JP5542029B2 - (Meth) acryloyl group-containing polyurethane, method for producing (meth) acryloyl group-containing polyurethane, radical polymerizable resin composition, cured product - Google Patents

Description

  The present invention relates to a (meth) acryloyl group-containing polyurethane, a method for producing the same, a radical polymerizable resin composition containing a (meth) acryloyl group-containing polyurethane, and a cured product using the same.

A thermosetting resin capable of forming a cured product having a high tensile elongation and a high mechanical strength (elastic modulus, strength) can be used, for example, in the manufacture of a molded product having a complex shape or a large molded product, and Since it is difficult to cause cracks, it is expected to be applied to various fields including molding materials.
However, a cured product having a high tensile elongation obtained using a conventional thermosetting resin is usually not sufficient in terms of mechanical strength (elastic modulus, strength), and due to a strong external force, In some cases, the cured product may be deformed.
On the other hand, a cured product excellent in mechanical strength obtained by using a conventional thermosetting resin is not sufficient in terms of the tensile elongation, and is brittle. For example, mechanical parts, electric / electronic field members, railways / vehicles, etc. In some cases, the use is limited in applications such as materials, civil engineering and building materials. Therefore, development of resin which can form hardened | cured material which has high elongation rate and high mechanical strength was calculated | required.

In general, since a high tensile elongation and a high mechanical strength are in a trade-off relationship, development of a thermosetting resin capable of forming a high-toughness cured product satisfying both of them has been studied.
For example, urethane (meth) acrylate using a polycarbonate raw material and a resin composed of an unsaturated monomer are cured into a sheet shape, placed in a molding die, a sheet mold compound (SMC) is stacked thereon, and the sheet is heated. A sheet-like cured product obtained by integral molding with a sheet mold compound while being stretch-shaped is known (see Patent Document 1).
However, it is still difficult for the sheet-like cured product to achieve both high elongation and high mechanical strength, and the brittleness has not been improved sufficiently.

Examples of the thermosetting resin include (meth) acrylate oligomers such as vinyl ester oligomers and urethane (meth) acrylate oligomers, oligomers having at least one maleate ester and / or fumarate ester unit in the molecule, and polymerization. A radically polymerizable resin composition containing a reactive monomer is known, and the (meth) acrylate oligomer is specifically a urethane acrylate oligomer obtained by reacting tolylene diisocyanate, polyethylene glycol and hydroxypropyl acrylate. It is disclosed that can be used (refer patent document 2).
However, although the cured product obtained using the resin composition is excellent in terms of mechanical strength, it is still not sufficient in terms of tensile elongation, so that there are cases in which both cannot be achieved.
Moreover, as the thermosetting resin, a coating binder containing a polyester-based polyol and a urethane acrylate composed of an isocyanate compound has been reported (see Patent Document 3).
However, although the cured product obtained using the urethane acrylate was excellent in terms of tensile elongation, it was still not sufficient in terms of mechanical strength such as strength, and could not be used as a molding material.

JP 2001-288230 A Japanese Patent Laid-Open No. 2004-10771 JP-A-61-190519

  The present invention relates to a radical polymerizable resin composition capable of forming a cured product having both high tensile elongation and high mechanical strength such as tensile elastic modulus and tensile strength, a cured product using the same, and radical polymerization. It is an object of the present invention to provide a (meth) acryloyl group-containing polyurethane that can be used in a conductive resin composition and a method for producing the (meth) acryloyl group-containing polyurethane.

  The present invention relates to a (meth) acryloyl group-containing polyurethane (A) represented by the following general formula (I) and a radical polymerizable resin composition containing the same and a radical polymerizable unsaturated monomer (B). .

（一般式（Ｉ）中のＬは、数平均分子量９００〜２５００のポリカーボネート構造を表し、Ｍはポリカーボネート構造、ポリオキシアルキレン基及びアルキレン基（脂肪族環式構造を有するものも含む。）からなる群より選ばれる１種以上を有する構造であり、Ｔは直鎖状または分岐鎖状アルキレン基、脂肪族環式構造を有するアルキレン基または芳香族構造を有するアルキレン基である。Ｘは（メタ）アクリロイル基を含む原子団を表す。）

(L in the general formula (I) represents a polycarbonate structure having a number average molecular weight of 900 to 2500, and M consists of a polycarbonate structure, a polyoxyalkylene group and an alkylene group (including those having an aliphatic cyclic structure). And T is a linear or branched alkylene group, an alkylene group having an aliphatic cyclic structure, or an alkylene group having an aromatic structure, and X is (meth). (Represents an atomic group containing an acryloyl group.)

In the present invention, the polycarbonate polyol (a1) and the polyisocyanate (a2) have a molar ratio [isocyanate group / hydroxyl group] between the hydroxyl group of the polycarbonate polyol (a1) and the isocyanate group of the polyisocyanate (a2). A polyurethane (a3) having an isocyanate group at the molecular end is obtained by reacting in the range of 1.8 to 2.3, and then the polyurethane (a3), a number average having an aliphatic cyclic structure and a polycarbonate structure One or more polyols (a4) selected from the group consisting of polycarbonate polyols having a molecular weight of 500 to 1000, polyoxyalkylene polyols having a number average molecular weight of 100 to 550, and alkylene polyols having a number average molecular weight of 60 to 550, ( The polyurethane (a5) is obtained by reacting in a range where the molar ratio [isocyanate group / hydroxyl group] of the isocyanate group of 3) and the hydroxyl group of the polyol (a4) is 1.8 to 2.3, wherein the polyurethane (a5), a process for producing a hydroxyl group and (meth) above, wherein the obtained by reacting acryloyl group-containing compound (a6) (meth) acryloyl group-containing polyurethane (a).
Furthermore, the present invention relates to a cured product obtained by curing the radical polymerizable resin composition.

  The (meth) acryloyl group-containing polyurethane (A) of the present invention and the radically polymerizable resin composition containing the same can form a cured product having both high tensile elongation and high mechanical strength. It can be used for manufacturing various molded articles such as electric / electronic field members, railway / vehicle members, civil engineering and building field materials.

