WO2014208212A1 - Energy ray-curable resin composition and vibration damper sheet - Google Patents

Abstract

Provided is an energy ray-curable resin composition which is capable of providing a cured product having extremely excellent vibration damping properties when cured. An energy ray-curable resin composition which is characterized by containing a monofunctional urethane (meth)acrylate (A) having a hydrogenated polyolefin skeleton and a photoinitiator (B), and which is also characterized in that the monofunctional urethane (meth)acrylate (A) having a hydrogenated polyolefin skeleton is a urethane (meth)acrylate which is obtained by reacting a diol (X) having a hydrogenated polyolefin skeleton, a diisocyanate (Y), a hydroxy group-containing (meth)acrylate (Z) and a compound (L) that has one isocyanate reactive group in each molecule but does not have a photocurable functional group.

Description

Energy ray curable resin composition and vibration damping sheet

The present invention relates to an energy beam curable resin composition and a vibration damping sheet containing a cured product of the energy beam curable resin composition. This application claims the priority of Japanese Patent Application No. 2013-135570 for which it applied to Japan on June 27, 2013, and uses the content here.

Conventionally, for the purpose of imparting vibration damping to articles and parts exposed to vibration, articles and parts vulnerable to vibration, and preventing collapse of furniture, etc. Materials that can impart vibration damping properties such as sheets are widely used.

Regarding the above-described material capable of imparting vibration damping properties, for example, Patent Document 1 discloses a hydrogenated butadiene-based polymer having a plurality of photocurable functional groups, an oligomer having a single photocurable functional group, and light. A photocurable resin composition containing a polymerization initiator and an adhesive sheet comprising the same are disclosed. Further, for example, Patent Document 2 discloses a photocurable resin composition containing a hydrogenated butadiene-based polymer having a plurality of photocurable functional groups, a polythiol compound, and a photopolymerization initiator, and an adhesive sheet comprising the same. Has been. Furthermore, for example, in Patent Document 3, a hydrogenated butadiene-based polymer having a plurality of photocurable functional groups, a monomer having a single photocurable functional group, and a photocurable resin containing a photopolymerization initiator. An adhesive sheet comprising a cured product of the composition is disclosed. In the above document, it is described that any of these pressure-sensitive adhesive sheets can improve vibration damping characteristics (hysteresis loss).

JP 2011-32409 A JP 2011-32410 A JP 2012-62447 A

However, the pressure-sensitive adhesive sheets disclosed in the above-mentioned Patent Documents 1 to 3 all have a Tanδ value that is a vibration damping index of less than 1 and not sufficiently high, and are used in applications that require higher vibration damping properties. The current situation is that it cannot be used.

Accordingly, an object of the present invention is to provide an energy ray curable resin composition that can be cured to form a cured product having very excellent vibration damping properties.
Another object of the present invention is to provide a vibration damping sheet having very excellent vibration damping properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an energy ray curable resin composition containing a specific urethane (meth) acrylate and a photoinitiator as essential components is very excellent when cured. The present inventors have found that a cured product having excellent vibration damping properties can be formed.

That is, the present invention includes a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a photoinitiator (B). Diol (X) having a hydrogenated polyolefin skeleton, diisocyanate (Y), hydroxy group-containing (meth) acrylate (Z), one isocyanate-reactive group in the molecule, and a photocurable functional group. Provided is an energy ray-curable resin composition, which is a urethane (meth) acrylate obtained by reacting a compound (L) having no group.

Furthermore, the energy ray-curable resin composition is provided wherein the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton has a weight average molecular weight of 10,000 or more. Moreover, it provides also about the energy-beam curable resin composition containing a monofunctional urethane (meth) acrylate (A), a photoinitiator (B), a reactive diluent, and / or a volatile organic solvent.

The present invention also provides a vibration damping sheet containing a cured product of the energy beam curable resin composition.

