surface shape of a circuit board and is applied as a barrier to prevent harmful effects from environmental conditions on various circuit boards such as electronic circuit boards and electronic circuit mounting boards.

Here, the film made of the polymerizable resin composition has high adhesion to the copper corresponding to the wiring portion of the circuit board, and also has high adhesion to the glass epoxy portion that is the resin portion of the substrate. In addition, it has heat and moisture resistance, that is, high electrical insulation under high temperature and high humidity conditions. In addition, in addition to being able to exhibit sufficient properties even when cured by ultraviolet rays, by using moisture curing together, high protection performance can be exhibited even in dark areas of the circuit board that are not easily hit by ultraviolet rays.

The metal to which the polymerizable resin composition of the present embodiment adheres may, for example, be appropriately set according to the above-mentioned use. Examples of such metals include aluminum and its alloys, copper and its alloys, and the like.

Here, for example, when aluminum or its alloy is used as the material of the electric wire, the aluminum component is oxidized on the surface of the electric wire to form an insulating alumina layer, and the electrical resistance increases due to this alumina layer. As a result, fever may occur. However, even when it adheres to aluminum or its alloy, which easily generates heat, embrittlement and cracking of the vinyl chloride film covering the wire can be suppressed. From this point, the heat-and-moisture resistance of the cured product can be improved.

The polymerizable resin composition of the present embodiment may be polymerized and cured by at least one (one or two or more) of active energy rays, heating, and water (active hydrogen groups) in the air. Specifically, (meth)acryloyl groups can polymerize with each other by active energy rays. Isocyanate groups can polymerize with each other by heating or water in the air. In addition, the polymerizable resin composition of the present embodiment may be polymerized and cured in other ways than these.

Next, the cured product of this embodiment will be described. The cured product of the present embodiment is obtained by polymerizing and curing the polymerizable resin composition of the present embodiment.

For example, the cured product is obtained by applying the polymerizable resin composition onto the above-mentioned metal, polymerizing it, and curing it. Additionally, the cured product is obtained by applying the polymerizable resin composition onto the above-described circuit board, polymerizing it, and then curing it.

Methods for polymerizing the polymerizable resin composition include, as described above, polymerizing it using active energy rays, heating, or water in the air (active hydrogen groups). The polymerizable resin composition may be polymerized by applying at least any of these active energy rays, heating, and water in the air. However, the method of polymerizing the polymerizable resin composition is not particularly limited to the following method.

By irradiating an active energy ray to a polymerizable resin composition, (meth)acryloyl groups having a polymerizable double bond in the above compound can be polymerized. Examples of active energy rays include ultraviolet rays, electron beams, and microwaves. The irradiation amount of active energy rays can be appropriately set to a level where the polymerizable resin composition can be cured.

When irradiating ultraviolet rays, it is preferable that the polymerizable resin composition contains the polymerization initiator described above. This makes it easier to polymerize the polymerizable resin composition.

In addition, as described above, (meth)acryloyl groups may be polymerized by thermal polymerization using a thermal polymerization initiator, moisture polymerization using a moisture curing agent, or anaerobic polymerization when in contact with a metal surface under oxygen blocking.

By heating the polymerizable resin composition, thermal energy can be applied, thereby polymerizing the isocyanate groups of the above compound through water (active hydrogen group) in the air. Examples of heating means include heating the polymerizable resin composition by radiant heat during irradiation of infrared rays, hot air, microwaves, steam, or ultraviolet rays. Heating temperature and heating time can be appropriately set to a level where the polymerizable resin composition can be cured.

By contacting with water in the air, the isocyanate groups can be polymerized through the water (active hydrogen group) in the air. In this case, polymerization is started simply by bringing the applied polymerizable resin composition into contact with air. Therefore, in the applied polymerizable resin composition, even if there are parts where the above-mentioned active energy rays were not sufficiently irradiated or parts where the above-mentioned heating was not sufficiently applied, the isocyanate group can be polymerized simply by contact with air. there is.

Additionally, while performing the above-described heating, the polymerizable resin composition may be brought into contact with water in the air.

As described above, the polymerizable resin composition of the present embodiment contains a urethane acrylate compound obtained by reaction of an acrylate having a hydroxyl group, etc., a conjugated diene polymer polyol, etc., and a polyisocyanate, and is contained in the urethane acrylate compound. The amount of the (meth)acryloyl group relative to the total amount of the isocyanate group and (meth)acryloyl group is 12.5 to 50 mol%.

According to this structure, the urethane acrylate compound contained in the polymerizable resin composition has a (meth)acryloyl group at the terminal of the molecule. Accordingly, when the polymerizable resin composition is cured, the acryloyl groups react with each other due to the polymerizable double bond of the acryloyl group, thereby allowing polymerization.

Moreover, the urethane acrylate compound has an isocyanate group at the other terminal of the molecule. Accordingly, when the polymerizable resin composition is cured, the isocyanate groups react with each other through water (active hydrogen groups) in the air, thereby allowing polymerization.

Moreover, the urethane acrylate compound has a group originating from a conjugated diene polymer polyol or the like between the two terminals. As a result, in addition to polymerization resulting from the groups at both ends occurring as described above, the cured product obtained by curing the polymerizable resin composition has excellent adhesion to metal and is also excellent in heat-and-moisture resistance.

In addition, when the amount of the (meth)acryloyl group relative to the total amount of the isocyanate group and the (meth)acryloyl group contained in the urethane acrylate compound is 12.5 to 50 mol%, the adhesiveness of the cured product to the metal and heat-and-moisture resistance are improved. This becomes even more excellent.

Therefore, a polymerizable resin composition is provided that allows the cured product to have excellent adhesion to metal and also excellent heat-and-moisture resistance by containing the urethane acrylate compound having the above three groups.

In the polymerizable resin composition of this embodiment, the polyisocyanate may be an alicyclic polyisocyanate. As a result, the cured product more reliably has excellent adhesion to the metal and is also excellent in heat-and-moisture resistance.

In the polymerizable resin composition of this embodiment, acyclic (meth)acrylamide may be further contained as a diluent. Thereby, the viscosity of the polymerizable resin composition can be lowered while suppressing deterioration of heat-and-moisture resistance without increasing moisture permeability, and the elongation of the cured product can be increased.

The polymerizable resin composition of this embodiment is preferably used for coating metal. According to this, the said adhesiveness and heat-and-moisture resistance can be exhibited more reliably.

The polymerizable resin composition of this embodiment may be coated on the connection portion of the wire and the connection terminal in a wire harness provided with an electric wire and a connection terminal connected to an end of the wire.