3 is an IR spectrum diagram of polyurethane (I) obtained in Example 3. FIG. 6 is an IR spectrum diagram of polyurethane (I) obtained in Example 6. FIG.

  The (meth) acryloyl group-containing polyurethane (A) of the present invention is represented by the following general formula (I).

（一般式（Ｉ）中のＬは、数平均分子量９００〜２５００のポリカーボネート構造を表し、Ｍはポリカーボネート構造、ポリオキシアルキレン基及びアルキレン基からなる群より選ばれる１種以上を有する構造であり、Ｔは直鎖状または分岐鎖状アルキレン基、脂肪族環式構造を有するアルキレン基または芳香族構造を有するアルキレン基である。Ｘは（メタ）アクリロイル基を含む原子団を表す。）

(L in the general formula (I) represents a polycarbonate structure having a number average molecular weight of 900 to 2500, and M is a structure having at least one selected from the group consisting of a polycarbonate structure, a polyoxyalkylene group and an alkylene group, T is a linear or branched alkylene group, an alkylene group having an aliphatic cyclic structure, or an alkylene group having an aromatic structure, and X represents an atomic group containing a (meth) acryloyl group.

L in the general formula (I) is a polycarbonate structure having a number average molecular weight of 900 to 2500, preferably a number average molecular weight of 1000 to 2000. When L is not a polycarbonate structure but a (meth) acryloyl group-containing polyurethane having a polyester structure or a polyether structure, a cured product having a high tensile elongation can be obtained, but sufficient in terms of mechanical strength. It may not be.
On the other hand, even if the L has a polycarbonate structure, if the number average molecular weight is less than 900, the resulting cured product may have a decrease in tensile elongation, and if the number average molecular weight exceeds 2500, The cured resin product may become cloudy and cause a decrease in mechanical strength.
In the present specification and claims, the polycarbonate structure refers to a structure having a plurality of carbonate esters (—O—C (═O) —O—) in the structure.

Said L can be made into a polycarbonate structure by using a polycarbonate polyol as a polyol used when manufacturing the (meth) acryloyl group containing polyurethane (A) of this invention. As a polycarbonate polyol at the time of manufacture, what is mentioned as polycarbonate polyol (a1) mentioned later can be used.
The polycarbonate structure as L is preferably one having about 4 to 30 carbonate bonds in the structure.
Specifically, L preferably has a structure represented by the following general formula (V).

（式中、Ｒは炭素数２〜８のアルキレン基であり、ｎは４〜３０の整数である。式中の複数のＲは、それぞれ同じであっても、異なっていてもよい。）

(In the formula, R is an alkylene group having 2 to 8 carbon atoms, and n is an integer of 4 to 30. A plurality of R in the formula may be the same or different.)

Further, M in the general formula (I) is a structure having at least one selected from the group consisting of a polycarbonate structure, a polyoxyalkylene group and an alkylene group. The M may be any structure described above.
In the present specification and claims, an alkylene group is a divalent group formed by removing two hydrogen atoms bonded to two different carbon atoms of a methylene group or an aliphatic saturated hydrocarbon group. A group in which one hydrogen atom bonded to carbon atoms at both ends of a methylene group, an ethylene group, a linear and saturated aliphatic hydrocarbon group having 3 or more carbon atoms is removed (polymethylene group), other than the polymethylene group These chain-like divalent aliphatic saturated hydrocarbon groups and cyclic divalent aliphatic saturated hydrocarbon groups are collectively referred to.

  The M preferably has a relatively low molecular weight as compared with L in the general formula (I). Specifically, when the M has an aliphatic cyclic structure and a polycarbonate structure, the number average molecular weight is preferably 470 to 970, and when the M is a polyoxyalkylene group, the number average molecular weight is It is preferable that it is 70-520, and since the number average molecular weight is 30-520 when the said M is an alkylene group, since the mechanical strength of the hardened | cured material obtained can be improved, it is preferable.

More specifically, the M is preferably an alkylene group having a number average molecular weight of 30 to 520 in order to further improve the tensile strength. The alkylene group is a linear alkylene group or an aliphatic cyclic group. More preferably, it is a structure-containing alkylene group.
On the other hand, when further improving the tensile elongation rate of the obtained film or the like, the M is an aliphatic cyclic structure-containing polycarbonate polyol having a number average molecular weight of 500 to 1000 obtained by reacting cyclohexanedimethanol and carbonate. It is preferable to use a derived structure or a polyoxyethylene structure having a number average molecular weight of 70 to 520.

  As a polyol used when producing the (meth) acryloyl group-containing polyurethane (A) of the present invention, together with a polycarbonate polyol (a1) described later, a polyol having a polycarbonate structure, a polyoxyalkylene, an alkylene group or the like (a polyol (described later) By using a4)) in combination, the structure M described above can be formed.

T in the general formula (I) is a linear or branched alkylene group, an alkylene group having an aliphatic cyclic structure, or an alkylene group having an aromatic structure.
By using the polyisocyanate having an alkylene group as the polyisocyanate used in producing the (meth) acryloyl group-containing polyurethane (A) of the present invention, the above-described T structure can be formed.

  X in the general formula (I) is an atomic group containing a (meth) acryloyl group. Specific examples include a structure derived from a hydroxyl group and (meth) acryloyl group-containing compound (a6) described later, and this structure imparts a (meth) acryloyl group in the molecule of the polyurethane (A) of the present invention. It is preferable that one or two (meth) acryloyl groups exist at each molecular end of the polyurethane (A).

  As the (meth) acryloyl group-containing polyurethane (A), those having a molecular weight of 2000 to 8000 are preferably used, and those having a molecular weight of 2700 to 7200 are more preferably used. In addition, the said molecular weight points out the value calculated | required from the total amount based on the formula amount of the atom which comprises a (meth) acryloyl group containing polyurethane (A).