That is, the present invention relates to the following.
(1) A monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a photoinitiator (B) Diol (X) having a modified polyolefin skeleton, diisocyanate (Y), hydroxy group-containing (meth) acrylate (Z), one isocyanate-reactive group in the molecule, and a photocurable functional group An energy ray-curable resin composition, which is a urethane (meth) acrylate obtained by reacting with a compound (L) that does not.
(2) The component (A) is a urethane (meth) acrylate obtained by reacting the component (X), the component (Y), the component (Z), and the compound (L), and the component (A) The energy ray-curable resin composition according to (1), wherein the structure of
ZY- [XY] mL (where m represents an integer of 1 or more)
(3) The method of reacting the components (X) to (Z) and the compound (L) comprises reacting the component (X) and the component (Y) to form a urethane isocyanate prepolymer (urethane prepolymer) having isocyanate groups at both ends. After forming the polymer), the component (Z) is reacted with an amount that reacts with one isocyanate group of the urethane isocyanate prepolymer, and then the compound (L) is reacted with an amount that reacts with the remaining isocyanate group. The energy ray-curable resin composition according to (1) or (2).
(4) The method for synthesizing the urethane isocyanate prepolymer is charged with a component (X), a component (Y), and, if necessary, a reactive diluent and / or a volatile organic solvent in a reactor. This is a method of starting or advancing the reaction (urethanization) between the component (X) and the component (Y) by adding a urethanization catalyst after raising the temperature as necessary while stirring until uniform (3) The energy ray-curable resin composition described in 1.
(5) The method for synthesizing the urethane isocyanate prepolymer is prepared by uniformly charging the reactor with the component (Y), the urethanization catalyst, and, if necessary, a reactive diluent and / or a volatile organic solvent. The energy ray curable resin composition according to (3), which is stirred until the temperature reaches, then heated as necessary while stirring, and the component (X) is dropped and reacted.
(6) The reactive diluent is at least one selected from the group consisting of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, isobornyl acrylate, and normal octyl acrylate. The energy ray-curable resin composition according to (4) or (5), which is a seed.
(7) The energy ray-curable resin composition according to any one of (4) to (6), wherein the reactive diluent is at least one selected from the group consisting of isobornyl acrylate and normal octyl acrylate. object.
(8) The volatile organic solvent is selected from the group consisting of ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, xylene, and toluene. The energy ray-curable resin composition according to any one of (4) to (7), which is at least one kind.
(9) The energy beam curable resin composition according to (4) to (8), wherein the volatile organic solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, and toluene.
(10) When synthesizing the urethane isocyanate prepolymer, the component (X) and the component (Y) are reacted until the isocyanate group concentration in the reaction solution is equal to or lower than the end-point isocyanate group concentration (3) to (9) The energy beam curable resin composition as described in any one of these.
(11) In the method for synthesizing the urethane isocyanate prepolymer, the molar ratio of the component (X) to the component (Y) is 1.1-2. The energy ray-curable resin composition according to any one of (3) to (10), which is a method of using 0 mol, more preferably 1.2 to 1.5 mol.
(12) In the reaction of the urethane isocyanate prepolymer, the component (Z) and the compound (L), the amount (number of moles) of the component (Z) to be used is 1.0 with respect to 1 mol of the urethane isocyanate prepolymer. 1.1 mol, more preferably 1.0 to 1.05 mol, and the hydroxyl group of component (Z) and the isocyanate of compound (L) with respect to 1 mol of isocyanate groups of the urethane isocyanate prepolymer The energy ray according to any one of (3) to (11), wherein the number of moles (total amount) of the reactive group is 1.0 to 1.1 mol, more preferably 1.0 to 1.05 mol. Curable resin composition.
(13) The catalyst in the reaction for producing the component (A) is a reaction using at least one selected from the group consisting of dibutyltin dilaurate, tin octylate, and tin chloride, and the added amount of catalyst (use) The energy ray-curable resin composition according to any one of (4) to (12), wherein the amount is 1 to 3000 ppm (by weight), more preferably 50 to 1000 ppm.
(14) In any one of (3) to (13), the reaction of components (X) to (Z) and compound (L) is performed until the residual isocyanate group is 0.1% by weight or less. The energy beam curable resin composition described.
(15) The energy according to any one of (1) to (14), wherein the component (X) is a compound having a hydrogenated polyolefin skeleton in the molecule and having two hydroxy groups in the molecule. A linear curable resin composition.
(16) The energy ray curable resin composition according to any one of (1) to (15), wherein the component (X) is a compound obtained by hydrogenating a polyalkadiene having hydroxy groups at both ends.
(17) The energy ray-curable resin composition according to (16), wherein the polyalkadiene is polybutadiene and / or polyisoprene.
(18) The energy ray curable resin composition according to any one of (1) to (17), wherein the component (Y) is a compound having two isocyanate groups in the molecule.
(19) Component (Y) is at least one selected from the group consisting of a diisocyanate compound obtained by hydrogenating an alicyclic diisocyanate, a branched aliphatic diisocyanate, and an aromatic isocyanate ( 1) The energy ray curable resin composition according to any one of (18).
(20) Component (Y) is selected from the group consisting of isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate The energy ray-curable resin composition according to any one of (1) to (19), which is at least one selected from the group consisting of:
(21) Any one of (1) to (20), wherein component (Z) is a compound having one hydroxy group in the molecule and one (meth) acryloyl group in the molecule The energy ray-curable resin composition described in 1.
(22) Component (Z) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, bisphenol A diglycidyl mono The energy beam curable resin composition according to any one of (1) to (21), which is at least one selected from the group consisting of (meth) acrylates and hydrogenated products thereof.
(23) The compound (L) is a compound having at least one selected from the group consisting of a hydroxy group, an amino group containing active hydrogen, a functional group represented by> C═N—OH, and an amide group. (1) The energy beam curable resin composition according to any one of (22).
(24) Compound (L) is an alcohol compound, a phenol compound, an active methylene compound, a mercaptan compound, an acid amide compound, an acid imide compound, an imidazole compound, a pyrazole compound, a urea compound, or an oxime compound. The energy ray-curable resin composition according to any one of (1) to (23), which is at least one selected from the group consisting of a compound, an amine compound, an imine compound, and a pyridine compound.
(25) The energy ray curable resin composition according to any one of (1) to (24), wherein the compound (L) is an alcohol compound.
(26) The alcohol compound is an aliphatic monohydric alcohol having 1 or more carbon atoms and / or an alicyclic monohydric alcohol having 3 or more carbon atoms, and has a molecular weight of 70 to 400 (24 ) Or the energy ray-curable resin composition according to (25).
(27) The alcohol compound is methanol, ethanol, isopropanol, normal propanol, 1-butanol, 1-heptanol, 1-hexanol, normal octyl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), cyclohexane methanol, capryl alcohol. , Lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol (with 3 or more carbon atoms, iso isomers, normal isomers and other structural isomers) And the energy ray-curable resin composition according to any one of (24) to (26).
(28) The energy ray curable resin composition according to any one of (24) to (27), wherein the alcohol compound is isopropanol, 2-ethylhexyl alcohol, or a mixture thereof.
(29) The weight average molecular weight (Mw) of the component (A) is 10,000 or more, more preferably 15,000 to 100,000, still more preferably 30,000 to 60,000. ) The energy ray-curable resin composition according to any one of the above.
(30) The content (blending amount) of the component (A) in the energy beam curable resin composition is 40 to 99.75 based on the total nonvolatile weight (100% by weight) of the energy beam curable resin composition. The energy ray-curable resin composition according to any one of (1) to (29), which is 9% by weight, more preferably 45 to 99% by weight, and still more preferably 50 to 98% by weight.
(31) The content (blending amount) of the photoinitiator (B) in the energy beam curable resin composition is 100 parts by weight based on the total amount of radical polymerizable compounds contained in the energy beam curable resin composition. The energy ray curable resin composition according to any one of (1) to (30), which is 0.1 to 20 parts by weight, more preferably 1 to 5 parts by weight.
(32) The energy ray curable resin composition comprises the component (A), the photoinitiator (B), and further a reactive diluent and / or a volatile organic solvent. The energy ray-curable resin composition according to any one of the above.
(33) The reactive diluent contained in the energy ray curable resin composition is 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, isobornyl acrylate, and normal octyl acrylate The energy ray-curable resin composition according to (32), which is at least one selected from the group consisting of:
(34) The energy beam according to (32) or (33), wherein the reactive diluent contained in the energy beam curable resin composition is at least one selected from the group consisting of isobornyl acrylate and normal octyl acrylate. Curable resin composition.
(35) The content (blending amount) of the reactive diluent in the energy beam curable resin composition is preferably 1 to 99 parts by weight, more preferably 100 parts by weight of the total amount of the energy beam curable resin composition. The energy ray curable resin composition according to any one of (32) to (34), wherein 10 to 90 parts by weight, more preferably 15 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight.
(36) The volatile organic solvent contained in the energy ray curable resin composition is ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, xylene, And the energy ray-curable resin composition according to any one of (32) to (35), which is at least one selected from the group consisting of toluene and toluene.
(37) Any one of (32) to (36), wherein the volatile organic solvent contained in the energy ray curable resin composition is at least one selected from the group consisting of ethyl acetate, butyl acetate, and toluene. The energy ray-curable resin composition described in 1.
(38) The content (blending amount) of the volatile organic solvent in the energy ray curable resin composition is preferably 1 to 99 parts by weight, more preferably 100 parts by weight of the total amount of the energy ray curable resin composition. The energy ray-curable resin composition according to any one of (32) to (37), wherein is 10 to 90 parts by weight, more preferably 15 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight.
(39) The content (blending amount) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton in the energy ray curable resin composition is 100% by weight based on the total amount of the energy ray curable resin composition. 1 to 99% by weight is preferable, more preferably 10 to 90% by weight, still more preferably 30 to 85% by weight, and most preferably 50 to 80% by weight, and any one of (32) to (38) The energy ray-curable resin composition described in 1.
(40) A cured product of the energy ray-curable resin composition according to any one of (1) to (39), wherein Tan δ at 23 ° C. is 0.6 or more, more preferably 0.8 or more. More preferably, the cured product is 1.0 or more. (41) A coating material comprising a cured product of the energy beam curable resin composition according to any one of (1) to (39).
(42) A vibration damping sheet comprising a cured product of the energy beam curable resin composition according to any one of (1) to (39).

Since the energy ray curable resin composition of the present invention has the above-described configuration, a cured product having very excellent vibration damping properties can be formed by curing. In addition, since the energy ray curable resin composition of the present invention can be cured by irradiation with energy rays (particularly, ultraviolet rays), it is a coating material (cured product) having very high vibration damping properties with high productivity. Can be formed. In addition, the energy beam curable resin composition of the present invention can be applied to, for example, not only a planar article but also an article having a complicated shape such as a three-dimensional shape, and can be cured to form a coating material. It is possible to impart excellent vibration damping properties to a wide variety of articles. Furthermore, by using the energy ray curable resin composition of the present invention, a vibration damping sheet having a very excellent vibration damping property including a cured product of the resin composition can be obtained.