Since a wire harness is usually formed by connecting the end of an electric wire covered with a vinyl chloride film and a connection terminal (connector), the cured product formed by curing the polymerizable resin composition to cover the connection portion is vinyl chloride. It comes into contact with the film. Even in such a case, the cured product is unlikely to embrittle the film made of vinyl chloride, and thus the wire harness has excellent heat and moisture resistance.

In addition, if it is the polymerizable resin composition of this embodiment, sufficient adhesion is exhibited even if a silane coupling agent is not specifically interposed.

Here, in order to improve adhesion, it is conceivable to treat the surface of the connection portion with an acid-based material or to form a primer layer on the surface. However, forming a primer layer leads to an increase in cost and production tact, and treatment with an acid-based material may lead to corrosion of the connection portion. In contrast, according to the polymerizable resin composition of the present embodiment, the adhesion of the cured product to the connection portion is excellent even without forming a primer layer or treating with an acid-based material. Therefore, an increase in cost and production tact can be suppressed, and corrosion of the connection portion can also be suppressed.

From the above, the polymerizable resin composition becomes more useful when it is used to cover the connection portion of the wire harness.

The polymerizable resin composition of this embodiment may be used to cover and protect a circuit board.

According to this embodiment, since the urethane acrylate compound has a polymerizable double bond at one terminal and an isocyanate residue at the other terminal, it has high adhesion to copper corresponding to the wiring portion of the circuit board, It also has high adhesion to the glass epoxy part, which is the resin part of the substrate.

In addition, it has high electrical insulation even under the high temperature and high humidity conditions required for moisture-proof insulating resin, and is excellent in heat and moisture resistance.

In addition, in addition to being able to exhibit sufficient properties even when cured by ultraviolet rays, by using moisture curing together, high protection performance can be exhibited even in dark areas of the circuit board that are not easily hit by ultraviolet rays.

In this way, since it maintains high substrate adhesion and high electrical insulation even in a high temperature and high humidity environment, it is suitable as a protective material for circuit boards.

In addition, even if the amount of ultraviolet irradiation is low, a high polymerization rate is exhibited, and moisture curing is possible in addition to ultraviolet curing. Additionally, when used in combination with moisture curing, no change in physical properties such as adhesion occurs.

In addition, the polymerizable resin composition has excellent storage stability despite the isocyanate group remaining in the urethane acrylate compound.

In the polymerizable resin composition of this embodiment, it may be possible to polymerize and cure it by at least one of active energy rays, heating, and water in the air. According to this, the polymerizable resin composition becomes easy to harden.

The cured product of this embodiment is obtained by polymerizing and curing the polymerizable resin composition. According to the cured product of the present embodiment, a cured product that is excellent in adhesion to metal and is also excellent in heat-and-moisture resistance is provided.

As mentioned above, according to this embodiment, the polymerizable resin composition and its hardened|cured material which enable a hardened|cured material to have excellent adhesion to a metal and are also excellent in heat-and-moisture resistance are provided.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. In addition, in the examples, “%” and “part” mean mass standards unless otherwise specified.

[Synthesis Example 1] (Production of UA-1)

In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminal hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,400), 888.8 g (4.0 mol) of isophorone diisocyanate, and isoboronyl acrylate. 1287 g and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours (first stage reaction). After that, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours (second stage reaction). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-1 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, with respect to the total amount of the terminal acryloyl group (hereinafter sometimes referred to as free acryloyl group) and the terminal isocyanate group (hereinafter sometimes referred to as free isocyanate group) in the urethane acrylate compound, The injection amount of 2-hydroxyethyl acrylate was set so that the amount ratio of free acryloyl group was 25 mol% and the amount ratio of free isocyanate group was 75 mol%. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.98 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by reacting an excess amount of dibutylamine with isocyanate using bromophenol blue as an indicator and titrating the remaining amount with hydrochloric acid. While the theoretical value of the above ratio of free isocyanate groups was 0.98 mass%, the actual measured value was 0.98 mass%, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured as the amount of change in the absorption spectrum derived from the isocyanate group around 2260 cm ^-1 by FT-IR measurement using Nicolet6700, product name, manufactured by Samo Fisher. . As a result, while the theoretical value of the above ratio of free isocyanate groups was 75 mol%, the measured value was 75 mol% (amount of free acryloyl groups: 25 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 2] (Production of UA-2)

The same operation as in Synthesis Example 1 was performed except that the injected 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-2 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.65 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.65% by mass, but the actual measured value was 0.65%. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 50 mol% (amount of free acryloyl group: 50 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 3] (Production of UA-3)

The same operation as in Synthesis Example 1 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-3 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 1.44 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 1.44% by mass, while the actual measured value was It was 1.44% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 87.5 mol% (amount of free acryloyl group: 12.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 4] (Production of UA-4)

In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminal hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,400), 672.8 g (4.0 mol) of hexamethylene diisocyanate, and isoboronyl acrylate. 1218 g and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours. After that, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-4 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 1.02% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 1.02% by mass, but the actual measured value was 1.00. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 73.5 mol% (amount of free acryloyl group: 26.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 5] (Production of UA-5)

The same operation as in Synthesis Example 4 was performed except that the injected 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-5 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.34 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.34% by mass, but the actual value was 0.33. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 50 mol% (amount of free acryloyl group: 50 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 6] (Production of UA-6)

The same operation as in Synthesis Example 4 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-6 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.79 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.79% by mass, while the actual value was It was 0.78% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 86.4 mol% (amount of free acryloyl group: 13.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 7] (Synthesis of UA-7)

In a separable flask equipped with a stirring device, 4500 g (3.0 mol) of terminally hydroxylated polybutadiene (GI1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,500), 888.8 g (4.0 mol) of isophorone diisocyanate, and isoboronyl acrylic. 1362 g of nitrate and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours. After that, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-7 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.93% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.93% by mass, but the actual value was 0.93. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 76.2 mol% (amount of free acryloyl group: 23.8 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 8] (Production of UA-8)

The same operation as in Synthesis Example 7 was performed except that the injected 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-8 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.61 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.61% by mass, but the actual value was 0.62. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1. As a result, the theoretical value of the above ratio of isocyanate groups was 50 mol%, and the actual measurement was The value was 50.8 mol% (amount of free acryloyl group: 49.2 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 9] (Production of UA-9)

The same operation as in Synthesis Example 7 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-9 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 1.08 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 1.08% by mass, while the actual measured value was It was 1.09% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 87.5 mol% (amount of free acryloyl group: 12.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 10] (Production of UA-10)