  The (meth) acryloyl group-containing polyurethane (A) is, for example, a step [p] of obtaining a polyurethane (a3) having an isocyanate group at a molecular end by reacting a polycarbonate polyol (a1) and a polyisocyanate (a2). Polyurethane (a3), a polycarbonate polyol having an aliphatic cyclic structure and a polycarbonate structure, having a number average molecular weight of 500 to 1,000, a polyoxyalkylene polyol having a number average molecular weight of 100 to 550, and an alkylene polyol having a number average molecular weight of 60 to 550 A step [q] of obtaining a polyurethane (a5) having an isocyanate group at a molecular terminal by reacting with one or more polyols (a4) obtained from the group consisting of the above, and the polyurethane (a5), a hydroxyl group and (meta Acu Royle group-containing compound (a6) and can be prepared by undergoing the step [r] reacting.

The step [p] is a step of obtaining a polyurethane (a3) having an isocyanate group at the molecular end by reacting the polycarbonate polyol (a1) with the polyisocyanate (a2).
By controlling the structure of the (meth) acryloyl group-containing polyurethane (A) of the present invention to that represented by the general formula (I), the cured product obtained can have both high tensile elongation and high mechanical strength. Is realized.
Therefore, when manufacturing the said (meth) acryloyl group containing polyurethane (A), it is also important to supply the manufacturing raw material one by one and to make it react.

  In the reaction between the polycarbonate polyol (a1) and the polyisocyanate (a2), the molar ratio of the hydroxyl group of the polycarbonate polyol (a1) to the isocyanate group of the polyisocyanate (a2) is [isocyanate group / hydroxyl group] = Performing in the range of 1.8 to 2.3 produces the (meth) acryloyl group-containing polyurethane (A) represented by the general formula (I), and achieves both high tensile elongation and high mechanical strength. It is preferable for forming a cured product.

  In the step [p], for example, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and cibutyltin dilaurate, and further stannous chloride, Catalysts such as acids and alkalis such as stannous bromide and stannous iodide can be used as necessary. The amount of these catalysts added is preferably 10 to 10,000 ppm with respect to the total charge.

  In the step [p], for example, a polymerization inhibitor such as hydroquinone monomethyl ether, dt-butyl hydroquinone, pt-butyl catechol, phenothiazine and the like can be used as necessary. The amount of the polymerization inhibitor used is preferably 10 to 10,000 ppm with respect to the total charged amount.

The step [q] comprises reacting the polyurethane (a3) having an isocyanate group at the molecular end obtained in the step [p] with the polyol (a4) to react with the polyurethane having an isocyanate group at the molecular end (a5 ).
In the reaction of the polyurethane (a3) and the polyol (a4), the molar ratio of the isocyanate group of the polyurethane (a3) to the hydroxyl group of the polyol (a4) is [isocyanate group / hydroxyl group] = 1. The reaction in the range of 8 to 2.3 produces the (meth) acryloyl group-containing polyurethane (A) represented by the general formula (I) and has both high tensile elongation and high mechanical strength. It is preferable for forming a cured product.
In the step [q], 10 to 10,000 ppm of catalyst or polymerization inhibitor can be used as required with respect to the total charge. As these catalysts and polymerization inhibitors, those similar to those mentioned in the above step [p] can be used.

The step [r] is a step of reacting the polyurethane (a5) obtained in the step [q] with the hydroxyl group and (meth) acryloyl group-containing compound (a6).
Specifically, it is a step of reacting the isocyanate group possessed by the polyurethane (a5) at the molecular end with the hydroxyl group possessed by the hydroxyl group and the (meth) acryloyl group-containing compound (a6).
In the reaction, the molar ratio of the isocyanate group of the polyurethane (a5) to the hydroxyl group of the hydroxyl group and (meth) acryloyl group-containing compound (a6) is [isocyanate group / hydroxyl group] = 0.8 to 1. 3 to produce a (meth) acryloyl group-containing polyurethane (A) represented by the general formula (I), and a cured product having both high tensile elongation and high mechanical strength. It is preferable in forming.
In the step [r], 10 to 10,000 ppm of catalyst and polymerization inhibitor can be used as required with respect to the total charge. As these catalysts and polymerization inhibitors, those similar to those mentioned in the above step [p] can be used.

  The step of producing the (meth) acryloyl group-containing polyurethane (A) is preferably performed at a temperature of about 50 to 100 ° C. under a nitrogen atmosphere throughout. Any of the steps [p] to [r] can be performed in the absence of a solvent, but an organic solvent or a polymerizable unsaturated monomer (B) described later can also be used as a solvent if necessary. .

  Examples of the polycarbonate polyol (a1) that can be used for the production of the (meth) acryloyl group-containing polyurethane (A) include those obtained by reacting a carbonate with a polyol, and obtained by reacting phosgene and the like. Things can be used. The polycarbonate polyol (a1) can form L in the general formula (I).

As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.
Examples of the polyol capable of reacting with the carbonate ester include 1,2-ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, α, ω-diethylene glycol, α, ω-dipropylene glycol, neopentyl glycol. 1,3-butanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, cyclohexanedimethanol, 1,4 -Cyclohexanediol etc. can be used.

As the polycarbonate polyol (a1), it is preferable to use an aliphatic polycarbonate polyol or an aliphatic cyclic structure-containing polycarbonate polyol because the cured product has high mechanical strength.
As the polycarbonate polyol (a1), it is preferable to use a polycarbonate diol having one hydroxyl group at both ends of the molecule because a polyurethane (a1) having a controlled structure is obtained. Moreover, it is preferable that the hydroxyl value of the said polycarbonate polyol (a1) is the range of 40-130 KOHmg / g.
As said polycarbonate polyol (a1), when forming the polycarbonate structure of the number average molecular weight 900-2500 which is the structure L in general formula (I), the number average molecular weight calculated | required from the hydroxyl value is 930-2530. Preference is given to using polycarbonate polyols.