≪Energy ray curable resin composition≫
The energy ray-curable resin composition of the present invention comprises a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton (sometimes referred to as “component (A)”), a photoinitiator (B), Is a curable resin composition containing as an essential component. The energy beam curable resin composition of the present invention may contain a reactive diluent, a volatile organic solvent, and an additive described later in addition to the component (A) and the photoinitiator (B).

<Monofunctional urethane (meth) acrylate (A) having hydrogenated polyolefin skeleton>
The monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton in the energy ray curable resin composition of the present invention has a hydrogenated polyolefin skeleton in the molecule and one (meth) in the molecule. A urethane (meth) acrylate having an acryloyl group (that is, monofunctional). In the present specification, “(meth) acrylate” means acrylate and / or methacrylate (any one or both of acrylate and methacrylate), and the same applies to “(meth) acryloyl” and the like.

The monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is composed of a diol (X) having a hydrogenated polyolefin skeleton (sometimes referred to as “component (X)” or “X”) and a diisocyanate (Y ) (Sometimes referred to as “component (Y)” or “Y”), hydroxy group-containing (meth) acrylate (Z) (sometimes referred to as “component (Z)” or “Z”), and molecules Compound (L) having one isocyanate-reactive group and not having a photocurable functional group (“isocyanate-reactive compound”, “compound (L)”, “component (L)”, “L”) Is a urethane (meth) acrylate obtained by reacting. The structure of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is schematically shown as follows.
ZY- [XY] _m -L (where m represents an integer of 1 or more)

The method for reacting the above components (X) to (Z) and the component (L) is not particularly limited, and examples thereof include the following methods.
[Method 1] Method of mixing component (X), component (Y), component (Z), and component (L) and reacting them together [Method 2] reacting component (X) and component (Y), After the formation of a urethane isocyanate prepolymer having both ends isocyanate groups (urethane prepolymer), the component (Z) is reacted in an amount such that one isocyanate group of the urethane isocyanate prepolymer reacts, and then the remaining isocyanate groups are reacted. [Method 3] After reacting component (X) and component (Y) to form a urethane isocyanate prepolymer (urethane prepolymer) having isocyanate groups at both ends. And reacting the component (L) in such an amount that one isocyanate group of the urethane isocyanate prepolymer reacts, and then the remaining isocyanate [Method 4] A reaction of component (Y) with an amount of component (Z) with which one of the isocyanate groups of component (Y) reacts, schematically represents Y A prepolymer represented by —Z (hereinafter referred to as “prepolymer (YZ)”) is synthesized. On the other hand, the component (Y) is reacted with the component (L) in such an amount that one isocyanate group of the component (Y) reacts to give a prepolymer (hereinafter referred to as “prepolymer (Y -L) "). When increasing the number of repetitions of component (X) and component (Y), component (X) and component (Y) are further reacted separately to synthesize a urethane prepolymer having hydroxyl groups at both ends. Thereafter, the mixture of the prepolymer (YZ) and the prepolymer (YL) is reacted with the component (X) and / or the urethane prepolymer having hydroxyl groups at both ends.

[Method 2] is preferable among [Method 1] to [Method 4] described above. That is, the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton of the present invention reacts with one isocyanate group of a urethane isocyanate prepolymer (diisocyanate) with a hydroxy group-containing (meth) acrylate (Z), Then, it is preferable that it is urethane (meth) acrylate obtained by making a compound (L) react with the other isocyanate group. By adopting [Method 2], for example, viscosity increase prevention, resin appearance, suppression of by-products, transparency of cured products, heat resistance, etc. are significantly improved as compared with [Method 1] and [Method 3]. The effect of doing.

On the other hand, when produced by the above [Method 1], the obtained urethane (meth) acrylate has a high viscosity, stirring becomes difficult, or the reaction proceeds non-uniformly, and the probability of partial gelation is increased. In addition, the by-product amount of the urethane isocyanate prepolymer due to the repetition of the diol (X) having a hydrogenated polyolefin skeleton and the diisocyanate (Y) increases, and the vibration damping property of the cured product tends to decrease. Moreover, since various complicated compounds are irregularly generated, quality control becomes difficult when the product is used as a component of the energy ray curable resin composition.

Further, when the reaction is carried out by the above [Method 3], there is a possibility that the hydroxy group-containing (meth) acrylate (Z) may remain without reacting with the isocyanate group in the late stage of the reaction, which is not preferable. In addition, there is a tendency that a by-product (a reaction product of the component (X), the component (Y), and the component (L)) that does not contain the skeleton of the hydroxy group-containing (meth) acrylate (Z) tends to be by-produced. The curability of the energy ray curable resin composition tends to be lowered.

Furthermore, when the reaction is carried out by the above [Method 4], the reaction process becomes long, which is not industrially preferable.

In the above [Method 2], the method for synthesizing the urethane isocyanate prepolymer is not particularly limited, and examples thereof include the following methods.
[Method 2-1] Method in which component (X) and component (Y) are mixed and reacted at once [Method 2-2] Method in which component (Y) is dropped into component (X) and reacted [Method 2 -3] Method of dropping component (X) into component (Y) and reacting

In the case of the above [Method 2-2], since the diisocyanate (Y) is dropped into a large amount of the diol (X) having a hydrogenated polyolefin skeleton, the value of m among the molecules represented by the following formulas However, since a very large molecule is generated, it tends to be gelled and difficult to produce.
[XY] _m -X (m is an integer of 1 or more)

Therefore, [Method 2-1] and [Method 2-3] are preferably used in order to obtain the desired urethane isocyanate prepolymer in good yield.

For [Method 2-1]:
In the reactor, a diol (X) having a hydrogenated polyolefin skeleton, a diisocyanate (Y), and optionally a reactive diluent (eg, isobornyl acrylate, normal octyl acrylate, etc.) and / or a volatile organic solvent (eg, , Toluene, ethyl acetate, butyl acetate, etc.), and after stirring until homogeneous, the temperature rises as necessary, and then the urethanization catalyst is added to react the component (X) with the component (Y) (urethane) The method of initiating or advancing the conversion is preferable. The temperature may be increased as necessary after the urethanization catalyst is added.

When the urethanization catalyst is introduced from the beginning, the urethanization reaction proceeds in a state where the diol (X) having a hydrogenated polyolefin skeleton and the diisocyanate (Y) are in a non-uniform state at the charging stage of the diisocyanate (Y). The molecular weight and viscosity of the resulting urethane isocyanate prepolymer change, and the reaction may be terminated in a state where unreacted diisocyanate (Y) remains in the system. In such a case, since a by-product is generated due to the reaction of only the remaining diisocyanate (Y) with the hydroxy group-containing (meth) acrylate (Z) or compound (L) to be used later, It may lead to a drop, which is inconvenient. [Method 2-1] is industrially superior in that it can produce a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton in one pot.

For [Method 2-3]:
In the reactor, diisocyanate (Y), urethanization catalyst, and optionally a reactive diluent (eg, isobornyl acrylate, normal octyl acrylate, etc.) and / or a volatile organic solvent (eg, toluene, ethyl acetate, acetic acid) Butyl etc.) and stir until uniform. Next, while stirring, the temperature is raised as necessary, and the diol (X) having a hydrogenated polyolefin skeleton is added dropwise.

[Method 2-3] is preferable in that the supermacromolecule described in [Method 2-2] is not generated.

