JP6458339B2 - Curable resin composition, cured product and laminate - Google Patents

Description

  The present invention provides a cured product having stretchability capable of following deformation during three-dimensional processing and excellent in scratch resistance, surface hardness, appearance, mechanical properties (elastic modulus, elongation at break, etc.), etc. The present invention relates to a curable resin composition that can be used. Moreover, this invention relates to the hardened | cured material and laminated body obtained using this curable resin composition.

  The radical polymerization type curable resin composition can be cured in a short time by irradiation with active energy rays, and can provide a film or a molded article excellent in chemical resistance, stain resistance, weather resistance, heat resistance, etc. Therefore, it is widely used in various surface processing fields and cast molding applications. Among these curable resin compositions, among them, since the curability and work efficiency are good, a cured film obtained by precuring a resin composition containing polyurethane acrylate with an active energy ray is manufactured, surface treatment treatment, etc. A method of performing three-dimensional processing at room temperature or under heating conditions is used after applying the above. When such a method is used, the resulting cured film needs to have stretchability to follow deformation during three-dimensional processing.

  Patent Document 1 describes such a bifunctional urethane (meth) acrylate oligomer, monofunctional (meth) acrylate monomer, polyfunctional (meth) acrylate as having such stretchability and excellent scratch resistance and abrasion resistance. An active energy ray-curable hard coat resin composition containing a monomer and colloidal silica whose surface is modified with a photopolymerizable functional group is disclosed. Patent Document 2 discloses a photo-curing type having a stretchability, a bifunctional ethylenically unsaturated group-containing isocyanurate, and a (meth) acryloyl group in the side chain as having excellent scratch resistance and abrasion resistance. A composition for a decorative laminated film is disclosed.

JP 2013-82833 A JP 2011-225679 A

  According to detailed studies by the present inventors, the cured product obtained by curing the curable resin composition described in Patent Documents 1 and 2 can follow the deformation of three-dimensional processing. It has been found that there is a problem that the stretchability is insufficient and a curable resin composition that is excellent in both scratch resistance and surface hardness is not obtained. That is, the problem of the present invention is that it has stretchability that can follow the deformation of three-dimensional processing, and can provide a cured product that is excellent in scratch resistance, surface hardness, appearance, mechanical properties, and the like. It is providing the resin composition, hardened | cured material, and a laminated body.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have obtained a urethane (meth) acrylate oligomer obtained using a specific raw material and silica particles whose surface is modified with a (meth) acrylic compound. The present inventors have found that a curable resin composition containing a specific amount of can solve the above-mentioned problems, and have reached the present invention. That is, the gist of the present invention resides in the following [1] to [8].

[1] A curable resin composition comprising the following component (A) and component (B), and comprising 18.5 to 45% by weight of component (B) with respect to the total amount of component (A) and component (B). object.
Component (A): Reaction of at least (a-1) polyisocyanate, (a-2) a diol having 2 to 14 carbon atoms and a chain structure, and (a-3) hydroxyalkyl (meth) acrylate Urethane (meth) acrylate oligomer component (B) having a urethane bond amount of 24% by weight or more obtained in this manner: silica particles whose surface is modified with a compound having a (meth) acryloyl group

[2] The curable resin composition according to claim 1, wherein the urethane (meth) acrylate oligomer of component (A) has a number average molecular weight (Mn) of 500 to 15,000.

[3] The urethane (meth) acrylate oligomer of component (A) is (a-1) a polyisocyanate and (a-2) an aliphatic having 2 to 14 carbon atoms and reacting with a diol having a chain structure. The curable resin composition according to [1] or [2], which is obtained by reacting (a-3) hydroxy (meth) acrylate with a prepolymer.

[4] The curable resin composition according to any one of [1] to [3], wherein the (a-1) polyisocyanate is a polyisocyanate having an alicyclic structure.

[5] A cured product obtained by irradiating the curable resin composition according to any one of [1] to [4] with active energy rays.

[6] A laminate obtained by forming a layer made of the cured product according to [5] on a substrate.

[7] The laminate according to [6], wherein the base material is at least one selected from polyethylene terephthalate resin, acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin.

  According to the present invention, a cured product having stretchability capable of following the deformation of three-dimensional processing and excellent in scratch resistance, surface hardness, appearance, mechanical properties (elastic modulus, elongation at break, etc.), etc. Is provided. Moreover, according to this invention, the hardened | cured material and laminated body obtained using this curable resin composition are provided.

  The present invention will be described in detail below, but the following description is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. About “(meth) acryloyl” and “(meth) acryl” Is the same. Further, in the present invention, “to” is used in the sense of including numerical values described before and after it as a lower limit value and an upper limit value.