Examples of the polyisocyanate (a2) used in the step [p] include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Isomers, or a mixture of these and these isomers can be used, and these can be used alone or in combination of two or more.
Moreover, you may use together diisocyanate which has aromatic systems, such as 2, 4-tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, and naphthylene diisocyanate. As said polyisocyanate (a2), it is preferable to use an alicyclic or aliphatic polyisocyanate from the viewpoint of imparting the weather resistance and discoloration resistance of the resulting cured product, and isophorone diisodiisocyanate is preferably used. preferable.

Moreover, the said polyol (a4) used at process [q] is used when providing the structure M in the said general formula (I).
As said polyol (a4), what has 1 or more types chosen from the group which consists of a polycarbonate structure, a polyoxyalkylene group, and an alkylene group can be used.
Specifically, as the polyol (a4), polycarbonate polyol, polyether polyol, alkylene glycol, or the like can be used.

  As the polycarbonate polyol, the same ones as exemplified in the polycarbonate polyol (a1) can be used, and among them, a polycarbonate polyol having an aliphatic cyclic structure such as cyclohexane polycarbonate diol can be used. This is preferable because the tensile elongation can be further improved.

Examples of the polyoxyalkylene polyol (polyether polyol) that can be used for the polyol (a4) include polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A ethylene oxide, propylene oxide, butylene oxide (including tetrahydrofuran) adducts, and the like. Can be used.
Among these, it is preferable to use polyethylene glycol as the polyether polyol because the tensile elongation can be further improved.

Examples of the alkylene polyol (alkylene glycol) that can be used for the polyol (a4) include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1,4-butylene glycol, neopentyl glycol, 2-methyl 1,3-propylene glycol, 2,2′-diethyl 1,3-propylene glycol, 2-ethyl 2-butyl 1,3-propylene glycol, 1,5-pentanediol, 1,6-hexanediol, Cyclohexanedimethanol, hydrogenated bisphenol A, or the like can be used.
Among these, as the alkylene glycol, it is preferable to use a glycol having a linear alkylene group or an aliphatic cyclic structure-containing alkylene group, and using ethylene glycol, cyclohexanedimethanol, or hydrogenated bisphenol A, It is preferable for further improving the tensile strength of the obtained cured product.

  Examples of the hydroxyl group and (meth) acryloyl group-containing compound (a6) used in the step [r] include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxybutyl (meth). (Meth) acrylate having one hydroxyl group such as acrylate, mono (meth) acrylate of alcohol having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) ) Di (meth) acrylate of isocyanuric acid or trimethylolpropane, pentaerythritol tri (meth) acrylate, or the like can be used. Among them, it is preferable to use (meth) acrylate containing one hydroxyl group.

  The (meth) acryloyl group-containing polyurethane (A) of the present invention obtained by the above method can be used for various applications such as coating agents, adhesives and molding materials. Among these, the radical polymerizable resin composition containing the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B) is used exclusively for a cured product (molding material). Can do.

The radical polymerizable resin composition of the present invention includes the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B), and contains the (meth) acryloyl group. It is preferable that the polyurethane (A) is dissolved or dispersed in the radical polymerizable unsaturated monomer (B).
Examples of the radical polymerizable unsaturated monomer (B) include styrene, vinyl toluene, methyl styrene, paramethyl styrene, chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl, ketone methyl (meth) acrylate, and ethyl. (Meth) acrylate, methyl (meth) acrylate, acrylonitrile, (meth) acrylonitrile, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurphyryl (meth) acrylate, carbitol (meth) acrylate, phenoxy Chill (meth) acrylate, 1,3-butanedi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl Recall di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol di (meth) acrylate, methoxydiethylene glycol di (meth) acrylate, methoxytriethylene glycol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate may be used alone or in combination of two or more. it can. Of these, the use of styrene or methyl methacrylate is preferable for decreasing the resin solution viscosity, which is an important factor of moldability, and further increasing the tensile elongation.

  The radical polymerizable resin composition of the present invention is 30 to 70 parts by mass of the (meth) acryloyl group-containing polyurethane (A) with respect to 100 parts by mass of the radical polymerizable resin composition. It is preferable that the monomer (B) contains 70 to 30 parts by mass.

  In addition, a hydroxyl group-containing allyl ether compound can be used in combination as part of the component (a6) for the purpose of preventing curing inhibition by air when the radically polymerizable resin composition of the present invention is cured. Examples of the hydroxyl group-containing allyl ether compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene glycol. Monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, Multivalent such as glyceryl diallyl ether, pentaerythritol triallyl ether, etc. Alcohols such allyl ether compounds and the like, the allyl ether compound having one hydroxyl group are preferred.

The radical polymerizable resin composition of the present invention can be cured by any of the curing methods of curing with active energy rays, heat curing by using a peroxide, and room temperature curing by using a peroxide and a reducing agent. Can be obtained.
When heat-curing using a peroxide, for example, diacyl peroxide-based, peroxyester-based, hydroperoxide-based, dialkyl peroxide-based, ketone peroxide-based, peroxyketal-based, alkyl peroxide as a curing agent. Peroxides such as esters and percarbonates can be used.
The peroxide is preferably used in the range of 0.1 to 10 parts by mass, and in the range of 1 to 5 parts by mass, with respect to 100 parts by mass of the radical polymerizable composition of the present invention. More preferred.

Further, when the radical polymerizable composition of the present invention is cured at room temperature, the above-mentioned peroxide and a curing accelerator include organometallic salts such as cobalt naphthenate and cobalt octenoate, dimethylaniline, diethylaniline, and paratoluidine. Aromatic amine compounds such as can be used in combination.
It is preferable to use the said hardening accelerator in the range of 0.1-10 mass parts with respect to 100 mass parts of the radically polymerizable composition of this invention, and it is used in the range of 1-5 mass parts. More preferred.

When curing with active energy rays, it is preferable to use a photopolymerization initiator as a curing agent.
Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone. And thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- Hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butano Benzophen ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2, Acylphosphine oxides such as 4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenylacridine Etc. can be used.