In a separable flask equipped with a stirring device, 4500 g (3.0 mol) of terminally hydroxylated polybutadiene (GI1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,500), hexamethylene diisocyanate 672.8 (4.0 mol), and isoboronyl acrylate. 1300 g and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours. After that, 58 g (0.5 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-10 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.96% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.96% by mass, but the actual value was 0.95. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 74.2 mol% (amount of free acryloyl group: 25.8 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 11] (Production of UA-11)

The same operation as in Synthesis Example 10 was performed except that the injected 2-hydroxyethyl acrylate was changed to 116 g (1.0 mol). As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-11 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.33% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.33 mass%, but the actual measured value was 0.34. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 51.5 mol% (amount of free acryloyl group: 48.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 12] (Production of UA-12)

The same operation as in Synthesis Example 10 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-12 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.77% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the ratio of free isocyanate groups was 0.77% by mass, while the actual value was It was 0.76% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 86.4 mol% (amount of free acryloyl group: 13.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 13] (Production of UA-13)

In a separable flask equipped with a stirring device, 4500 g (3.0 mol) of polytetramethylene glycol (PTMG1500 manufactured by Mitsubishi Chemical Corporation, molecular weight 1,500), 888.8 (4.0 mol) of isophorone diisocyanate, 1362 g of isoboronyl acrylate, and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 3 hours. After that, 116 g (1 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one end, an isocyanate group at the other end, and a group derived from polytetramethylene glycol (PTMG) between both ends, a diluent having an acryloyl group, Polymerizable resin composition UA-13 containing a polymerization inhibitor was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.31 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.31% by mass, but the actual value was 0.30. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 48.4 mol% (amount of free acryloyl group: 51.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 14] (Production of UA-14)

The same operation as in Synthesis Example 13 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, polymerization has a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group derived from PTMG between both ends, a diluent having an acryloyl group, and a polymerization inhibitor in the molecule. Resin composition UA-14 was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.72% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.72% by mass, while the actual measured value was It was 0.73% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 88.7 mol% (amount of free acryloyl group: 11.3 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 15] (Production of UA-15)

In a separable flask equipped with a stirring device, 4500 g (3.0 mol) of polyethylene glycol (PEG1500 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., molecular weight 1,500), 888.8 (4.0 mol) of isophorone diisocyanate, 1362 g of isoboronyl acrylate, and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 3 hours. After that, 116 g (1 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was performed at 70°C for 2 hours. As a result, a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group derived from polyethylene glycol (PEG) between both ends, a diluent having an acryloyl group, and polymerization are prohibited. A polymerizable resin composition UA-15 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.31 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.31% by mass, but the actual value was 0.30. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 48.4 mol% (amount of free acryloyl group: 51.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 16] (Production of UA-16)

The same operation as in Synthesis Example 15 was performed except that the injected 2-hydroxyethyl acrylate was changed to 29 g (0.25 mol). As a result, polymerization has a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a PEG-derived group between both ends, a diluent having an acryloyl group, and a polymerization inhibitor in the molecule. Resin composition UA-16 was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.72% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.72% by mass, while the actual measured value was It was 0.70% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 85.1 mol% (amount of free acryloyl group: 14.9 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 17] (Production of UA-17)

In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminal hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,400), 888.8 g (4.0 mol) of isophorone diisocyanate, and isoboronyl acrylate. 1287 g and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours. After that, 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was carried out at 70°C for 2 hours. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-17 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 10 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 10 mol%, and the ratio of the amount of free isocyanate group is 90 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.95 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.95% by mass, while the actual measured value was It was 0.94% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 90 mol% while the theoretical value was 90 mol%. , the measured value was 89.9 mol% (amount of free acryloyl group: 10.1 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the isocyanate group.

[Synthesis Example 18] (Production of UA-18)

The same operation as in Synthesis Example 17 was performed except that the injected 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was changed to 139 g (1.2 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-18 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 60 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 60 mol%, and the ratio of the amount of free isocyanate group is 40 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.52% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.52% by mass, while the actual measured value was It was 0.50% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 40 mol% while the theoretical value was 40 mol%. , the measured value was 38.5 mol% (amount of free acryloyl group: 61.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 19] (Production of UA-19)

In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminal hydroxylated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,400), 672.8 g (4.0 mol) of hexamethylene diisocyanate, and isoboronyl acrylate. 1233 g and 1.8 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 3 hours. After that, 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was carried out at 70°C for 2 hours. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-19 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 10 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 10 mol%, and the ratio of the amount of free isocyanate group is 90 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.96% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the ratio of free isocyanate groups was 0.96% by mass, while the actual value was It was 0.96% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 90 mol% while the theoretical value was 90 mol%. , the measured value was 90 mol% (amount of free acryloyl group: 10 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 20] (Production of UA-20)

The same operation as in Synthesis Example 19 was performed except that the injected 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was changed to 139 g (1.2 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-20 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 60 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 60 mol%, and the ratio of the amount of free isocyanate group is 40 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.27 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.27% by mass, while the actual measured value was It was 0.26% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 40 mol% while the theoretical value was 40 mol%. , the measured value was 38.5 mol% (amount of free acryloyl group: 61.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 21] (Production of UA-21)

The same operation as in Synthesis Example 1 was performed except that isoboronyl acrylate in Synthesis Example 1 was changed to tetrahydrofurfuryl acrylate. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-21 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.65 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.65% by mass, but the actual measured value was 0.65%. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 75 mol% (amount of free acryloyl group: 25 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 22] (Production of UA-22)

The same operation as in Synthesis Example 1 was performed except that the amount of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was changed to 232 g (2.0 mol). Thereby, a polymerizable resin composition UA- is prepared, which has within the molecule a urethane acrylate compound having an acryloyl group at both ends and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. I got 22.

The ratio of the amount of 2-hydroxyethyl acrylate injected corresponded to 100 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 100 mol%, and the ratio of the amount of free isocyanate group is 0 mol% (free isocyanate The injection amount of 2-hydroxyethyl acrylate was set so that the group does not exist. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0 mass%, but the actual measured value was 0.1. It was % by mass or less, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group. Additionally, it was found that almost no free isocyanate existed.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 0 mol%. The actual measured value was 0 mol% (amount of free acryloyl group: 100 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group. Additionally, it was found that almost no free isocyanate existed.