[Curable resin composition]
The curable resin composition of the present invention includes the following component (A) and component (B), and 18.5 to 45 of component (B) with respect to the total amount of component (A) and component (B). Including weight percent.
Component (A): urethane (meth) obtained by reacting at least (a-1) polyisocyanate, (a-2) an aliphatic diol having 2 to 14 carbon atoms and (a-3) hydroxyalkyl (meth) acrylate Acrylate oligomer Component (B): Silica particles whose surface is modified with a compound having a (meth) acryloyl group

  The curable resin composition of the present invention has stretchability that can follow deformation during three-dimensional processing, and is excellent in scratch resistance, surface hardness, appearance, mechanical properties (high elastic modulus), and the like. In particular, the stretchability that can follow deformation during three-dimensional processing is significantly superior to the curable resin compositions described in Patent Documents 1 and 2. The reason why the curable resin composition of the present invention exhibits the excellent effects as described above is not clear, but particularly stretchability capable of following deformation during three-dimensional processing, scratch resistance, surface hardness, and mechanical properties. The balance with (high elastic modulus) is considered to be due to the following reason. That is, the urethane (meth) acrylate oligomer of component (A) has excellent stretchability and scratch resistance that can follow deformation during three-dimensional processing by desorbing hydrogen bonds derived from urethane bonds formed between molecules. Although it has a balance with surface hardness and mechanical properties (high elastic modulus), it alone is not sufficient in scratch resistance, surface hardness, mechanical properties (high elastic modulus) and the like. In the present invention, a large amount of silica particles whose surface is modified with a compound having a (meth) acryloyl group as component (B) is added to component (A) as long as the stretchability and appearance based on component (A) are not impaired. Thus, when the curable resin composition is cured, the organic component of the urethane (meth) acrylate oligomer is hardened by a covalent bond with the (meth) acryloyl group that modifies the silica particles that are the hard inorganic particles. It is considered that a cured product having a balance between stretchability that can form a network and can follow deformation during three-dimensional processing, and scratch resistance, surface hardness, and mechanical properties (high elastic modulus) can be obtained. It is done.

<Component (A): Urethane (meth) acrylate oligomer>
The urethane (meth) acrylate oligomer used in the curable resin composition of the present invention includes at least (a-1) polyisocyanate, (a-2) aliphatic diol having 2 to 14 carbon atoms, and (a-3) hydroxyalkyl. It is obtained using (meth) acrylate.

[(A-1) Polyisocyanate]
The (a-1) polyisocyanate used as a raw material for the component (A) is a compound having a substituent containing two or more isocyanate groups and / or isocyanate groups in one molecule. In the present invention, the isocyanate group and the substituent containing the isocyanate group may be collectively referred to as “isocyanate groups”. (A-1) In one molecule of polyisocyanate, the isocyanate groups may be the same or different. (A-1) One type of polyisocyanate may be used, or two or more types may be used.

  As a substituent containing an isocyanate group, a C1-C5 alkyl group, a C1-C5 alkenyl group, or a C1-C5 alkoxyl group containing 1 or more isocyanate groups is mentioned, for example. Among these, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.

  Examples of (a-1) polyisocyanates include chain aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.

  A chain aliphatic polyisocyanate is a compound having a chain aliphatic structure and two or more isocyanate groups bonded thereto. A chain aliphatic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance of a cured product obtained by curing the curable resin composition and imparting flexibility. The chain aliphatic structure in the chain aliphatic polyisocyanate is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of such chain aliphatic polyisocyanates include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; chain fatty acids such as tris (isocyanatohexyl) isocyanurate Group triisocyanate and the like.

An alicyclic polyisocyanate is a compound having an alicyclic structure and two or more isocyanate groups bonded thereto. The alicyclic structure in the alicyclic polyisocyanate is not particularly limited, but preferably has 5 to 15 carbon atoms, more preferably 6 or more carbon atoms, and particularly preferably 7 or more carbon atoms. Moreover, it is more preferable that it is C14 or less, and it is especially preferable that it is C13 or less. Furthermore, the alicyclic structure is preferably a cycloalkylene group. Examples of the polyisocyanate having an alicyclic structure include alicyclic diisocyanates such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate; and alicyclic rings such as tris (isocyanate isophorone) isocyanurate. Group triisocyanate and the like. The alicyclic polyisocyanate is also preferable from the viewpoint of enhancing the weather resistance of a cured product obtained by curing the curable resin composition.