When curing by active energy rays, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate together with the photopolymerization initiator as necessary. Well-known photosensitizers such as amyl 4-dimethylaminobenzoate and 4-dimethylaminoacetophenone may be used.
The photopolymerization initiator and the photosensitizer are each preferably used in an amount of 0.1 to 10 parts by weight, and 1 to 5 parts by weight, with respect to 100 parts by weight of the radical polymerizable composition of the present invention. It is more preferable to use within the range of parts.

  Moreover, you may use a polymerization inhibitor for the radically polymerizable resin composition of this invention as needed. Examples of the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol, and the like. . The amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the radical polymerizable composition. Examples include methylphenol. The amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the resin composition.

  The radically polymerizable resin composition of the present invention is cured by adding a commonly used known curing agent. For example, as a hardening | curing agent, the 1 or more types selected from the said peroxide are mentioned. 0.1-10 mass parts is preferable with respect to 100 mass parts of resin compositions, and, as for the usage-amount of a hardening | curing agent, 1-5 mass parts is more preferable.

  The radically polymerizable resin composition of the present invention includes generally known unsaturated polyester resins, vinyl ester resins, vinyl urethane resins, polyester (meth) acrylate resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins. , Urea resins, melanin resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers; cellulose derivatives such as nitrocellulose, cellulose acetate butyrate; linseed oil, tung oil Other conventional natural and synthetic polymer compounds such as oils and fats such as soybean oil, castor oil, epoxidized oil, and the like can be added.

Moreover, 5-70 mass% of glass fiber, carbon fiber, organic fiber, metal fiber, etc. can be added to the radically polymerizable resin composition of the present invention as a reinforcing material to form a molded product. These fiber reinforcing materials are preferably used in combination with organic fiber reinforcing materials from the viewpoint of the environment.
The radical polymerizable resin composition of the present invention contains a filler such as calcium carbonate, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand. It can be used as putty, sealing agent, adhesive and lining material. It is also effective as a material for impregnating and reinforcing cloth and kraft paper. Further, other additives such as zinc stearate, titanium white, zinc white, various pigment stabilizers, flame retardants, and the like can be added.

The method for obtaining a cured product (molded product) from the radical polymerizable resin composition of the present invention is not particularly limited, but specific examples include so-called hand lay-up, spray-up molding, and RTM (resin transfer molding) molding. And various molding methods such as cast molding, continuous molding, and pultrusion molding. In addition, it can be applied on various base films, and the various base films can be stacked on top of each other and cured by heat or light. In addition, putty and adhesive are molded by brush, iron, etc. The method of doing can also be mentioned.
In addition, the resin composition can be used as a so-called film coating material in which the resin composition is diluted with a solvent in some cases, coated with a film base material, and cured by ultraviolet rays or radiation.
The radically polymerizable resin composition of the present invention is not limited in use, and may be used for coating materials such as top coat, gel coat, putty, adhesive, lining material, coating agent, paint, etc. It is preferable to use the resin composition for molding applications because of the high toughness of the cured product. Examples of the molded product to be obtained include indoor molded products, electric and electronic parts, boat members, automobile members, motorcycle members, indoor members, bathtubs, waterproof pans, kitchen counters, wash counters, vanities, and various artificial marbles. Examples include molded products, separate plates, corrugated plates, flat plates, lining materials, civil engineering and building materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following, “parts” and “%” indicate “mass” standards.

(Synthesis Example 1) Preparation of polycarbonate skeleton-containing urethane resin (I) having a methacryloyl group A polycarbonate diol (Ube) was added to a 2-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Kosan UH-CARB100, hydroxyl value 112, number average molecular weight 1002 (converted from hydroxyl value) 401 parts are charged, isophorone diisocyanate 178 parts, tin catalyst 0.05 parts as a reaction promoting catalyst is added to suppress heat generation. The reaction was carried out at 80 ° C. for 2 hours. The NCO equivalent was 723 which was almost the same as the theoretical value and stabilized. Cooled to 70 ° C, added 21 parts neopentyl glycol, 0.05 parts hydroquinone and 652 parts styrene, added 0.1 part tin catalyst, The reaction was carried out at 80 ° C. for 5 hours. Since the NCO equivalent became 1550 and stabilized, it was cooled to 70 ° C., 52 parts of 2-hydroxyethyl methacrylate and 0.05 part of a tin-based catalyst were added, and reacted at 90 ° C. for 5 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which the polycarbonate skeleton-containing urethane resin (I) having a methacryloyl group was dissolved in styrene was obtained.

(Synthesis Example 2) Preparation of Polyurethane Skeleton-Containing Urethane Resin (II) Having Methacryloyl Group 401 parts of the polycarbonate diol used in Synthesis Example 1 were charged into the same reaction apparatus as in Synthesis Example 1, and 178 parts of isophorone diisocyanate were reacted. 0.05 parts of a tin-based catalyst was added as a promotion catalyst and reacted at 80 ° C. for 2 hours while suppressing heat generation. The NCO equivalent was 723, which was the same as the theoretical value, and was stable. Cooled to 70 ° C, 29 parts of cyclohexanedimethanol, 0.05 part of hydroquinone and 660 parts of styrene were added, 0.1 part of a tin-based catalyst was added, Reacted for hours. Since the NCO equivalent became 1590 and stabilized, it was cooled to 70 ° C., 52 parts of 2-hydroxyethyl methacrylate and 0.05 part of a tin-based catalyst were added, and reacted at 90 ° C. for 9 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (II) having a methacryloyl group was dissolved in styrene was obtained.