[Synthesis Example 23] (Production of UA-23)

By adding 2 parts of isophorone diisocyanate to 100 parts of UA-22 obtained in Synthesis Example 22, a urethane acrylate compound having an acryloyl group at both terminals and a group resulting from terminal hydroxypolybutadiene between both terminals is produced in the molecule. A polymerizable resin composition UA-23 containing a polyisocyanate, a diluent having an acryloyl group, and a polymerization inhibitor was obtained. That is, there is no free isocyanate group in the urethane acrylate compound, but 0.37 mass% (50 mol%) of free isocyanate is present in a polyisocyanate separate from the compound, relative to the amount of acryloyl groups at both ends of the urethane acrylate compound. A polymerizable resin composition UA-23 containing an isocyanate group was obtained.

[Synthesis Example 24] (Synthesis of UA-24)

In a separable flask equipped with a stirring device, 4200 g (3.0 mol) of terminally hydrogenated polybutadiene (G1000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 1,400), 888.8 g (4.0 mol) of isophorone diisocyanate, and isoboronyl acrylate. 1287 g and 2 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 4 hours. After that, 65 g (0.5 mol) of 2-hydroxyethyl methacrylate (HEMA, manufactured by Nippon Catalyst Co., Ltd., molecular weight 130) was further added, and reaction was further performed at 70°C for 2 hours. As a result, a urethane acrylate compound having a methacryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydrogenated polybutadiene between both ends, a diluent having an acryloyl group, and polymerization. A polymerizable resin composition UA-24 containing an inhibitor was obtained.

The amount of 2-hydroxyethyl methacrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free methacryloyl group to the total amount of free methacryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%. The injection amount of 2-hydroxyethyl methacrylate was set as much as possible. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.65% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.65% by mass, but the actual measured value was 0.65%. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of free isocyanate group and free methacryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 75.1 mol% (amount of free methacryloyl group: 24.9 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free methacryloyl group.

[Synthesis Example 25] (Production of UA-25)

The same operation as Synthesis Example 24 was performed except that the injected 2-hydroxyethyl methacrylate was changed to 130 g (1.0 mol). As a result, polymerization is prohibited between a urethane acrylate compound having a methacryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a molecule having a methacryloyl group at one end, an isocyanate group at the other end A polymerizable resin composition UA-25 having the following was obtained.

The amount of 2-hydroxyethyl methacrylate injected corresponded to 50 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free methacryloyl group to the total amount of free methacryloyl group and free isocyanate group in the urethane acrylate compound is 50 mol%, and the ratio of the amount of free isocyanate group is 50 mol%. The injection amount of 2-hydroxyethyl methacrylate was set as much as possible. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.32% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.32% by mass, but the actual value was 0.31. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of free isocyanate group and free methacryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 50 mol%, The actual measured value was 50 mol% (amount of free methacryloyl group: 50 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free methacryloyl group.

[Synthesis Example 26] (Production of UA-26)

The same operation as Synthesis Example 24 was performed except that the injected 2-hydroxyethyl methacrylate was changed to 32.5 g (0.25 mol). As a result, polymerization is prohibited between a urethane acrylate compound having a methacryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a molecule having a methacryloyl group at one end, an isocyanate group at the other end A polymerizable resin composition UA-26 having the following was obtained.

The amount of 2-hydroxyethyl methacrylate injected corresponded to 12.5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free methacryloyl group to the total amount of free methacryloyl group and free isocyanate group in the urethane acrylate compound is 12.5 mol%, and the ratio of the amount of free isocyanate group is 87.5 mol%. The injection amount of 2-hydroxyethyl methacrylate was set as much as possible. At this time, if the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.76 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.76 mass%, while the actual measured value was It was 0.76% by mass, and the theoretical value and the actual measured value were approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free methacrylate group.

The amount of free isocyanate groups remaining at the terminals of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the above ratio of free isocyanate groups was found to be 87.5 mol% while the theoretical value was 87.5 mol%. , the measured value was 87.4 mol% (amount of free methacryloyl group: 12.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free methacrylate group.

[Synthesis Example 27] (Production of UA-27)

In a separable flask equipped with a stirring device, 4500 g (1.5 mol) of terminal hydroxylated polybutadiene (G3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3,000), 555.5 g (2.5 mol) of isophorone diisocyanate, and isoboronyl acrylate. 1264 g and 1.8 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 3 hours. After that, 58 g (0.50 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-27 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.99% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.99% by mass, but the actual value was 0.98. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 74.2 mol% (amount of free acryloyl group: 25.8 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 28] (Production of UA-28)

UA-28 was obtained through the same synthesis as UA-27 except that the isoboronylacrylate in Synthesis Example 27 was replaced with diethylacrylamide.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.99% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.99% by mass, but the actual measured value was 1.00. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 75.8 mol% (amount of free acryloyl group: 24.2 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 29] (Production of UA-29)

In a separable flask equipped with a stirring device, 4650 g (1.5 mol) of terminally hydroxylated polybutadiene (GI3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3,100), 555.5 g (2.5 mol) of isophorone diisocyanate, and isoboronyl acrylic. 1301 g of nitrate and 1.8 g of hydroquinone monomethyl ether were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 3 hours. After that, 58 g (0.50 mol) of 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Catalyst Co., Ltd., molecular weight 116) was further added, and reaction was further performed at 70°C for 2 hours. As a result, polymerization is prohibited between a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group resulting from terminal hydroxylated polybutadiene between both ends, a diluent having an acryloyl group, and A polymerizable resin composition UA-29 having the following was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.97 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titrimetric method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.97 mass%, but the actual measured value was 0.95. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 73.5 mol% (amount of free acryloyl group: 26.5 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 30] (Production of UA-30)

UA-30 was obtained by synthesizing in the same manner as in Synthesis Example 29 except that the diluted monomer was changed from isoboronyl acrylate to diethylacrylamide.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.97 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.97 mass%, but the actual measured value was 0.96. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 74 mol% (amount of free acryloyl group: 26 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 31] (Production of UA-31)

The same operation as Synthesis Example 13 was performed except that the injected 2-hydroxyethyl acrylate was changed to 58 g (0.50 mol). As a result, polymerization has a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a group derived from PTMG between both ends, a diluent having an acryloyl group, and a polymerization inhibitor in the molecule. Resin composition UA-31 was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.93% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.93% by mass, but the actual value was 0.91. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 73.4 mol% (amount of free acryloyl group: 26.6 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 32] (Production of UA-32)

The same operation as in Synthesis Example 15 was performed except that the injected 2-hydroxyethyl acrylate was changed to 58 g (0.50 mol). As a result, polymerization has a urethane acrylate compound having an acryloyl group at one end, an isocyanate group at the other end, and a PEG-derived group between both ends, a diluent having an acryloyl group, and a polymerization inhibitor in the molecule. Resin composition UA-32 was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 25 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 25 mol%, and the ratio of the amount of free isocyanate group is 75 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 0.93% by mass.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 0.93% by mass, but the actual value was 0.90. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 75 mol%. The actual measured value was 72.6 mol% (amount of free acryloyl group: 27.4 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[Synthesis Example 33] (Production of UA-33)

The same operation as in Synthesis Example 1 was performed except that the injected 2-hydroxyethyl acrylate was changed to 11.6 g (0.1 mol). Thereby, a urethane acrylate compound having within the molecule an acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from terminal hydroxypolybutadiene between both ends, a diluent having an acryloyl group, and a polymerization inhibitor. A polymerizable resin composition UA-33 having was obtained.