In any of the above methods, when the urethane isocyanate prepolymer is synthesized by the reaction of the diol (X) having a hydrogenated polyolefin skeleton and the diisocyanate (Y), the diol (X) having a hydrogenated polyolefin skeleton and the diisocyanate ( Y) is preferably reacted until the isocyanate group concentration in the reaction solution is equal to or lower than the end-point isocyanate group concentration.

“End-point isocyanate group concentration” is a theoretical isocyanate group concentration (hereinafter referred to as “theoretical end-point isocyanate group concentration”) assuming that all of the hydroxyl groups (hydroxyl groups) charged into the system are urethaned. And the isocyanate group concentration when the isocyanate group concentration in the reaction solution no longer changes, whichever is the higher isocyanate group concentration.

From the above viewpoint, the molar ratio of the diol (X) having a hydrogenated polyolefin skeleton and the diisocyanate (Y) is not particularly limited, but the diisocyanate (Y) is used with respect to 1 mole of the diol (X) having a hydrogenated polyolefin skeleton. Is preferably used in an amount of 1.1 to 2.0 mol, more preferably 1.2 to 1.5 mol.

Also, the monofunctional urethane (meth) acrylate (A) having a target hydrogenated polyolefin skeleton is prepared by reacting the urethane isocyanate prepolymer, the hydroxy group-containing (meth) acrylate (Z), and then the compound (L). When a large amount of unreacted isocyanate groups remain in the reaction solution in the end, there is a possibility that problems such as gelation or poor curing of the coating film may occur.

In the above reaction (reaction between urethane isocyanate prepolymer, hydroxy group-containing (meth) acrylate (Z) and compound (L)), hydroxy group-containing (meth) acrylate (Z) is added to urethane isocyanate prepolymer as a component. The reaction is carried out in a stoichiometric relationship such that the number of (meth) acryloyl groups in the molecule of (A) is 1, and the residual isocyanate group in the reaction solution is 0.1% by weight or less. There is a need. For example, in the above [Method 2], there is a method of adjusting the amount of the compound (L) to be finally reacted while monitoring the residual isocyanate concentration in the reaction solution. In the above reaction, the amount (number of moles) of the hydroxy group-containing (meth) acrylate (Z) to be used is preferably 1.0 to 1.1 mol, more preferably 1 mol with respect to 1 mol of urethane isocyanate prepolymer. 1.0 to 1.05 mol. In the above reaction, the number of moles (total amount) of the hydroxyl group of the hydroxy group-containing (meth) acrylate (Z) and the isocyanate reactive group of the compound (L) with respect to the number of moles of the isocyanate group of the urethane isocyanate prepolymer. ) Is not particularly limited, but is preferably 1.0 to 1.1 mol, more preferably 1.0 to 1.05 mol.

The reaction for producing the component (A) (particularly the reaction between the urethane isocyanate prepolymer and the component (Z)) is a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, dibutylhydroxytoluene and the like for the purpose of preventing polymerization. It is preferable to proceed in the presence of. The addition amount (use amount) of these polymerization inhibitors is preferably 1 to 10,000 ppm (weight basis), more preferably 100 to 1000 ppm, and still more preferably 400 to 500 ppm, with respect to the component (A) to be produced. By setting the addition amount of the polymerization inhibitor to 1 ppm or more, a sufficient polymerization inhibition effect tends to be obtained. On the other hand, by setting it to 10000 ppm or less, there is a tendency that an adverse effect derived from the polymerization inhibitor does not easily affect the physical properties of the product.

For the same purpose, this reaction is preferably performed in a gas atmosphere containing molecular oxygen. The oxygen concentration is appropriately selected in consideration of safety.

This reaction may be carried out using a catalyst in order to obtain a sufficient reaction rate. Examples of the catalyst include dibutyltin dilaurate, tin octylate, tin chloride and the like. Of these, dibutyltin dilaurate is preferable from the viewpoint of reaction rate. The addition amount (use amount) of the catalyst is not particularly limited, but is usually preferably 1 to 3000 ppm (weight basis), more preferably 50 to 1000 ppm. When the amount of the catalyst added is 1 ppm or more, a sufficient reaction rate tends to be obtained. On the other hand, by setting it to 3000 ppm or less, there is a tendency that an adverse effect derived from the catalyst does not easily affect the physical properties of the product.

The reaction for producing component (A) can proceed in the presence of a known volatile organic solvent. The volatile organic solvent is not particularly limited, and examples thereof include ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, xylene, toluene and the like. It is done. Of these, ethyl acetate, butyl acetate, toluene and the like are preferable from the viewpoints of boiling point and economy. In addition, a volatile organic solvent can be distilled off by pressure reduction etc. after manufacture of a component (A). Further, the volatile organic solvent remaining in the energy ray curable resin composition can be removed by drying after applying the resin composition to an article, a part, or the like. In addition, a volatile organic solvent means the organic solvent whose boiling point in a normal pressure does not exceed 200 degreeC.

In the reaction for producing the component (A), a reactive diluent can be used in place of the volatile organic solvent or in a combined mode. The reactive diluent is not particularly limited, and examples thereof include 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, isobornyl acrylate, normal octyl acrylate, and the like. From the viewpoint of adjusting the viscosity of the energy ray curable resin composition, isobornyl acrylate and normal octyl acrylate are preferable. When a reactive diluent is used, a composition containing a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a reactive diluent is obtained as a product. The reactive diluent is a monofunctional urethane (metafunctional) having a hydrogenated polyolefin skeleton, if necessary, for the purpose of adjusting the viscosity of the energy ray-curable resin composition described later and adjusting the hardness of the cured product. ) It can also be blended after the acrylate (A) is produced.

Commercially available products may be used as the reactive diluent. For example, 1,6-hexanediol diacrylate (for example, product name “HDDA” manufactured by Daicel Cytec Co., Ltd.), trimethylolpropane triacrylate (for example, the company) Product name “TMPTA”), tricyclodecane dimethanol diacrylate (for example, product name “IRR214-K”), isobornyl acrylate (for example, product name “IBOA-B”), Normal octyl acrylate (for example, product name “NOAA” manufactured by Osaka Organic Chemical Industry Co., Ltd.) is available from the market.

The above reaction (reaction of components (X) to (Z) and component (L)) is not particularly limited, but is preferably allowed to proceed at a temperature (reaction temperature) of 130 ° C. or lower, more preferably from 40 to 130 ° C. is there. By setting the reaction temperature to 40 ° C. or higher, the reaction rate tends to be further improved. On the other hand, by setting the reaction temperature to 130 ° C. or lower, radical polymerization due to heat is suppressed, and the formation of gelled product tends to be more efficiently suppressed.

The above reaction (reactions of components (X) to (Z) and component (L)) is usually performed until the residual isocyanate group is 0.1% by weight or less as described above. The residual isocyanate group concentration can be analyzed by, for example, gas chromatography or titration.

[Diol (X) having hydrogenated polyolefin skeleton]
The diol (X) having a hydrogenated polyolefin skeleton is a compound having a hydrogenated polyolefin skeleton in the molecule and two hydroxy groups in the molecule. As the diol (X) having a hydrogenated polyolefin skeleton, for example, a compound obtained by hydrogenating a polyalkadiene (polybutadiene, polyisoprene, etc.) having hydroxy groups at both ends can be used. The diol (X) having a hydrogenated polyolefin skeleton as a raw material for the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton can be used alone or in combination of two or more. Can also be used.