  An aromatic polyisocyanate is a compound having an aromatic structure and two or more isocyanate groups bonded thereto. Although the aromatic structure in aromatic polyisocyanate is not specifically limited, It is preferable that it is a C6-C13 bivalent aromatic group. Examples of such aromatic polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate.

  The aromatic polyisocyanate is preferable from the viewpoint of increasing the mechanical strength of a cured product obtained by curing the active energy ray-curable resin composition. Examples of such aromatic polyisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate. Can be mentioned. (A-1) The polyisocyanate preferably contains an alicyclic polyisocyanate from the viewpoint of the mechanical strength of the resulting cured product among the above-mentioned ones.

  (A-1) The molecular weight per isocyanate group of the polyisocyanate is preferably 50 or more, more preferably 75 or more, from the viewpoint of the balance between the strength and the elastic modulus of the obtained cured product. It is preferably 500 or less, and more preferably 250 or less.

  (A-1) The molecular weight per isocyanate group of the polyisocyanate is calculated from the chemical formula in the case of a polyisocyanate composed of a single monomer, and in the case of a polyisocyanate composed of two or more monomers. Can be obtained from the calculated value from NCO%. NCO% can be measured by the following method.

A measurement sample of 1.0 to 1.5 g is precisely weighed in a 200 mL stoppered flask and 0.1 mol / L.
After adding 20 mL of di-N-butylamine (toluene solution), the mixture is stirred for 15 minutes. To this, 100 mL of acetone is added, and titrated with 0.1 mol / L hydrochloric acid using a potentiometric titrator. Separately, titrate a blank. NCO% is calculated using the following equation.
NCO% (weight%) = (Vb−Vs) × f × N × 4.2 / W
Vb: Titration volume of hydrochloric acid required for blank test (mL)
Vs: Titration volume of hydrochloric acid required for this test (mL)
f: Factor of hydrochloric acid used for titration (−)
N: HCl concentration used for titration (mol / L)
W: Weight of measurement sample (g)

[(A-2) C2-C14 aliphatic diol]
The (a-2) aliphatic diol having 2 to 14 carbon atoms used as a raw material for the component (A) is not particularly limited as long as it is a compound having 2 to 14 carbon atoms in one molecule and having two hydroxyl groups. (A-2) Examples of the aliphatic diol having 2 to 14 carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2 -Methyl-1,3-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5- Pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanedio 3,3-dimethylol heptane, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1-10 decanediol, 1,11-undecanediol, 1, Aliphatic diols such as 12-dodecanediol and 1,14-tetracandiol; cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedipropanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, Cyclopentanediethanol, cyclopentanedipropanol, cyclopentanedibutanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol Cyclohexenediol, cyclohexenedimethanol, cyclohexenediethanol, cyclohexenedipropanol, cyclohexenedibutanol, cyclohexadienediol, cyclohexadienedimethanol, cyclohexadienediethanol, cyclohexadienedipropanol, cyclohexadienedibutanol, hydrogenated bisphenol A, tricyclodecanediol And alicyclic diols such as adamantyldiol.

  Among the above, in applications where scratch resistance of the cured product is required, from the viewpoint of imparting toughness to the cured product, (a-2) the carbon number of the aliphatic diol having 2 to 14 carbon atoms is preferably 2 to 12, 6-12 are more preferable, 8-12 are especially preferable, and 10-12 are the most preferable. In addition, as exemplified above, the (a-2) aliphatic diol is a diol having a chain structure and a cyclic structure, whether it is a diol having a chain structure or a diol having a cyclic structure. However, a diol having a chain structure is preferable.

  Among the above (a-2) aliphatic diols having 2 to 14 carbon atoms, ethylene glycol, 1,12-dodecanediol, and 1,4-cyclohexanedimethanol are preferable. Further, ethylene glycol is particularly preferable from the viewpoint of improving the surface hardness, and 1,12-dodecanediol is particularly preferable from the viewpoint of imparting toughness and improving scratch resistance.

[(A-3) Hydroxyalkyl (meth) acrylate]
The (a-3) hydroxyalkyl (meth) acrylate used as a raw material for the component (A) is a compound having one or more hydroxyl groups, one or more (meth) acryloyl groups and an alkyl group. Here, the alkyl group of the hydroxyalkyl (meth) acrylate is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. It is more preferably a group, and particularly preferably an alkyl group having 2 to 8 carbon atoms.

(A-3) As hydroxyalkyl (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) Acrylate, cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, glycidyl ether and (meth) acrylic Addition reaction product with acid, mono (meth) acrylate of glycol, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate And the like.

  Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol A hydroxyalkyl (meth) acrylate having a C2-C4 alkylene group between a hydroxyl group and a (meth) acryloyl group such as penta (meth) acrylate is particularly preferred from the viewpoint of the mechanical strength of the resulting cured product. In particular, hydroxyalkyl poly (meth) having two or more (meth) acryloyl groups such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Acrylate is particularly preferred. Hydroxyalkyl poly (meth) acrylate has a good cross-linked structure due to the involvement of multiple (meth) acryloyl groups in the effective reaction when obtaining a cured product, and physical properties such as appearance, scratch resistance, and abrasion resistance Can be made good.

  (A-3) The molecular weight of hydroxyalkyl (meth) acrylate is preferably 100 or more, and more preferably 110 or more. On the other hand, the molecular weight of (a-3) hydroxyalkyl (meth) acrylate is preferably 800 or less, and more preferably 400 or less, from the viewpoint of mechanical strength of the resulting cured product. In the case where (a-3) hydroxyalkyl (meth) acrylate is the above addition reactant or polymer, the molecular weight means a number average molecular weight by gel permeation chromatography measurement (GPC measurement). .

[Other raw material compounds]
In the raw material compound of the urethane (meth) acrylate oligomer used in the present invention, the (a-1) polyisocyanate and (a-2) aliphatic diol having 2 to 14 carbon atoms as long as the effects of the present invention are not significantly impaired. And (a-3) You may use other raw material compounds other than a hydroxyalkyl (meth) acrylate. Examples of such other raw material compounds include polyalkylene glycol, other high molecular weight polyols (hereinafter referred to as “other high molecular weight polyols”), chain extenders, and the like.

  Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. These may be used alone or in combination of two or more.

  Examples of other high molecular weight polyols include polyether diol, polyester diol, polyether ester diol, polyolefin polyol, and silicon polyol. These may be used alone or in combination of two or more.

A chain extender is a compound having two or more active hydrogens that react with isocyanate groups. Examples of the chain extender include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples include aromatics such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 4,4′-diphenylmethanediamine. Group diamine; ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; And 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-dicyclohexylmethane Min, isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bis-aminomethyl cyclohexane, alicyclic diamines such as tricyclodecane diamine. These may be used alone or in combination of two or more.

[Physical properties of urethane (meth) acrylate oligomer]
The number average molecular weight (Mn) of the urethane (meth) acrylate oligomer of component (A) is preferably 500 or more, more preferably 1,000 or more, still more preferably 2,000 or more, On the other hand, it is preferably 15,000 or less, more preferably 10,000 or less, and still more preferably 8,000 or less. When the number average molecular weight of the urethane (meth) acrylate oligomer is not less than the above lower limit value, the stretchability of the resulting cured product tends to be good. When the number average molecular weight of the urethane (meth) acrylate oligomer is not more than the above upper limit, the scratch resistance and surface hardness of the cured product obtained from the curable resin composition tend to be good. The number average molecular weight of the urethane (meth) acrylate oligomer is the distance between crosslink points of the network structure that affects the stretchability, scratch resistance, surface hardness and mechanical properties (high elastic modulus) of the cured product obtained by using the urethane (meth) acrylate oligomer. The lower the number average molecular weight, the shorter the distance between the crosslinking points, and the higher the number average molecular weight, the longer the distance between the crosslinking points. The reason why the number average molecular weight affects stretchability, scratch resistance, surface hardness and mechanical properties (high elastic modulus) is because the structure between the cross-linking points is long and the structure is flexible and easily stretched. If this distance is shortened, the network structure becomes a strong structure, and therefore it is presumed that the scratch resistance, surface hardness and mechanical properties (high elastic modulus) are excellent. In addition, a urethane (meth) acrylate oligomer number average molecular weight can be calculated | required by gel permeation chromatography measurement (GPC measurement), and a more detailed measuring method is shown in the below-mentioned Example.

  The urethane bond amount of the urethane (meth) acrylate oligomer is preferably 10 to 30% by weight, more preferably 15 to 25% by weight. When the amount of urethane bonds is not less than the above lower limit value, mechanical properties (high elastic modulus) and contamination resistance tend to be improved, and when it is not more than the above upper limit value, elongation tends to be improved. In addition, said urethane bond amount is controllable by adjusting the raw material mixing | blending of a urethane (meth) acrylate oligomer.