The amount of 2-hydroxyethyl acrylate injected corresponded to 5 mol% of the total amount of isocyanate groups at both terminals of the intermediate (urethane compound) obtained in the first step reaction. That is, the ratio of the amount of free acryloyl group to the total amount of free acryloyl group and free isocyanate group in the urethane acrylate compound is 5 mol%, and the ratio of the amount of free isocyanate group is 95 mol%, The injection amount of 2-hydroxyethyl acrylate was set. At this time, when the ratio of free isocyanate groups is expressed in mass, it corresponds to 1.25 mass%.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same titration method as in Synthesis Example 1. As a result, the theoretical value of the above ratio of free isocyanate groups was 1.25% by mass, while the actual measured value was 1.30. It is mass%, and the theoretical value and the actual measured value are approximately identical. As a result, it was found that the theoretical value and the actual measured value approximately coincide with the ratio of the free isocyanate group and the free acryloyl group.

The amount of free isocyanate groups remaining at the terminal of the obtained urethane acrylate compound was measured by the same FT-IR measurement as in Synthesis Example 1, and the theoretical value of the above ratio of free isocyanate groups was 95 mol%. The actual measured value was 94.8 mol% (amount of free acryloyl group: 5.2 mol%). From this result, it was found that the theoretical value and the actual measured value roughly coincide with the ratio of the free isocyanate group and the free acryloyl group.

[First Embodiment] (Use for covering connection parts in wire harness)

The following components were further added to the polymerizable resin compositions of Synthesis Examples 1 to 26 to prepare the polymerizable resin compositions of each Example and Comparative Example.

[Example 1]

To 100 parts of UA-1 obtained in Synthesis Example 1, as a photopolymerization initiator, 3 parts of 1-hydroxycyclohexylphenylketone (Irgacure 184, manufactured by BASF), and dimorpholinodiethyl ether DMDEE, manufactured by Mitsui Chemical Fine Co., Ltd. ) 0.1 part was added and dissolved uniformly to obtain a polymerizable resin composition.

[Examples 2 to 16, Comparative Examples 1 to 10]

The polymerizable resin compositions of Examples 2 to 16 and Comparative Examples 1 to 10 were obtained in the same manner as in Example 1 except that UA-1 was changed to UA-2 to 26 shown in Table 1 below.

The polymerizable resin compositions obtained in each Example and Comparative Example were polymerized and cured by the following method, and evaluated by the following method. The results are shown in Table 1.

[Material used]

As a base material made of aluminum, A1050P (manufactured by TP Mechanical Engineering Co., Ltd.) specified in the JIS standard was used.

As a copper base material, C1020P (manufactured by TP Engineering & Construction Co., Ltd.) specified in the JIS standard was used.

As a resin substrate, PET film (Lumirror, T-60, 100 μm, manufactured by Toray Industries, Ltd.) was used.

As a resin substrate, a soft vinyl chloride film with a thickness of 1 mm was used.

[curing device]

As a curing device for curing the polymerizable resin composition, an ultraviolet (UV) irradiation device was used. As the UV irradiation device, a belt conveyor type UV curing device equipped with a metal halide lamp (trade name CSN2-40A, manufactured by GS Yuasa) was used. The irradiation conditions were that the integrated illuminance was 200 mJ/cm2.

[Curing conditions]

If conditions were not specifically specified, the polymerizable resin composition was cured by irradiating ultraviolet rays at an integrated illumination intensity of 200 mJ/cm2, and then the obtained cured product was heated at 85°C for 5 minutes.

[Storage Stability]

The polymerizable resin compositions (samples) obtained in each Example and Comparative Example were placed in an airtight glass container, stored in a constant temperature room at 50°C for 3 months, and changes in viscosity were confirmed after accelerated deterioration by heating. did. Viscosity was measured using a corn plate type viscometer. (Measurement temperature 25℃)

If the change in viscosity after heating compared to before starting heating (initial value) is within 10%, the storage stability is evaluated as excellent and is indicated with "◎", and when it exceeds 10% and is within 20%, the storage stability is evaluated as good. It was evaluated and expressed as “○”. When it exceeded 20%, it was evaluated as having slightly good storage stability and expressed as “△”. When polymerization occurred and gelation occurred, it was evaluated as having poor storage stability and indicated as “×”.

[Adhesion]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to each of the above-mentioned substrates to a film thickness of 100 μm using an applicator, and then each polymerizable resin composition was cured by irradiating ultraviolet rays ( sample).

The cross-cut test specified in JIS-K5600-5-6 was conducted on the cured product (cured material layer) on the substrate in each sample, and the number of remaining masses was taken as adhesion.

[Gel fraction]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a PET film to a film thickness of 100 μm using an applicator, and then cured by irradiation with ultraviolet rays (sample). The sample was immersed in methylene chloride for 18 hours, then taken out, recovered, and dried.

By subtracting the mass reduction of the cured product after immersion from the mass of the cured product before immersion, the mass of the cured (crosslinked) portion of the polymerizable resin composition is calculated, and the percentage of this mass relative to the mass before immersion is calculated as the gel fraction. did. That is, the mass before immersion is A, the mass after immersion and drying is B, and the gel fraction was calculated using a calculation formula expressed as 100 - (A - B) × 100/A.

[Surface specific resistance value]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a PET film with a film thickness of 100 μm and then cured by irradiation with ultraviolet rays (sample). Thereafter, the sample was placed in a constant temperature and humidity oven at a temperature of 85°C and a humidity of 85%RH for 0 to 500 hours, then taken out from the oven at predetermined intervals and incubated for 1 hour in an environment of a room temperature of 20°C and a humidity of 60%RH. The surface specific resistance value of the sample after leaving and controlling humidity was measured. Measurements were performed on a sample before installation in the oven (initial value), a sample 100 hours after installation, and a sample 500 hours after installation. The surface specific resistance was measured using R-503 manufactured by Kawaguchi Electric Works.