(Synthesis Example 3) Preparation of Polyurethane Skeleton-Containing Urethane Resin (III) Having Methacryloyl Group 401 parts of the polycarbonate diol used in Synthesis Example 1 were charged into the same reaction apparatus as in Synthesis Example 1, and 178 parts of isophorone diisocyanate were reacted. 0.05 parts of a tin-based catalyst was added as an accelerating catalyst and reacted at 80 ° C. for 3 hours while suppressing heat generation. Since the NCO equivalent was 723 which was almost the same as the theoretical value and was stabilized, it was cooled to 70 ° C., and 193 parts of cyclohexane polycarbonate diol (UC-CARB100, Ube Industries, Ltd., hydroxyl value 116, number average molecular weight 967 (converted from the hydroxyl value)) 05 parts and 824 parts of styrene were added, 0.1 part of a tin-based catalyst was added, and reacted at 80 ° C. for 3.5 hours. Since the NCO equivalent became 1930 and stabilized, the mixture was cooled to 70 ° C., 52 parts of 2-hydroxyethyl methacrylate and 0.05 part of a tin-based catalyst were added, and reacted at 90 ° C. for 6 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (III) having a methacryloyl group was dissolved in styrene was obtained.

(Synthesis Example 4) Preparation of a resin composition in which a polycarbonate skeleton-containing urethane resin (I) having a methacryloyl group was dissolved in methyl methacrylate In Synthesis Example 1, 652 parts of methyl methacrylate was added instead of styrene, and a polycarbonate having a methacryloyl group A resin composition in which the skeleton-containing urethane resin (I) was dissolved in methyl methacrylate was obtained.

(Synthesis Example 5) Preparation of Polycarbonate Skeleton-Containing Urethane Resin (IV) Having Methacryloyl Group 401 parts of polycarbonate diol used in Synthesis Example 1 were charged into the same reaction apparatus as in Synthesis Example 1, and 178 parts of isophorone diisocyanate were reacted. 0.05 parts of a tin-based catalyst was added as a promotion catalyst and reacted at 80 ° C. for 2 hours while suppressing heat generation. The NCO equivalent was 723, which was almost the same as the theoretical value, and stabilized. Cooled to 70 ° C, 12 parts of ethylene glycol, 0.05 part of hydroquinone and 643 parts of styrene were added, 0.1 part of tin-based catalyst was added, and Reacted for hours. Since the NCO equivalent became 1477 and stabilized, it was cooled to 70 ° C., 84 parts of 2-hydroxyethyl methacrylate was added, and the mixture was reacted at 90 ° C. for 3 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (IV) having a methacryloyl group was dissolved in styrene was obtained.

(Synthesis Example 6) Preparation of Polycarbonate Skeleton-Containing Urethane Resin (V) Having Methacryloyl Group 401 parts of the polycarbonate diol used in Synthesis Example 1 were charged into the same reaction apparatus as in Synthesis Example 1, and 178 parts of isophorone diisocyanate were reacted. 0.05 parts of a tin-based catalyst was added as a promotion catalyst and reacted at 80 ° C. for 2 hours while suppressing heat generation. Since the NCO equivalent was 723 which was almost the same as the theoretical value and was stabilized, it was cooled to 70 ° C., and 81 parts of polyethylene glycol (hydroxyl value 277, number average molecular weight 405 (converted from the hydroxyl value)) 81 parts hydroquinone 0.05 parts styrene Then, 0.1 part of a tin-based catalyst was added and reacted at 80 ° C. for 4 hours. Since the NCO equivalent became 1649 and stabilized, it was cooled to 70 ° C., 52 parts of 2-hydroxyethyl methacrylate was added, and the mixture was reacted at 90 ° C. for 7 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (V) having a methacryloyl group was dissolved in styrene was obtained.

(Comparative Synthesis Example 1) Preparation of Unsaturated Polyester Resin (VI) In the same reactor as in Synthesis Example 1, 263 parts of propylene glycol, 190 parts of ethylene glycol, 533 parts of phthalic anhydride, and 235 parts of maleic anhydride were charged. The reaction was performed while dehydrating condensed water for about 7 hours at 220 ° C. in a nitrogen atmosphere. When the acid value reached 20, the reaction was terminated, and after cooling to 170 ° C., 100 ppm of hydroquinone was added, Obtained. Further, the obtained unsaturated polyester resin was diluted with a styrene monomer so that the nonvolatile component was 65%, and a resin composition in which the unsaturated polyester resin (VI) was dissolved in styrene was obtained.

(Comparative Synthesis Example 2) Preparation of Epoxy Acrylate Resin (VII) In the same reactor as in Synthesis Example 1, 830 parts of bisphenol A epoxy resin (epoxy equivalent 390), 365 parts of methacrylic acid, 350 ppm of dibutylhydroxytoluene, 2- 1000 ppm of methylimidazole was added and reacted at 110 ° C. for about 5 hours. When the acid value reached 4, the reaction was terminated to obtain an epoxy methacrylate resin. The obtained epoxy methacrylate resin was diluted with a styrene monomer so that the non-volatile component would be 60% to obtain a resin composition in which the epoxy methacrylate resin (VII) was dissolved in styrene.

(Comparative Synthesis Example 3) Preparation of Polyether Skeleton-Containing Urethane Resin (VIII) In the same reactor as in Synthesis Example 1, 701 parts of polypropylene glycol (hydroxyl value 160, number average molecular weight 700 (converted from hydroxyl value)) 296 parts of tolylene diisocyanate and 67 parts of isophorone diisocyanate were charged, the reaction temperature was maintained at 80 ° C. in a nitrogen atmosphere, and a theoretical NCO equivalent of 532 was confirmed after 5 hours. The mixture was cooled to 30 ° C., charged with 273 parts of 2-hydroxyethyl methacrylate, 720 parts of styrene, 0.2 part of a tin-based catalyst and 0.05 part of hydroquinone, and reacted at 80 ° C. for 4 hours. When NCO% became 0.3% or less, the reaction was terminated to obtain a resin composition in which a polyether skeleton-containing urethane resin (VIII) was dissolved in styrene.