In the present invention, the urethane bond amount is calculated as follows. The urethane (meth) acrylate oligomer used in the present invention uses (a-1) polyisocyanate, (a-2) aliphatic diol having 2 to 14 carbon atoms, and (a-3) hydroxyalkyl (meth) acrylate as raw materials. The constituent unit in the urethane (meth) acrylate oligomer obtained can be regarded as the raw material composition used is kept as it is. From this, the total amount of urethane bonds (total number of moles of polyisocyanate and isocyanate of polyisocyanate ) in the total amount of components of urethane (meth) acrylate oligomer (sum of the product of the number of moles of each raw material component and the molecular weight of each component) Calculated by the ratio of the number of radicals and the molecular weight of the urethane bond (59)).

[Method for producing urethane (meth) acrylate oligomer]
The urethane (meth) acrylate oligomer used in the present invention includes the (a-1) polyisocyanate, the (a-2) aliphatic diol having 2 to 14 carbon atoms and the (a-3) hydroxyalkyl (meth) acrylate. Can be produced by addition reaction. In addition, the charging ratio of each raw material compound at that time is usually substantially the same or the same as the composition of the target urethane (meth) acrylate oligomer.

These addition reactions can be carried out using any of the known methods for producing urethane (meth) acrylate oligomers. Examples of such a method include the following methods (1) to (3).
(1) Urethane prepolymer having an isocyanate terminal by reacting the (a-1) polyisocyanate with (a-2) an aliphatic diol having 2 to 14 carbon atoms under conditions such that the isocyanate group becomes excessive. The urethane prepolymer having an isocyanate terminal is then reacted with the (a-3) hydroxyalkyl (meth) acrylate. (2) A method in which all raw material compounds are added simultaneously and reacted.
(3) Urethane (meth) in which the (a-1) polyisocyanate and the (a-3) hydroxyalkyl (meth) acrylate are reacted first to have a (meth) acryloyl group and an isocyanate group in the molecule at the same time. After synthesizing the acrylate prepolymer, (a-2) a method of reacting an aliphatic diol having 2 to 14 carbon atoms with the obtained prepolymer.

  Among these, according to the method (1), the urethane prepolymer is obtained by urethanizing (a-1) polyisocyanate and (a-2) an aliphatic diol having 2 to 14 carbon atoms. . The target urethane (meth) acrylate oligomer has a structure obtained by urethanation reaction with a urethane prepolymer having an isocyanate group at the terminal and (a-3) hydroxyalkyl (meth) acrylate. The method (1) is preferable because the molecular weight can be easily controlled and a cured product can be easily obtained because (meth) acryloyl groups can be introduced at both ends.

  When (a-1) polyisocyanate and (a-2) an aliphatic diol having 2 to 14 carbon atoms are urethanized, (a-1) polyisocyanate and (a-2) 2 to 14 carbon atoms are used. The molar ratio ([(a-1) moles of polyisocyanate]: [(a-2) moles of aliphatic diol having 2 to 14 carbon atoms]) of 3 to 50 is usually 3 to 50. : 49, preferably 2: 1 to 30:29, more preferably 3: 2 to 25:24. When the molar ratio of (a-1) polyisocyanate to (a-2) aliphatic diol having 2 to 14 carbon atoms is within the above range, the terminal group and the molecular weight can be controlled.

  Further, when the obtained urethane prepolymer and (a-3) hydroxyalkyl (meth) acrylate are reacted, (a-1) polyisocyanate and (a-3) hydroxyalkyl ( The molar ratio with [meth) acrylate ([(a-1) moles of polyisocyanate]: [(a-3) moles of hydroxyalkyl (meth) acrylate]) is usually from 3: 4 to 25: 1. , Preferably 1: 1 to 15: 1, more preferably 3: 2 to 25: 2. When the molar ratio of (a-1) polyisocyanate to (a-3) hydroxyalkyl (meth) acrylate is within the above range, (meth) acryloyl derived from (a-3) hydroxyalkyl (meth) acrylate at the terminal The group can be efficiently introduced, and as a result, the curability of the urethane (meth) acrylate tends to be good.

  The amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually theoretically equimolar. For this reason, the amount of (a-1) polyisocyanate, (a-2) aliphatic diol having 2 to 14 carbon atoms and (a-3) hydroxyalkyl (meth) acrylate and other raw material compounds used as raw materials is The amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the amount of all functional groups reacting therewith is an amount that is 50 to 200 mol% in terms of equimolar or mol% of the all functional groups relative to the isocyanate group.

  Further, when a chain extender is used, (a-2) an aliphatic diol having 2 to 14 carbon atoms, (a-2) a diol component other than an aliphatic diol having 2 to 14 carbon atoms, and other polyol components It is preferable that the amount of all polyols used is 70 mol% or more based on the total amount of the compounds in which all the polyols (compounds having two or more alcoholic hydroxyl groups) and the chain extender are combined. % Or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. When the total polyol amount is not less than the lower limit, the liquid stability of the curable resin composition tends to be improved.