Commercially available products may be used as the diol (X) having a hydrogenated polyolefin skeleton, such as the product name “Epol” (manufactured by Idemitsu Kosan Co., Ltd.); the product names “NISSO-PB GI-1000”, “NISSO”. -PB GI-2000 "," NISSO-PB GI-3000 "(manufactured by Nippon Soda Co., Ltd.), etc., but are not limited thereto.

[Diisocyanate (Y)]
Diisocyanate (Y) is a compound having two isocyanate groups in the molecule. Among them, those that do not exhibit crystallinity are preferable from the viewpoints of resin appearance, cured product transparency, and the like. Specifically, for example, alicyclic diisocyanates, branched chain aliphatic diisocyanates, and aromatic isocyanates. And at least one selected from the group consisting of diisocyanate compounds obtained by hydrogenation. Examples of the alicyclic diisocyanate include isophorone diisocyanate. The aliphatic diisocyanate having a branched chain is not particularly limited, and examples thereof include 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Examples of the diisocyanate compound obtained by hydrogenating the aromatic isocyanate include hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate. On the other hand, when a large amount of diisocyanates other than the above, particularly those showing crystallinity, are used, there may be a problem in the appearance of the cured product and the transparency of the cured product. In addition, diisocyanate (Y) can also be used individually by 1 type as a raw material of the monofunctional urethane (meth) acrylate (A) which has hydrogenated polyolefin frame | skeleton, and can also be used in combination of 2 or more type. .

Commercially available products can be used as the diisocyanate (Y), and examples thereof include a product name “VESTANAT IPDI” (isophorone diisocyanate, manufactured by Evonik).

[Hydroxy group-containing (meth) acrylate (Z)]
The hydroxy group-containing (meth) acrylate (Z) is a compound having one hydroxy group in the molecule and one (meth) acryloyl group in the molecule. In addition, as a raw material of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, the hydroxy group-containing (meth) acrylate (Z) can be used alone or in combination of two or more. Can also be used.

The hydroxy group-containing (meth) acrylate (Z) is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol Examples thereof include epoxy acrylates such as mono (meth) acrylate and bisphenol A diglycidyl mono (meth) acrylate, and hydrogenated products thereof.

As the hydroxy group-containing (meth) acrylate (Z), a commercially available product can be used. For example, the product name “BHEA” (2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.), the product name “CHDMA” ( And cyclohexane dimethanol monoacrylate, manufactured by Nippon Kasei Kogyo Co., Ltd.).

[Compound (L) (isocyanate-reactive compound)]
As described above, the compound (L) is a compound having one isocyanate-reactive group in the molecule and not having a photocurable functional group (particularly, a (meth) acryloyl group). The compound (L) is mainly used for the purpose of inactivating (sealing) excess isocyanate groups in the urethane isocyanate prepolymer. Examples of the isocyanate-reactive group include known or commonly used functional groups having reactivity with an isocyanate group, and are not particularly limited. For example, a hydroxyl group, an amino group containing active hydrogen, and> C═N—OH. Functional groups, amide groups and the like. That is, examples of the compound (L) include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, Examples include oxime compounds, amine compounds, imine compounds, and pyridine compounds. Among these, alcohol compounds are preferable because they are easy to handle and hardly cause side reactions. In addition, a compound (L) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Examples of the alcohol compound include aliphatic monohydric alcohols having 1 or more (preferably 3 or more) carbon atoms, alicyclic monohydric alcohols having 3 or more carbon atoms, and the molecular weight thereof is 70. To 400. When the alcohol has 3 or more carbon atoms or has a molecular weight of 70 or more, volatilization during the synthesis of the component (A) tends to be efficiently prevented. On the other hand, when the molecular weight is 400 or less, good reactivity with an isocyanate group is ensured, and the productivity tends to be further improved. In addition, when a large amount of an alcohol having an aromatic ring is used as the alcohol compound, for example, the weather resistance of the resulting component (A) may be inferior, which may not be preferable.

Specifically, examples of the alcohol compound include methanol, ethanol, isopropanol, normal propanol, 1-butanol, 1-heptanol, 1-hexanol, normal octyl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), Cyclohexane methanol, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol Other structural isomers are also included) and mixtures thereof. Of these, isopropanol and 2-ethylhexyl alcohol are preferable from the viewpoints of boiling point, price, and availability.

Examples of the phenolic compound include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester, and the like. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of the mercaptan compound include butyl mercaptan and dodecyl mercaptan. Examples of the acid amide compound include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and the like. Examples of the acid imide compound include succinimide and maleic imide. Examples of the imidazole compound include imidazole and 2-methylimidazole. Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole, and the like. Examples of the urea compound include urea, thiourea, and ethylene urea. Examples of the oxime compounds include formaldehyde oxime, acetoald oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and the like. Examples of the amine compound include diphenylamine, aniline, and carbazole. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

In addition, it is also possible to use a polyol other than the diol (X) having a hydrogenated polyolefin skeleton as a raw material for the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton. However, from the viewpoint of vibration damping properties of the cured product, the ratio of the component (X) to the total amount (100% by weight) of the polyol (including the component (X)) is preferably 90 to 100% by weight, more preferably 95 to It is 100% by weight, more preferably 98% by weight or more.

Also, it is possible to use a polyisocyanate other than diisocyanate (Y) as a raw material for the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton. However, from the viewpoint of damping properties of the cured product, the ratio of the component (Y) to the total amount (100% by weight) of the polyisocyanate (including the component (Y)) is preferably 90 to 100% by weight, more preferably 95%. It is ˜100% by weight, more preferably 98% by weight or more.

As the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, a solution obtained by reacting the components (X) to (Z) and the component (L) can be used as it is. It can also be used after being purified by a conventional method.

The weight average molecular weight (Mw) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is not particularly limited, but is preferably 10,000 or more, more preferably 15,000 to 100,000, still more preferably Is 30,000 to 60,000. When the Mw of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is 10,000 or more, the vibration damping property of the cured product tends to be further improved. On the other hand, by setting the Mw of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton to 100,000 or less, the crosslinking density can be increased in an appropriate range, and the curability is further improved. There exists a tendency for a shape change to be suppressed more under high temperature of hardened | cured material. In addition, Mw of monofunctional urethane (meth) acrylate (A) which has hydrogenated polyolefin frame | skeleton can be measured on the conditions as described in an Example.

In the energy ray-curable resin composition of the present invention, the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton can be used alone or in combination of two or more. You can also.

The content (blending amount) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton in the energy beam curable resin composition of the present invention is not particularly limited, but is non-volatile in the energy beam curable resin composition. It is preferably 40 to 99.9% by weight, more preferably 45 to 99% by weight, and still more preferably 50 to 98% by weight, based on the total weight (100% by weight) of the minute. When the content of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is 40% by weight or more, the vibration damping property of the cured product tends to be further improved. On the other hand, by setting the content of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton to 99.9% by weight or less, the content of the photoinitiator (B) can be relatively increased. The curability tends to be improved. The “nonvolatile content” of the energy ray curable resin composition is a component other than the volatile content in the resin composition, and remains in the cured product as a component of the cured product (for example, the present invention). Ingredients obtained by removing the volatile organic solvent from the active energy curable resin composition.

When the energy ray curable resin composition contains a reactive diluent, the content (blending amount) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is not particularly limited, but is energy ray curable. It is preferably 40 to 99.9% by weight, more preferably 45 to 90% by weight, and still more preferably 50 to 80% by weight, based on the total weight (100% by weight) of the nonvolatile content of the resin composition.