(Comparative Synthesis Example 4) Preparation of Polycarbonate Skeleton-Containing Urethane Resin (IX) Having Methacryloyl Group 401 parts of the polycarbonate diol used in Synthesis Example 1 was charged in the same reactor as in Synthesis Example 1, and 178 parts of isophorone diisocyanate was added. The reaction was carried out at 80 ° C. for 4 hours while suppressing the exotherm. The NCO equivalent was 732 which was almost the same as the theoretical value and stabilized. Cooled to 40 ° C, added 104 parts 2-hydroxyethyl methacrylate, 455 parts styrene, 0.2 parts tin catalyst, 0.05 parts hydroquinone. And reacted at 90 ° C. for 7 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (IX) having a methacryloyl group was dissolved in styrene was obtained. The resulting polycarbonate skeleton-containing urethane resin (IX) is formed by bonding isophorone diisocyanate to both ends of the polycarbonate diol and then bonding hydroxyethyl methacrylate, so there is no M structure in the general formula (I). The molecular weight was about half that of the polycarbonate skeleton-containing urethane resins of Synthesis Examples 1-6.

(Comparative Synthesis Example 5) Preparation of polycarbonate skeleton-containing urethane resin (X) having a methacryloyl group Polycarbonate diol (UH-CARB50, hydroxyl value 223, number average molecular weight 504 (manufactured by Ube Industries) was added to the same reactor as in Synthesis Example 1. 302 parts) was added, and 266 parts of isophorone diisocyanate was added and reacted at 80 ° C. for 4 hours while suppressing heat generation. Since the NCO equivalent was 450 which was almost the same as the theoretical value and stabilized, it was cooled to 40 ° C., 156 parts of 2-hydroxyethyl methacrylate, 0.05 part of hydroquinone, and 0.2 part of tin-based catalyst were added, and 90 ° C. for 5 hours. Reacted. The reaction was terminated when NCO% became 0.3% or less, and 483 parts of styrene was added to obtain a resin composition in which a polycarbonate skeleton-containing urethane resin (X) having a methacryloyl group was dissolved in styrene.

(Comparative Synthesis Example 6) Preparation of polycarbonate skeleton-containing urethane resin (XI) having a methacryloyl group 401 parts of polycarbonate diol used in Synthesis Example 1, 21 parts of neopentyl glycol, 2 in the same reaction apparatus as in Synthesis Example 1 -52 parts of hydroxyethyl methacrylate, 0.05 part of hydroquinone and 652 parts of styrene were charged together and heated to 70 ° C to dissolve neopentyl glycol in styrene.
After cooling to 40 ° C., 178 parts of isophorone diisocyanate and 0.1 part of a tin-based catalyst were added and reacted at 90 ° C. for 7 hours while suppressing heat generation. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (XI) having a methacryloyl group was dissolved in styrene was obtained. The obtained polycarbonate skeleton-containing urethane resin (XI) was formed by randomly combining polycarbonate diol, neopentyl glycol, and hydroxyethyl methacrylate with isophorone diisocyanate.

(Comparative Synthesis Example 7) Preparation of Polyurethane Skeleton-Containing Urethane Resin (XII) Having Methacryloyl Group 201 parts of polycarbonate diol (UH-CARB500, number average molecular weight 504, manufactured by Ube Industries) was charged in the same reaction apparatus as in Synthesis Example 1. 178 parts of isophorone diisocyanate was added and reacted at 80 ° C. for 4 hours while suppressing heat generation. The NCO equivalent was 472, which was almost the same as the theoretical value and stabilized. Cooled to 50 ° C., 21 parts of neopentyl glycol, 0.05 part of hydroquinone, 452 parts of styrene and 0.05 part of a tin-based catalyst were added. Reacted for hours. Since the NCO equivalent became 1038 and stabilized, the mixture was cooled to 50 ° C., 52 parts of 2-hydroxyethyl methacrylate and 0.05 part of a tin-based catalyst were added, and reacted at 90 ° C. for 5 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (XII) having a methacryloyl group was dissolved in styrene was obtained.

(Comparative Synthesis Example 8) Preparation of polycarbonate skeleton-containing urethane resin (XIII) having methacryloyl group Polycarbonate diol (UH-CARB300 manufactured by Ube Industries, hydroxyl value 38, number average molecular weight 2945 (same as Synthesis Example 1) 589 parts) (converted from the hydroxyl value)), 89 parts isophorone diisocyanate and 0.05 parts tin-based catalyst were added, and reacted at 80 ° C. for 4 hours while suppressing heat generation. The NCO equivalent was 1663 which was almost the same as the theoretical value and stabilized. Cooled to 50 ° C, added 11 parts of neopentyl glycol, 0.05 part of hydroquinone, 715 parts of styrene and 0.05 part of tin-based catalyst. Reacted. Since the NCO equivalent became 3346 and stabilized, the mixture was cooled to 50 ° C., and 26 parts of 2-hydroxyethyl methacrylate and 0.1 part of a tin-based catalyst were added and reacted at 90 ° C. for 7 hours. The reaction was terminated when NCO% became 0.3% or less, and a resin composition in which a polycarbonate skeleton-containing urethane resin (XIII) having a methacryloyl group was dissolved in styrene was obtained.

Example 1
To 100 parts of the resin composition obtained in Synthesis Example 1, 0.3 part of 6% cobalt naphthenate was added and mixed so as to be uniform, and radical curing agent 328E (trade name, organic peroxide curing agent, chemical 1 part of Yaku Akzo Co., Ltd.) was added and mixed, and the resin was poured in accordance with the following cast plate strength evaluation method to obtain a cured product, and physical properties of the cured resin product were evaluated.

(Examples 2 to 6)
Except having used the resin composition obtained by the synthesis examples 2-6, the cured | curing material was obtained like Example 1 and the physical property evaluation of each cured | curing material was performed.

(Comparative Examples 1-8)
A cured product was obtained in the same manner as in Example 1 except that the resin compositions obtained in Comparative Synthesis Examples 1 to 8 were used, and physical properties of each cured product were evaluated.

(Viscosity evaluation)
Using the resins before curing in Examples 1 to 6 and Comparative Examples 1 to 8, the viscosity was measured according to JIS-K-6901.