  In addition, said raw material ratio becomes a standard at the time of manufacturing a urethane (meth) acrylate oligomer. Actually, it is preferable to finely adjust the raw material blending ratio in the above range depending on the desired physical properties.

  In the production of the urethane (meth) acrylate oligomer, an organic solvent can be used for the purpose of adjusting the viscosity. An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. As the organic solvent, any known organic solvent can be used as long as the effects of the present invention are obtained. Preferred organic solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and N-methylpyrrolidone. The organic solvent can be used usually at 300 parts by weight or less with respect to 100 parts by weight of the solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer, the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compound is preferably 20% by weight or more, more preferably 40% by weight or more based on the total amount of the reaction system. More preferably. The upper limit of the total content is usually 100% by weight. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compounds to be at least the above lower limit value because the reaction rate tends to increase and the production efficiency tends to improve.

  A catalyst can be used in the production of the urethane (meth) acrylate oligomer. The catalyst can be selected from the range in which the effects of the present invention can be obtained. For example, tin-based catalysts such as dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate; bismuth tris (2- And bismuth-based catalysts such as ethylhexanoate). A catalyst may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, dioctyltin dilaurate and bismuth tris (2-ethylhexanoate) are preferable from the viewpoints of environmental adaptability, catalytic activity, storage stability, and the like. The upper limit of the amount of the catalyst used is usually 2,000 ppm or less, preferably 1,000 ppm or less, and the lower limit is usually 10 ppm or more, preferably 30 ppm or more with respect to the total content of the raw material compounds (both are weight). ppm). In addition, when manufacturing by the method of said (1), especially reaction which makes the said (a-1) polyisocyanate and (a-2) C2-C14 aliphatic diol react, and obtains a urethane prepolymer, It is preferable to use the catalyst in both reactions when the (a-3) hydroxyalkyl (meth) acrylate is added to the urethane prepolymer.

  In addition, when a compound containing a (meth) acryloyl group such as (a-3) hydroxyalkyl (meth) acrylate is used in the reaction system during the production of the urethane (meth) acrylate oligomer, a polymerization inhibitor should be used in combination. Is preferred. Examples of such a polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese acetate. Manganese salts, nitro compounds, nitroso compounds and the like can be mentioned. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor. The amount of the polymerization inhibitor used is usually 3,000 ppm or less, preferably 1,000 ppm or less, particularly preferably 500 ppm or less, while the lower limit is usually 50 ppm, based on the total content of the raw material compounds. As mentioned above, Preferably it is 100 ppm or more (all are weight ppm).

In the production of the urethane (meth) acrylate oligomer, the reaction temperature is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and still more preferably 60 ° C. or higher. It is preferable for the reaction temperature to be at least the above lower limit value because the reaction rate increases and the production efficiency tends to improve. The reaction temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. It is preferable for the reaction temperature to be equal to or lower than the above upper limit value because side reactions such as an allohanato reaction hardly occur. When the reaction system contains an organic solvent, the reaction temperature is preferably not higher than the boiling point of the organic solvent, and (a-3) a compound having a (meth) acryloyl group such as hydroxyalkyl (meth) acrylate. When included, it is preferably 70 ° C. or lower from the viewpoint of preventing the (meth) acryloyl group from reacting excessively. The reaction time is usually 5 to 20 hours.

<Component (B): Silica particles whose surface is modified with a compound having a (meth) acryloyl group>
The curable resin composition of this invention contains the silica particle by which the surface is modified with the compound which has a (meth) acryloyl group as a component (B).

  Although the manufacturing method in particular of a component (B) is not restrict | limited, For example, it can manufacture by carrying out a hydrolytic condensation reaction of the silica particle disperse | distributed to the solvent and the silane compound which has a (meth) acryloyl group. The manufacturing method of a component (B) is well-known, For example, it describes in Unexamined-Japanese-Patent No. 2006-249322. More specifically, the silica particles obtained by modifying the surface of the component (B) with a compound having a (meth) acryloyl group first have a (meth) acryloyl group in the silica particles using an organic solvent as a dispersion medium. It can be obtained by adding a silane compound, further adding water and acetylacetone aluminum as a hydrolysis catalyst, and allowing the hydrolysis reaction to proceed while stirring under heating.