[Heat resistance]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a soft vinyl chloride film at a film thickness of 100 μm using an applicator, and then cured by irradiation with ultraviolet rays (sample). After that, the samples were left to stand in an oven set in an air atmosphere at 150°C for 24 to 300 hours, taken out at regular intervals shown in Table 1, and the flexibility of the taken out samples was evaluated.

To evaluate flexibility, take out a sample after each time period and repeatedly bend the sample to an angle of 90 degrees or 180 degrees to check whether there is cracking or rupture due to embrittlement of the base material or peeling of the coating film. did.

If neither cracking or rupture due to embrittlement of the substrate nor peeling of the coating film occurred, heat resistance was evaluated as excellent and indicated as "◎". If there was no peeling of the coating film but cracks occurred in the substrate, heat resistance was evaluated as good and indicated as "◎". It is indicated as ○”, and when cracking or rupture of the base material and peeling of the coating film occur, heat resistance is evaluated as poor and indicated as “×”.

[Flexibility]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a PET film at a film thickness of 100 μm using an applicator, and then cured by irradiation with ultraviolet rays in a nitrogen atmosphere (sample). Thereafter, the sample was evaluated for bending resistance (cylindrical mandrel method) according to JIS K5600-5-1-2013, and the diameter (mm) of the mandrel when a crack in the coating film occurred was recorded.

[Liquidity 1]

The polymerizable resin compositions obtained in each Example and Comparative Example were injected into a glass beaker to a thickness of 100 μm without irradiation of ultraviolet rays (sample), and the sample was placed in a constant temperature and humidity oven at a temperature of 85°C and a humidity of 85%RH. It was left to stand for 0.5 to 24 hours, samples were taken out at predetermined times shown in Table 1, and the presence or absence of flow in the taken samples and the presence or absence of tack by touching (touching) with a finger were confirmed.

Regarding the presence or absence of flow, after cooling to room temperature of 20°C, the beaker was held so that the sample surface on the bottom of the beaker was in a vertical direction, and if the sample was flowing after 1 hour, it was evaluated as fluid, and if not, it was evaluated as non-flow.

If there is neither flow nor flow, the fluidity is evaluated as good and indicated as 「◎」. If there is tack but no flow, the liquidity is evaluated as good and indicated as 「○」. If there is neither flow nor flow, the fluidity is poor. It was evaluated as “×” and indicated as “×”.

[Liquidity 2]

The fluidity was evaluated in the same manner as [Liquidity 1] except that the constant temperature and humidity oven was set to a temperature of 25°C and a humidity of 60%.

If there is neither flow nor flow, the fluidity is evaluated as good and indicated as 「◎」. If there is tack but no flow, the liquidity is evaluated as good and indicated as 「○」. If there is neither flow nor flow, the fluidity is poor. It was evaluated as “×” and indicated as “×”.

[Evaluation results]

In the urethane acrylate compounds of Examples 1 to 12 and 14 to 16, terminal hydroxylated polybutadiene or terminal hydroxylated polybutadiene is used as the diol that becomes the component constituting the main skeleton of the cured product, and these are respectively dissolved in isophorone diisocyanate ( IPDI) and hexamethylene diisocyanate (HMDI), a first step reaction of urethanizing both ends with an isocyanate group is performed, and then a second step reaction of blocking one end with an acryloyl group or methacryloyl group. In the reaction, the amount of terminal isocyanate groups was adjusted by changing the amount of 2-hydroxyethyl acrylate (HEA) or 2-hydroxyethyl methacrylate (HEMA).

Additionally, in Example 13, in the first step reaction, tetrahydrofurfuryl acrylate was used as a diluent instead of isoboronylacrylate to produce a urethane acrylate compound.

As shown in Table 1, examples having an acryloyl group (polymerizable double bond) at one end of the molecule, an isocyanate group at the other end, and a group resulting from a conjugated diene polymer polyol or the like between both ends. 1 to 16 and Comparative Examples 5 to 8, the polymerizable resin composition was excellent in storage stability, and the cured product was excellent in gel fraction, surface specific resistance, adhesion, heat resistance, flexibility, and fluidity.

On the other hand, the polymerizable resin compositions of Comparative Examples 1 to 4, which do not have groups resulting from conjugated diene polymer polyol or the like between both terminals, and Comparative Example 9, which has an acryloyl group at both terminals (and does not have an isocyanate group at the terminals). The polymerizable resin composition of Examples 1 to 16 and Comparative Examples 5 to 8 had a tendency for the cured product to be inferior in each of the above properties.

Comparing Example 1 and Comparative Example 9, the main skeleton is the same, but by introducing an acryloyl group at one end of both terminals (i.e., leaving an isocyanate group at the other end), the adhesion to metal is particularly improved. A marked improvement was observed.

Comparing Example 2 and Comparative Example 10, even if isocyanate was added to the compound of Comparative Example 10 in which acryloyl groups were introduced at both ends so that the free isocyanate group was the same as in Example 2, the adhesion to metal was not improved. didn't For this reason, it is thought that in Comparative Example 10, when the polymerizable resin composition is cured, the isocyanate is simply homopolymerized and does not participate in the affinity between the urethane acrylate compound, which is the main skeleton, and the metal.

The results for each evaluation item are as follows.

Regarding storage stability, it can be said that the smaller the increase in viscosity over time, the more stable it is.

As shown in Table 1, in Examples 1 to 16, the increase in viscosity over time was small and tended to be stable. Additionally, the smaller the amount of free isocyanate groups in the urethane acrylate compound, the more stable it tended to be.

On the other hand, in Comparative Examples 1 to 4, which had a glycol-based structure in the main skeleton, the viscosity tended to increase over time compared to Examples 1 to 16. For this reason, the skeleton itself, which has a structure derived from glycol, has lower heat resistance than the skeleton of an alkyl system such as butadiene or hydrogenated butadiene, and for this reason, Comparative Examples 1 to 4 were reduced in molecular weight by decomposition, It is thought that this is due to the fact that it is easily influenced by the increase in cross-linking points.

Regarding the gel fraction, when sufficient ultraviolet rays were irradiated, a generally sufficient value tended to appear in any of Examples 1 to 16 and Comparative Examples 1 to 10.