When the energy ray curable resin composition contains a volatile organic solvent, the content (blending amount) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton is not particularly limited, but is energy ray curable. 70 to 99.9% by weight is preferable, more preferably 80 to 99% by weight, still more preferably 85 to 98% by weight, and most preferably based on the total weight (100% by weight) of the nonvolatile content of the resin composition. Is 90 to 97% by weight.

The content (blending amount) of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton in the energy beam curable resin composition of the present invention is not particularly limited, but is the total amount of the energy beam curable resin composition. (For example, the total amount of component (A), photoinitiator (B), reactive diluent, volatile organic solvent, etc.) is preferably 1 to 99% by weight, more preferably 10 to 90% by weight with respect to 100% by weight. %, More preferably 30 to 85% by weight, most preferably 50 to 80% by weight. By setting the content of the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton within the above range, the vibration damping property of the cured product tends to be further improved.

<Photoinitiator (B)>
As the photoinitiator (B) (photopolymerization initiator) in the energy ray-curable resin composition of the present invention, a known or conventional photoradical polymerization initiator can be used, and is not particularly limited. -Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether Ether, benzoin isopropyl ether, benzoin n- butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, and acrylated benzophenone. In the energy ray curable resin composition of the present invention, the photoinitiator (B) can be used alone or in combination of two or more.

The content (blending amount) of the photoinitiator (B) in the energy beam curable resin composition of the present invention is not particularly limited, but is the total amount of radical polymerizable compounds contained in the energy beam curable resin composition ( (For example, monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, reactive diluent, etc.) is preferably 0.1 to 20 parts by weight, more preferably 1 to 5 parts by weight. It is. By setting the content of the photoinitiator (B) to 0.1 parts by weight or more, the curability of the energy ray curable resin composition is further improved, and the photoinitiator (B) tends to be sufficiently cured. On the other hand, by setting the content of the photoinitiator (B) to 20 parts by weight or less, residual odor or coloring of the photoinitiator (B) in the cured product is suppressed, and various physical properties of the cured product are adversely affected. It tends to be suppressed.

<Reactive diluent>
The energy beam curable resin composition of the present invention may contain a reactive diluent as long as the effects of the present invention are not impaired. Examples of the reactive diluent include those similar to those exemplified in the section “Monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton”. In the energy beam curable resin composition of the present invention, one type of reactive diluent can be used alone, or two or more types can be used in combination. The content (blending amount) of the reactive diluent is not particularly limited. For example, the total amount of the energy beam curable resin composition (for example, the component (A), the photoinitiator (B), the reactive diluent, etc.) The total amount is preferably from 1 to 99 parts by weight, more preferably from 10 to 90 parts by weight, still more preferably from 15 to 80 parts by weight, and particularly preferably from 20 to 60 parts by weight. By setting the reactive diluent within the above range, the viscosity of the energy ray curable resin composition is lowered and handling becomes good, and in addition, drying and curing time are shortened, which is more advantageous in cost. Tend.

<Volatile organic solvent>
The energy beam curable resin composition of the present invention may contain a volatile organic solvent. Examples of the volatile organic solvent include those similar to the volatile organic solvent exemplified in the above-mentioned section of “Monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton”. In the energy beam curable resin composition of the present invention, the volatile organic solvent can be used alone or in combination of two or more. The content (blending amount) of the volatile organic solvent is not particularly limited. For example, the total amount of the energy ray curable resin composition (for example, component (A), photoinitiator (B), volatile organic solvent, etc.) The total amount is preferably from 1 to 99 parts by weight, more preferably from 10 to 90 parts by weight, still more preferably from 15 to 80 parts by weight, particularly preferably from 20 to 60 parts by weight. By setting the volatile organic solvent within the above range, the viscosity of the energy ray curable resin composition is lowered, and the handling is improved.

<Additives>
The energy beam curable resin composition of the present invention may contain various additives as required. Examples of such additives include fillers, dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, and thixotropic agents. The content (blending amount) of these additives is not particularly limited, but is preferably 0 to 20% by weight, more preferably 0.05 to 10% with respect to the energy ray curable resin composition (100% by weight). % By weight.

The energy beam curable resin composition of the present invention includes a monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, a photoinitiator (B), and other reactive diluents as necessary. Can be obtained by mixing the components. As mixing means, known or commonly used means can be used, and is not particularly limited. For example, means such as various mixers such as a dissolver and a homogenizer, kneaders, rolls, bead mills, self-revolving stirrers and the like can be used. Moreover, conditions, such as temperature and the rotation speed in the case of mixing, are not specifically limited, It can set suitably.

≪Hardened product≫
A cured product (cured resin product; sometimes referred to as “cured product of the present invention”) is obtained by irradiating the energy beam curable resin composition of the present invention with an energy beam (active energy beam) and curing it. Can do. Since the cured product of the present invention has very excellent vibration damping properties, for example, a cured product layer obtained by curing the energy ray curable resin composition of the present invention (a cured product layer formed by the cured product of the present invention). ) Can be preferably used as a coating layer for the purpose of imparting vibration damping properties to articles, parts, etc., vibration damping sheets, and the like.

Tan δ at 23 ° C. of the cured product of the present invention is not particularly limited, but is preferably 0.6 or more (for example, 0.6 to 2.0), more preferably 0.8 or more, and further preferably 1.0 or more. It is. By setting Tan δ to be 0.6 or more, vibration damping tends to be further improved. Tan δ can be measured by the same method as described in the examples.

≪Coating agent≫
Since the energy beam curable resin composition of the present invention can be cured to form a cured product having extremely excellent vibration damping properties, for example, a coating capable of imparting vibration damping properties to various articles. It can be preferably used as a coating agent (damping imparting coating agent) for forming a material. For example, the energy ray curable resin composition (coating agent) of the present invention is applied (coated) to the surface of an article or a part, or the gap between the above parts of an article composed of two or more parts, and the energy ray. By irradiating and curing, it becomes possible to impart excellent vibration damping properties to articles and parts. In particular, the energy ray curable resin composition of the present invention can be applied to not only a planar article but also an article having a complicated shape such as a three-dimensional shape to form a coating material. It is possible to impart excellent vibration damping properties to various articles. In addition, since the energy ray curable resin composition of the present invention can be cured by irradiation with energy rays (particularly, ultraviolet rays), it is a coating material (cured product) having a very excellent vibration damping property with high productivity. Can be formed.

The application is not particularly limited, and can be performed using known or conventional means such as airless spray, air spray, roll coat, bar coat, gravure coat, die coat and the like. In addition, the application can be performed by a so-called in-line coating method that is performed during the manufacturing process of the article or component, or is applied to the already manufactured article or component (the manufacture of the article or component and the like). Can be applied by a so-called off-line coating method.

The film thickness (coating film thickness) when the energy beam curable resin composition of the present invention is applied to the surface of an article or a part is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm. It is. By setting the thickness to 100 μm or less, the amount of the resin composition to be applied can be kept small, and drying and curing times are shortened, which tends to be more advantageous in cost. On the other hand, by setting the thickness to 1 μm or more, the vibration damping property of the cured product tends to be more effectively exhibited.