  Examples of silica particles dispersed in a solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, ethylene glycol, xylene dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, ethylene glycol mono n-propyl ether silica sol, propylene Examples thereof include silica particles dispersed in a solvent such as glycol monomethyl ether, ethyl acetate, propylene glycol monomethyl ether acetate, toluene, and cyclohexanone. These can be obtained as commercial products. Examples thereof include methanol silica sol MA-ST-M, isopropyl alcohol silica sol IPA-ST, ethylene glycol silica sol EG-ST, xylene / manufactured by Nissan Chemical Industries, Ltd. Butanol silica sol XBA-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST, ethylene glycol mono n-propyl ether silica sol NPC-ST-30, propylene glycol monomethyl ether silica sol PGM-ST, Ethyl acetate silica sol EAC-ST, propylene glycol monomethyl ether acetate PMA-ST, toluene silica sol TOL-ST, cyclohexano It can be used silica sol CHO-ST-M, or the like. These may be used alone or in combination of two or more.

Further, the silica particles dispersed in the solvent preferably have an average primary particle diameter of 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, and 200 nm or less. It is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. When the average primary particle diameter of the silica particles is not less than the above lower limit value, the scratch resistance and surface hardness tend to be improved, and when it is not more than the above upper limit value, the transparency of the cured product tends to be good. . In addition, the average primary particle diameter of the silica particles dispersed in the solvent in the present invention is a value obtained as a converted value from the following formula by obtaining a specific surface area measurement value (based on JIS Z8830) by a BET adsorption method.
[Average primary particle diameter (nm)] = 6,000 / [[specific surface area (m ² / g)] × [density (g /
cm ³ )]]

  Examples of the silane compound having a (meth) acryloyl group include β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, and β- (meth) acryloyloxyethyldimethyl. Methoxysilane, β- (meth) acryloyloxyethyldimethylethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxysilane , Γ- (meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (me T) Acrylyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and the like can be used. These may be used alone or in combination of two or more.

  In the production of component (B), the hydrolysis reaction temperature is preferably 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. It is preferable for the hydrolysis reaction temperature to be at least the above lower limit value because the reaction rate increases and the production efficiency tends to improve. The hydrolysis reaction temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 70 ° C. or lower. It is preferable for the hydrolysis reaction temperature to be not more than the above upper limit value because side reactions such as polymerization of (meth) acryloyl groups are less likely to occur. Moreover, when an organic solvent is included in the reaction system, the hydrolysis reaction temperature is preferably not higher than the boiling point of the organic solvent. The hydrolysis reaction time is usually 2 to 10 hours.

  The amount of (meth) acryloyl groups modified on the surface of the silica particles of component (B) (the amount of double bonds (g) per gram of silica particles whose surface is modified with a compound having a (meth) acryloyl group) is: The calculated value from the charged value is preferably 0.1 to 2 mmol / g, more preferably 0.2 to 1.5 mmol / g, still more preferably 0.3 to 1 mmol / g. If the amount of the (meth) acryloyl group modified on the surface of the silica particles is above the above lower limit value, the scratch resistance and hardness tend to be improved. If the amount is below the upper limit value, the deformation during three-dimensional processing can be followed. It tends to improve the stretchability and is preferable.

  The said component (B) can also be obtained as a commercial item. As a commercial item applicable to a component (B), Nissan Chemical Industries Co., Ltd. product MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y etc. are mentioned, for example.

  Content of the said component (B) is 18.5 to 45 weight% with respect to the total amount of a component (A) and a component (B). When the content of component (B) is 18.5% by weight or more, the scratch resistance and surface hardness are good, and when it is 45% by weight or less, the stretchability that can follow the deformation during three-dimensional processing is improved. In addition, the transparency of the cured product is improved. From the viewpoint of further enhancing these effects, 19% by weight or more is preferable, 25% by weight or more is more preferable, 42% by weight or less is preferable, and 35% by weight or less is more preferable.

<Organic solvent>
The curable resin composition of the present invention preferably contains an organic solvent. By using an organic solvent, the urethane (meth) acrylate oligomer of component (A) is dissolved well, and the coating film is applied when the urethane (meth) acrylate oligomer is cured by irradiation with active energy rays or the like as will be described later. The viscosity for forming can be adjusted, and a uniform cured product can be obtained.