Regarding the surface specific resistance, it was found that Examples 1 to 16 had higher surface specific resistance under heating and humidification conditions and were superior in insulation properties than Comparative Examples 1 to 4.

Regarding adhesion, it was found that Examples 1 to 16 had superior adhesion to metal than Comparative Examples 1 to 4. Moreover, in all of Examples 1 to 16 and Comparative Examples 1 to 4, the adhesion to vinyl chloride was excellent.

The heat resistance is equivalent to the ability to suppress embrittlement of vinyl chloride under heating conditions, but also regarding this heat resistance, Examples 1 to 16 having groups resulting from the above-mentioned conjugated diene polymer polyol, etc. are better than the comparative examples not having this group. It was found to have superior durability than 1 to 4. That is, in Examples 1 to 16, vinyl chloride was not embrittled over a long period of time in a high temperature environment of 150°C, and heat resistance was excellent.

Moreover, from a comparison between Examples 1 to 3 and Examples 4 to 6, when isophorone diisocyanate is used as a starting material as the polyisocyanate, embrittlement of vinyl chloride is more fully suppressed than when hexamethylene diisocyanate is used. I could see that there was a tendency to do it.

Regarding flexibility, it was found that the cured products of Examples 1 to 12 having a group originating from the above-mentioned conjugated diene polymer polyol or the like had superior flexibility to the cured products of Comparative Examples 1 to 4 that did not have this group. It was found that cracks in the cured product had excellent durability.

In the fluidity test assuming curing in a state where ultraviolet rays are not sufficiently irradiated, that is, curing in the dark area (dark area curing), in the fluidity test (1) at high temperature and humidity, even without irradiation of ultraviolet rays (i.e. , also in the dark portion), Examples 1 to 16, and Comparative Examples 1 to 4 were all able to achieve curing. In addition, in the test of fluidity (2), which confirmed curability (polymerizability) under conditions close to an indoor environment, it was found that curing can be achieved even without irradiation of ultraviolet rays when placed in a constant humidity environment. In this fluidity test (2), Examples 1 to 16 tended to be easier to harden than Comparative Examples 1 to 4.

Additionally, the ease of curing in a humid environment appears to be correlated with the amount of free isocyanate groups.

Accordingly, it was found that the polymerizable resin composition containing a urethane acrylate compound having a (meth)acryloyl group at one terminal and an isocyanate group at the other terminal is easy to cure even under conditions in which ultraviolet rays are not sufficiently irradiated. . In this regard, for example, when manufacturing a wire harness using bundled wires, when ultraviolet rays are irradiated on the applied polymerizable resin composition, parts that are difficult to be irradiated with ultraviolet rays due to the ultraviolet rays becoming a shadow, etc. It was found that even if there were parts that were difficult to be irradiated with ultraviolet rays, such as the deep part of the thickly applied polymeric resin composition, these parts could be more sufficiently cured.

In the comparison of Examples 1 to 3 and Comparative Examples 5 and 6, and the comparison of Examples 4 to 6 and Comparative Examples 7 and 8, if the proportion of free isocyanate groups is in the range of 50 to 87.5 mol%, It was found that both adhesion and heat resistance can be improved compared to cases outside of this range. Additionally, there was a tendency for it to be excellent in properties other than these.

In the comparison between Examples 1 to 3 and Examples 14 to 16, even when methacrylate having a hydroxyl group was used, excellent results could be obtained in each characteristic, as in the case of using acrylate having a hydroxyl group. could know that

As a result of the above, the polymerizable resin composition containing a urethane acrylate compound having a (meth)acryloyl group at one terminal, an isocyanate group at the other terminal, and a group resulting from the above-mentioned conjugated diene polymer polyol or the like between both ends is resistant to metal. It can be seen that a polymerizable resin composition is obtained that not only has excellent adhesion to heat and heat resistance in terms of improving insulation and suppressing embrittlement of vinyl chloride, but also has excellent polymerizability (curability) while maintaining storage stability. there was.

In addition, since this polymerizable resin composition has excellent curing properties even in dark areas where ultraviolet rays are not sufficiently irradiated, it was found to be suitable as an insulating material for automobile wiring and other electrical wiring.

[Second Embodiment] (Use for covering circuit boards)

The following components were further added to the polymerizable resin compositions of Synthesis Examples 1 to 4, 7 to 10, 18, and 27 to 33 to prepare the polymerizable resin compositions of each Example and Comparative Example.

[Example 21]

To 100 parts of UA-1 obtained in Synthesis Example 1, as a photopolymerization initiator, 3 parts of 1-hydroxycyclohexylphenyl ketone (Irgacure 184 manufactured by BASF), and dimorpholinodiethyl ether (manufactured by Mitsui Chemicals Fine) 0.1 part of DMDEE) was added and dissolved uniformly to obtain a polymerizable resin composition.

[Examples 22 to 32, Comparative Examples 21 to 24]

Except that UA-1 was changed to UA-2 to 4, 7 to 10, 18, and 27 to 33 shown in Table 2 below, the same procedure as in Example 21 was performed, and the results of Examples 22 to 32 and Comparative Examples 21 to 24 were obtained. A polymerizable resin composition was obtained.

The polymerizable resin compositions obtained in each Example and Comparative Example were polymerized and cured by the following method, and evaluated by the following method. The results are shown in Table 2.

[Material used]

As a copper base material, C1020P (manufactured by TP Engineering & Construction Co., Ltd.) specified in the JIS standard was used.

As a glass epoxy substrate, green epoxy material E568 (manufactured by Hitachi Chemical Company) was used. Other descriptions are the same as in the first embodiment.

[curing device]

As a curing device for curing the polymerizable resin composition, an ultraviolet (UV) irradiation device was used. As the UV irradiation device, a belt conveyor type UV curing device equipped with a metal halide lamp (trade name CSN2-40A, manufactured by GS Yuasa) was used. The irradiation conditions were that the integrated illuminance was 400 mJ/cm2.

[Curing conditions]

In cases where conditions were not specifically specified, the ultraviolet curing conditions were irradiated with ultraviolet rays at an integrated illumination intensity of 400 mJ/cm2 to cure the polymerizable resin composition.

As for curing conditions by combined use of moisture curing, after curing with ultraviolet rays under the above conditions, the curing was left to stand in a humidity-controlled environment with room temperature of 25°C and humidity of 60%RH for 24 hours.

[Storage Stability]

Evaluation was performed in the same manner as in Example 1.

[viscosity]

The viscosity of the polymerizable resin composition obtained in each example and comparative example was measured using a corn plate type viscometer. The measurement temperatures were 25°C and 40°C.