In the production of the coating material (cured product) described above, when the energy ray curable resin composition of the present invention contains a reactive diluent and / or a volatile organic solvent, after applying the resin composition, Usually, heat drying with hot air or the like is performed. Thereafter, the applied energy ray-curable resin composition can be cured in an extremely short time by irradiating it with energy rays such as ultraviolet rays and electron beams. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like can be used as a light source when performing ultraviolet irradiation. The energy beam irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but it is several tens of seconds at most, and usually several seconds. Usually, an irradiation source with a lamp output of about 80 to 300 W / cm is used. For example, in the case of electron beam irradiation, it is preferable to use an electron beam having an energy in the range of 50 to 1000 KeV and to give an irradiation amount of 2 to 5 Mrad. After energy beam irradiation, heating may be performed as necessary to further promote curing.

≪Vibration control sheet≫
For example, a cured product obtained by curing the energy beam curable resin composition of the present invention into a sheet or by curing the energy beam curable resin composition of the present invention (the energy beam curable of the present invention). A vibration damping sheet containing the cured product of the present invention (sometimes referred to as “the vibration damping sheet of the present invention”) is obtained by molding and processing a cured product of the resin composition into a sheet. The “sheet” in the vibration damping sheet of the present invention includes various planar shapes such as “film” and “plate”. That is, the vibration damping sheet of the present invention includes articles having various planar shapes such as “damping film” and “damping plate”. The vibration damping sheet of the present invention only needs to contain at least the cured product of the present invention, and may be formed only by the sheet-shaped cured product of the present invention, or the sheet-shaped cured product of the present invention. It may be a laminate of an object and another sheet. Further, the vibration damping sheet of the present invention may have a single-layer configuration or a multilayer configuration. In addition, the thickness (total thickness, thickness of the sheet-like cured product of the present invention) of the vibration damping sheet of the present invention is not particularly limited, and can be appropriately selected depending on the use and the like.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Synthesis example of monofunctional urethane (meth) acrylate having hydrogenated polyolefin skeleton]
Below, the synthesis example of the monofunctional urethane (meth) acrylate which has hydrogenated polyolefin frame | skeleton is demonstrated.

(Measurement of isocyanate group concentration)
The isocyanate group concentration was measured as follows. In addition, the measurement was performed under stirring with a stirrer in a 100 mL glass flask.
The blank value was measured as follows. First, 15 mL of a THF solution (0.1 N) of dibutylamine was added to 15 mL of THF. Further, after adding 3 drops of bromophenol blue (diluted in 1% by weight of methanol) to give a blue color, titration was performed with an aqueous HCl solution having a normality of 0.1N. The titration amount of the aqueous HCl solution when the color change was observed was defined as V _b (mL).
The measured isocyanate group concentration was measured as follows. First, a sample of W _s (g) was weighed and dissolved in 15 mL of THF, and 15 mL of dibutylamine in THF (0.1 N) was added. After confirming that the solution was formed, 3 drops of bromophenol blue (diluted in 1% by weight of methanol) were added to give a blue color, followed by titration with an aqueous HCl solution having a normality of 0.1N. The titer of the aqueous HCl solution when the color change was observed was defined as V _s (mL).
Using the measured value obtained above, the isocyanate group concentration in the sample was calculated by the following calculation formula.
Isocyanate group concentration (% by weight) = (V _b −V _s ) × 1.005 × 0.42 ÷ W _s

(Measurement of weight average molecular weight)
The weight average molecular weight was determined by GPC (gel permeation chromatography) method based on standard polystyrene under the following measurement conditions.
Equipment used: TOSO HLC-8220GPC
Pump: DP-8020
Detector: RI-8020
Column type: Super HZM-M, Super HZ4000, Super HZ3000, Super HZ2000
Solvent: Tetrahydrofuran Phase flow rate: 1 mL / min Column pressure: 5.0 MPa
Column temperature: 40 ° C
Sample injection volume: 10 μL
Sample concentration: 0.2 mg / mL

The raw materials used in the examples are as follows.
(Diol having hydrogenated polyolefin skeleton)
NISSO PB GI-1000 (GI-1000): product name “NISSO PB GI-1000” (manufactured by Nippon Soda Co., Ltd.), hydrogenated 1,2-polybutadiene glycol (hydroxyl value 66 mgKOH / g, estimated molecular weight 1,700)
NISSO PB GI-3000 (GI-3000): Product name “NISSO PB GI-3000” (manufactured by Nippon Soda Co., Ltd.), hydrogenated 1,2-polybutadiene glycol (hydroxyl value 29.7 mgKOH / g, estimated molecular weight 3, 778)
(Diisocyanate)
IPDI: Product name “VESTANAT IPDI” (manufactured by Evonik), isophorone diisocyanate (molecular weight 222)
(Hydroxy group-containing (meth) acrylate)
HEA: Product name “BHEA” (manufactured by Nippon Shokubai Co., Ltd.), 2-hydroxyethyl acrylate (molecular weight 116)
(Isocyanate-reactive compound)
IPA: isopropyl alcohol (molecular weight 60)

In addition, as the molecular weight of the diol having a hydrogenated polyolefin skeleton, an estimated molecular weight calculated from the hydroxyl value as each molecule having two hydroxy groups in the molecule was used. The calculation formula of the estimated molecular weight is as follows.
Estimated molecular weight = 56.1 (KOH molecular weight) ÷ hydroxyl value (mgKOH / g) × 1000 × 2

[Synthesis Example 1: Preparation of monofunctional urethane acrylate solution (UA1) having hydrogenated polybutadiene skeleton]
466.7 g of toluene, 645.0 g of NISSO-PB GI-3000, 47.4 g of IPDI, and 0.560 g of BHT (butylhydroxytoluene) were placed in a 2 L separable flask equipped with a thermometer and a stirrer. Prepared. After the above raw materials were uniformly mixed under gentle stirring, 0.210 g of DBTDL (dibutyltin dilaurate) was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and the mixture was heated to 50 ° C. Heating was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 5.0 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C., and the stirring was maintained at the same temperature for 1 hour under gentle stirring.
Further, 2.7 g of IPA was added with gentle stirring at the same temperature. Thereafter, the reaction was continued at 70 ° C. for 1 hour or more until the isocyanate group concentration (NCO%) became 0.1% or less.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity of the resulting monofunctional urethane acrylate solution (UA1) having a hydrogenated polybutadiene skeleton at 25 ° C. was 1,400 mPa · s. Moreover, the weight average molecular weight of the monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution was 37247.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-3000 / IPDI / HEA / IPA = 4/5/1/1
Therefore, the repeating structure of each raw material in the obtained monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
IPA / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / HEA

[Synthesis Example 2: Preparation of monofunctional urethane acrylate solution having hydrogenated polybutadiene skeleton (UA2)]
666.7 g toluene, 858.9 g NISSO-PB GI-1000, 128.2 g IPDI, and 0.800 g BHT were charged to a 2 L separable flask equipped with a thermometer and stirrer. After the above raw materials were uniformly mixed under gentle stirring, 0.300 g of DBTDL was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and heating to 50 ° C. was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 8.4 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C., and the stirring was maintained at the same temperature for 1 hour under gentle stirring.
Further, 4.5 g of IPA was added with gentle stirring at the same temperature. Thereafter, the reaction was continued at 70 ° C. for 1 hour or more until the isocyanate group concentration (NCO%) became 0.1% or less.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity of the resulting monofunctional urethane acrylate solution (UA2) having a hydrogenated polybutadiene skeleton at 25 ° C. was 1,700 mPa · s. Moreover, the weight average molecular weight of the monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution was 38632.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-1000 / IPDI / HEA / IPA = 7/8/1/1
Therefore, the repeating structure of each raw material in the obtained monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
IPA / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / HEA