Moreover, the (meth) acryloyl group containing polyurethane obtained in Example 3 and 6 was identified by the measurement of IR spectrum on the following conditions. The IR spectrum of Example 3 is shown in FIG. 1, and the IR spectrum of Example 6 is shown in FIG. 1 and 2, the horizontal axis represents the wavelength (cm ⁻¹ ), and the peaks in the spectrum are as follows.
(IR spectrum measurement conditions)
Measuring instrument: Infrared spectrophotometer FT / IR-460 (manufactured by JASCO Corporation).
Measurement method: Transmission method using KBr plate.
Integration count: 16 times.
(Peak attribution)
[Peak derived from carbonate structure]
1745 cm ⁻¹ : C═O group of carbonyl group of carbonate [peak derived from cyclohexanedimethanol]
3030-3080 cm < ^-1 >: C-H vibration [peak of urethane bond formation confirmation]
1720cm ^-1: C = O group ^{1530cm -1: ~N (H) -C} = O~.
[Peak confirming disappearance of isocyanate group]
2260-2270 cm < ^-1 >: NCO group.

The toughness was evaluated by measuring the physical properties of the casting plate, which is the basis of various molded products.
(Strength property evaluation of cast plate)
The casting plate was prepared as follows. That is, a release agent was applied to two glass plates of 30 cm × 30 cm in size, a synthetic rubber tube was sandwiched between the glass plates, and a gap was adjusted to 3 mm using a spacer, as shown in Examples and Comparative Examples. Each resin composition was poured and cured at room temperature for 1 day. Post-curing was performed at 120 ° C. for 2 hours in a dryer, and after cooling, the glass plate was removed to obtain a smooth molded product having a thickness of 3 mm.
A test piece was cut from the obtained molded product, and a tensile test was sequentially performed by the test method of JIS-K-7113 using the test piece to measure physical properties.
Specifically, using the test piece, the tensile strength, the tensile modulus, the tensile elongation (material) according to the tensile test method of JIS-7113 using test equipment: Autograph AG-I (manufactured by Shimadzu Corporation) (Elongation rate until breakage).
(Production method)
The sequential reaction described in the table refers to a method in which the raw materials described in the table are sequentially mixed and reacted under predetermined conditions for the purpose of controlling the structure of the resulting compound.

  As can be seen from the above table, it was confirmed that the cast plate obtained from the resin composition of the present invention was excellent in the balance between the tensile elongation and the mechanical strength such as the tensile elastic modulus and tensile strength.

  INDUSTRIAL APPLICABILITY The present invention can be used in a wide range of fields such as a mechanical field, a medical field, an electric / electronic field, and a civil engineering structure that require a tensile elongation rate and mechanical strength such as a tensile elastic modulus and tensile strength.

Claims (11)

A (meth) acryloyl group-containing polyurethane represented by the following general formula (I) (A).

(L in the general formula (I) represents a polycarbonate structure having a number average molecular weight of 900 to 2500, and M consists of a polycarbonate structure, a polyoxyalkylene group and an alkylene group (including those having an aliphatic cyclic structure). And T is a linear or branched alkylene group, an alkylene group having an aliphatic cyclic structure, or an alkylene group having an aromatic structure, and X is (meth). (Represents an atomic group containing an acryloyl group.)   M in the general formula (I) is a structure having an aliphatic cyclic structure and a polycarbonate structure having a number average molecular weight of 470 to 970, a polyoxyalkylene group having a number average molecular weight of 70 to 520, or a number average molecular weight of 30 to 520. The (meth) acryloyl group-containing polyurethane (A) according to claim 1, which is an alkylene group.   (Meth) according to claim 2, wherein M in the general formula (I) is a linear alkylene group having a number average molecular weight of 30 to 520 or an aliphatic cyclic structure-containing alkylene group having a number average molecular weight of 30 to 520. Acryloyl group-containing polyurethane (A). The polycarbonate polyol (a1) and the polyisocyanate (a2) have a molar ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polycarbonate polyol (a1) and the isocyanate group of the polyisocyanate (a2) of 1.8-2. To obtain a polyurethane (a3) having an isocyanate group at the molecular end by reacting in the range of 3.
Subsequently, the polyurethane (a3), a polycarbonate polyol having an aliphatic cyclic structure and a polycarbonate structure having a number average molecular weight of 500 to 1,000, a polyoxyalkylene polyol having a number average molecular weight of 100 to 550, and a number average molecular weight of 60 to 550 The molar ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyurethane (a3) and the hydroxyl group of the polyol (a4) of one or more polyols (a4) selected from the group consisting of alkylene polyols is 1. A polyurethane (a5) is obtained by reacting in the range of 8 to 2.3,
The polyurethane (a5) is then reacted with a hydroxyl group and (meth) acryloyl group-containing compound (a6) to produce the (meth) acryloyl group-containing polyurethane (A) according to claim 1. Method.   The production according to claim 4, wherein the polycarbonate polyol having a number average molecular weight of 500 to 1000 having an aliphatic cyclic structure and a polycarbonate structure is obtained by reacting 1,4-cyclohexanedimethanol and a carbonate ester. Method.   The production method according to claim 4, wherein the polyoxyalkylene polyol having a number average molecular weight of 100 to 550 is polyoxyethylene glycol.   The production method according to claim 4, wherein the alkylene polyol having a number average molecular weight of 60 to 550 is ethylene glycol, cyclohexanedimethanol or hydrogenated bisphenol A.   The radically polymerizable resin composition containing the (meth) acryloyl group containing polyurethane (A) of any one of Claims 1-3, and a radically polymerizable unsaturated monomer (B).   The radical according to claim 8, wherein 30 to 70 parts by mass of the (meth) acryloyl group-containing polyurethane (A) is contained and 70 to 30 parts by mass of the radical polymerizable unsaturated monomer (B) is contained. Polymerizable resin composition.   The radically polymerizable resin composition according to claim 8, wherein the radically polymerizable unsaturated monomer (B) is styrene or methyl methacrylate.   Hardened | cured material obtained by hardening | curing the radically polymerizable resin composition as described in any one of Claims 8-10.

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