[Adhesion]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a film thickness of 100 μm using an applicator on a copper substrate and a glass epoxy substrate, respectively, and then cured by irradiating ultraviolet rays. (sample). In addition, samples cured under curing conditions using combined moisture curing were also produced.

The cross-cut test specified in JIS-K5600-5-6 was performed on the cured product (cured material layer) on the substrate in each sample, and the number of remaining masses was taken as adhesion.

[Gel fraction]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a PET film to a film thickness of 100 μm using an applicator, and then cured by irradiation with ultraviolet rays (sample). In addition, samples cured under curing conditions using combined moisture curing were also produced. For each sample, the gel fraction was calculated using the same evaluation method as described in Example 1.

[Tensile test]

A cured film was produced by applying a film thickness of 100 μm on release paper using an applicator and then curing it by irradiating ultraviolet rays. The produced film was cut into strips with a length of 5 cm and a width of 0.5 mm. The cut test piece was subjected to a tensile test (tensile speed: 50 mm/min) using an Autograph (precision universal testing machine) manufactured by Shimadzu Corporation, and the elongation and strength when the test piece broke were recorded.

[Surface specific resistance value]

The polymerizable resin compositions obtained in each Example and Comparative Example were applied to a PET film with a film thickness of 100 μm and then cured by irradiation with ultraviolet rays (sample). Afterwards, the sample was placed in a constant temperature and humidity oven at a temperature of 85°C and a humidity of 85%RH for 500 hours, then taken out from the oven and left for 1 hour in an environment of a room temperature of 20°C and a humidity of 60%RH. The surface specific resistance value was measured. Measurements were also performed on samples (initial values) before installation in the oven. The surface specific resistance was measured using R-503 manufactured by Kawaguchi Electric Works.

[Migration Test]

The polymerizable resin compositions obtained in each Example and Comparative Example were coated on a type II comb electrode according to JIS Z3284-3 and then cured by irradiating ultraviolet rays to form a cured film (sample) with a film thickness of 30 μm. was manufactured. In addition, samples cured under curing conditions using combined moisture curing were also produced. For each sample, a voltage of 100 V was applied for 1000 hours in an environment of temperature 80°C and humidity 95%RH, and changes in resistance value were confirmed. Changes in insulation resistance and the presence or absence of corrosion on the exterior were evaluated.

Those whose resistance value is maintained at 10 ⁹ Ω are designated as “○”, those who cannot maintain 10 ⁹ Ω but maintained at 10 ⁸ Ω are designated as “△”, and those whose resistance value falls below 10 ⁷ Ω are designated as “×”.

The appearance after the migration test was evaluated with the naked eye. Those with no abnormalities in the coating resin were marked as "○". Those in which necking, cracks, or rust that short-circuits the combs were generated were given “×”.

[Water permeability]

The moisture permeability of the cured film was measured according to JIS Z0208. Using release paper as a base, it was applied to a film thickness of 50 μm and then cured by 400 mJ/cm 2 ultraviolet ray irradiation to prepare a test piece.

[Evaluation results]

As shown in Table 2, Examples 21 to 32, which have an acryloyl group at one terminal within the molecule, an isocyanate group at the other terminal, and groups originating from a conjugated diene polymer polyol or the like between both terminals, have their polymerizability. The resin composition had excellent storage stability, and the cured product was excellent in moisture permeability, gel fraction, tensile properties, adhesion, surface specific resistance, and heat-and-moisture resistance (migration test).

More specifically, Examples 21 to 32 have high adhesion to both the copper substrate and the glass epoxy substrate, have low moisture permeability, and have a high surface specific resistance value after being left under high temperature and high humidity conditions, and in the migration test, Since the change in resistance value was also small, it was found that it had high electrical insulation even under high temperature and high humidity conditions and was excellent in heat and moisture resistance.

In addition, not only did it exhibit sufficient properties even when cured by ultraviolet rays, but there was little change in physical properties such as adhesion even when combined with moisture curing. Additionally, the storage stability of the polymerizable resin composition was excellent.

Therefore, it can be seen that the polymerizable resin compositions of Examples 21 to 32 are suitably used for covering and protecting circuit boards.

On the other hand, in the polymerizable resin compositions of Comparative Examples 21 and 22 that did not have groups resulting from conjugated diene polymer polyol or the like between both terminals, the cured products tended to be inferior in each of the above properties. In Comparative Example 23, the amount of isocyanate groups in the urethane acrylate compound was too large, resulting in poor storage stability, and the amount of acryloyl groups was too small, making it impossible to maintain the film shape after ultraviolet curing. In Comparative Example 24, the amount of isocyanate groups in the urethane acrylate compound was small, and the adhesion was poor.

In the comparison between Example 21 and Example 24, and the comparison between Example 26 and Example 29, it was found that the larger the molecular weight of the conjugated diene polymer polyol or the like constituting the urethane acrylate compound, the lower the viscosity of the polymerizable resin composition. Could know.

In the comparison of Example 24 and Example 25, and the comparison of Example 29 and Example 30, by using acyclic (meth)acrylate as a diluent, the viscosity of the polymerizable resin composition can be lowered without worsening the moisture permeability. Moreover, it was found that the elongation of the hardened product can be increased.

Claims (8)

At least one of an acrylate having a hydroxyl group and a methacrylate having a hydroxyl group,
A compound obtained by reacting at least one of a conjugated diene polymer polyol and its hydrogenated product with a polyisocyanate,
Contains at least one of acrylate and methacrylate as a diluent,
A polymerizable resin composition in which the amount of acryloyl group and methacryloyl group relative to the total amount of isocyanate group, acryloyl group, and methacryloyl group contained in the above compound is 12.5 to 50 mol%. According to claim 1,
A polymerizable resin composition wherein the polyisocyanate is an alicyclic polyisocyanate. The method of claim 1 or 2,
A polymerizable resin composition further containing at least one of acyclic acrylamide and acyclic methacrylamide. The method of claim 1 or 2,
A polymerizable resin composition used for coating metals. According to claim 4,
A polymerizable resin composition used for covering a connection portion of an electric wire and a connection terminal in a wire harness provided with an electric wire and a connection terminal connected to an end of the wire. The method of claim 1 or 2,
A polymerizable resin composition used for covering and protecting circuit boards. The method of claim 1 or 2,
A polymerizable resin composition that can be polymerized and cured by at least one of active energy rays, heating, and water in the air. A cured product obtained by polymerizing and curing the polymerizable resin composition according to claim 1 or 2.