[Synthesis Example 3: Preparation of monofunctional urethane acrylate solution having hydrogenated polybutadiene skeleton (UA3)]
428.6 g isobornyl acrylate, 858.9 g NISSO-PB GI-1000, 128.2 g IPDI, and 0.800 g BHT were charged into a 2 L separable flask equipped with a thermometer and stirrer. . After the above raw materials were uniformly mixed under gentle stirring, 0.300 g of DBTDL was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and heating to 50 ° C. was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 8.4 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C., and the stirring was maintained at the same temperature for 1 hour under gentle stirring.
Further, 4.5 g of IPA was added with gentle stirring at the same temperature. Thereafter, the reaction was continued at 70 ° C. for 1 hour or more until the isocyanate group concentration (NCO%) became 0.1% or less.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity at 60 ° C. of the monofunctional urethane acrylate solution (UA3) having a hydrogenated polybutadiene skeleton was 22.4 Pa · s. Moreover, the weight average molecular weight of the monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution was 50570.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-1000 / IPDI / HEA / IPA = 7/8/1/1
Therefore, the repeating structure of each raw material in the obtained monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
IPA / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / HEA

[Synthesis Example 4: Preparation of monofunctional urethane acrylate solution having hydrogenated polybutadiene skeleton (UA4)]
428.6 g normal octyl acrylate, 858.9 g NISSO-PB GI-1000, 128.2 g IPDI, and 0.800 g BHT were charged into a 2 L separable flask equipped with a thermometer and stirrer. After the above raw materials were uniformly mixed under gentle stirring, 0.300 g of DBTDL was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and heating to 50 ° C. was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 8.4 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C., and the stirring was maintained at the same temperature for 1 hour under gentle stirring.
Further, 4.5 g of IPA was added with gentle stirring at the same temperature. Thereafter, the reaction was continued at 70 ° C. for 1 hour or more until the isocyanate group concentration (NCO%) became 0.1% or less.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity of the resulting monofunctional urethane acrylate solution (UA4) having a hydrogenated polybutadiene skeleton at 25 ° C. was 39.7 Pa · s. The weight average molecular weight of the monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution was 46423.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-1000 / IPDI / HEA / IPA = 7/8/1/1
Therefore, the repeating structure of each raw material in the obtained monofunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
IPA / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / HEA

[Comparative Synthesis Example 1: Preparation of bifunctional urethane acrylate solution having hydrogenated polybutadiene skeleton (UA5)]
180.0 g toluene, 247.9 g NISSO-PB GI-3000, 18.2 g IPDI, and 0.2160 g BHT were charged into a 0.5 L separable flask equipped with a thermometer and stirrer. After the above raw materials were uniformly mixed under gentle stirring, 0.081 g of DBTDL was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and heating to 50 ° C. was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 3.8 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C. and kept at this temperature for 1 hour with gentle stirring until the isocyanate group concentration (NCO%) became 0.1% or less, and the reaction was continued.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity of the resulting bifunctional urethane acrylate solution (UA5) having a hydrogenated polybutadiene skeleton at 25 ° C. was 1,400 mPa · s. Moreover, the weight average molecular weight of the bifunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution was 34922.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-3000 / IPDI / HEA = 4/5/2
Therefore, the repeating structure of each raw material in the obtained bifunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
HEA / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / GI-3000 / IPDI / HEA

[Comparative Synthesis Example 2: Preparation of bifunctional urethane acrylate solution (UA6) having hydrogenated polybutadiene skeleton]
160.0 g toluene, 205.3 g NISSO-PB GI-1000, 30.6 g IPDI, and 0.192 g BHT were charged into a 0.5 L separable flask equipped with a thermometer and stirrer. After the above raw materials were uniformly mixed under gentle stirring, 0.072 g of DBTDL was added under a mixed gas of nitrogen and oxygen (oxygen concentration 2.5%), and heating to 50 ° C. was started. After the temperature reached 50 ° C., stirring was maintained at this temperature for 1 hour.
Then 4.0 g of HEA was added with gentle stirring at the same temperature. Thereafter, the mixture was heated to 70 ° C. and kept at this temperature for 1 hour with gentle stirring until the isocyanate group concentration (NCO%) became 0.1% or less, and the reaction was continued.
Then, heating and stirring were stopped, and the obtained product (solution) was poured into another container to complete the reaction. The viscosity of the resulting bifunctional urethane acrylate solution (UA6) having a hydrogenated polybutadiene skeleton at 25 ° C. was 1,700 mPa · s. In addition, the bifunctional urethane acrylate having a hydrogenated polybutadiene skeleton in the solution had a weight average molecular weight of 38768.
In addition, the molar ratio of the raw material calculated from the charged weight and molecular weight is as follows.
GI-1000 / IPDI / HEA = 7/8/2
Therefore, the repeating structure of each raw material in the obtained bifunctional urethane acrylate having a hydrogenated polybutadiene skeleton is as follows.
HEA / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / GI-1000 / IPDI / HEA

[Examples and Comparative Examples: Preparation of energy beam curable resin composition and production of film]
<Preparation of energy ray curable resin composition>
Using a suitable mixer, the solutions UA1 to 6 obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 and the photoinitiator were mixed in the composition shown in Table 1 to obtain a compound (energy beam). A curable resin composition) was prepared. As the photoinitiator, as shown in Table 1, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, product name “IRGACURE184”) was used.

<Production of film>
Each energy ray-curable resin composition obtained above was poured into an aluminum disposable cup (manufactured by Anton Paar) so that the thickness after drying was 1 mm. Then, it is dried in an oven at 80 ° C. for 10 minutes, and subsequently, using a UV irradiator (product name “EYE INVERTOR GRANDAGE ECS-401GX” manufactured by Eye Graphics Co., Ltd.), a peak illuminance of 400 mW / cm ² and an integrated light amount of 860 mJ A film (damping sheet) was produced by curing by irradiating with ultraviolet rays under the conditions of / cm ² .

[Evaluation of damping characteristics Tanδ (23 ° C)]
The film obtained above is set in a rheometer (product name “Physica MCR300”, manufactured by Anton Paar), and using a parallel plate (PP7) under the conditions of gap 1 mm, dynamic strain 1%, frequency 1 Hz− Measurement was performed at 30 ° C. to 80 ° C., and the value of Tan δ at 23 ° C. was measured. The results are shown in Table 2. The greater the value of Tan δ at 23 ° C., the better the damping characteristics.

The energy beam curable resin composition of the present invention can be cured to form a cured product having very excellent vibration damping properties. For this reason, the energy beam curable resin composition of the present invention can be particularly preferably used for applications such as a coating agent for imparting vibration damping properties and a raw material for vibration damping sheets.

Claims (4)

1. A monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton and a photoinitiator (B);
   A monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, a diol (X) having a hydrogenated polyolefin skeleton, a diisocyanate (Y), a hydroxy group-containing (meth) acrylate (Z), and an intramolecular It is a urethane (meth) acrylate obtained by reacting with a compound (L) having one isocyanate-reactive group and not having a photocurable functional group. .
2. The energy ray-curable resin composition according to claim 1, wherein the monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton has a weight average molecular weight of 10,000 or more.
3. The monofunctional urethane (meth) acrylate (A) having a hydrogenated polyolefin skeleton, a photoinitiator (B), a reactive diluent, and / or a volatile organic solvent are further included. Energy ray curable resin composition.
4. A vibration damping sheet comprising a cured product of the energy beam curable resin composition according to any one of claims 1 to 3.