Any known organic solvent can be used as the organic solvent as long as the effects of the present invention are obtained. Preferably, the solubility parameter (hereinafter referred to as “SP value”) is 8.0.
An organic solvent that is ˜11.5. An SP value of 8 or more is preferable from the viewpoint of the solubility of the urethane (meth) acrylate oligomer, and an SP value of 11.5 or less is preferable from the viewpoint of the transparency of the solution. Examples of the organic solvent in the above range include toluene (SP value: 9.1), xylene (SP value: 9.1), ethyl acetate (SP value: 8.7), butyl acetate (SP value: 8.7). ), Cyclohexanone (SP value: 9.8), methyl ethyl ketone (SP value: 9.0), methyl isobutyl ketone (SP value: 8.7), N-methylpyrrolidone (SP value: 11.2), and the like. It is done. In the present invention, the SP value represents a solubility parameter, and the value is calculated by the method proposed by Fedors et al. Specifically, it is a value obtained by referring to “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”. The SP value is a physical property value determined by the content of the hydrophobic group or hydrophilic group of the molecule. When a mixed solvent is used, it means a value as a mixture of a solvent having a small SP value and a large solvent. .

  The organic solvent can usually be used in an amount of 10 to 900 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. “Solid content” as used herein means not only urethane acrylate (meth) acrylate oligomers but also all components excluding solvents, not only in solid state but also in semi-solid or viscous liquid form Is also included. In addition, it is preferable to use an organic solvent so that the solid content concentration is preferably 10 to 90% by weight, more preferably 20 to 80% by weight.

<Other ingredients>
The curable resin composition of the present invention is a silica particle obtained by modifying the urethane (meth) acrylate oligomer and the surface with a compound having a (meth) acryloyl group, as long as the effects of the present invention are not significantly impaired. And components other than the organic solvent (may be referred to as “other components” in the present invention). Examples of other components include an active energy ray reactive monomer, an active energy ray curable oligomer (excluding the urethane (meth) acrylate oligomer used in the present invention), a polymerization initiator, a photosensitizer, an epoxy compound, and others. And the like.

  Further, in the curable resin composition of the present invention, the content of the total amount of the active energy ray-reactive component including the urethane (meth) acrylate oligomer is excellent in the curing rate and surface curability as the composition, and the tack remains. From the standpoint of absence, it is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and 95% by weight or more based on the total amount of the composition. Even more preferably. In addition, the upper limit of this content is 100 weight%.

  Any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer as long as the effects of the present invention are obtained. These active energy ray-reactive monomers are used for the purpose of adjusting the hydrophilicity / hydrophobicity of the urethane (meth) acrylate oligomer and the physical properties such as surface hardness and elongation when the resulting composition is cured. An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Examples of such active energy ray reactive monomers include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene. Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate Ester monomers; Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; Allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth) acrylamide, N, N-dimethylacrylamide N, N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine (Meth) acrylamides such as methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl , (Meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Stearyl, tetrahydrofurfuryl (meth) acrylate, (meth) a Morpholyl laurate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate , (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) Monofunctional (meth) acrylic acid such as phenyl acrylate And ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ( n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (meth) Polypropylene glycol acrylate (n = 5-14), di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid polybutylene glycol ( n = 3-16), di (meth) acrylic acid poly Li (1-methylbutylene glycol) (n = 5-20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) acrylic acid Neopentyl glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate , Propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri Black decanedimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate.

Among these, in particular, in applications where coating properties are required for the composition of the present invention, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, ( In the molecule, such as trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. Monofunctional (meth) acrylates having a ring structure are preferred, and di (meth) acrylic acid-1,4-butanediol and di (meth) acrylic are used in applications where mechanical strength of the resulting cured product is required. Acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonane Dipentaglycol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Multifunctional (meth) acrylates such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferred, and in applications where flexibility of the resulting cured product is required, di ( Poly (ethylene glycol) acrylate (n = 5-14), polypropylene glycol di (meth) acrylate (n = 5-14), poly (butylene glycol di (meth) acrylate (n = 3-16), di (meth) )acrylic Poly (1-methyl-butylene glycol) (n = 5 to 20) Polyether (meth) acrylates are preferable.

  In the curable resin composition of the present invention, the content of the active energy ray-reactive monomer is the total amount of the composition from the viewpoint of adjusting the viscosity of the composition and adjusting the physical properties such as surface hardness and elongation of the resulting cured product. On the other hand, it is preferably 50% by weight or less, more preferably 30% by weight or less, further preferably 20% by weight or less, and further more preferably 10% by weight or less.

  The active energy ray-curable oligomer may be used alone or in combination of two or more. Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers. In the curable resin composition of the present invention, the content of the active energy ray-reactive oligomer is 50% with respect to the total amount of the composition from the viewpoint of adjusting physical properties such as surface hardness and elongation of the obtained cured product. % Or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

  The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used as long as the effects of the present invention can be obtained. It is. A polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together radical photopolymerization initiator and a photosensitizer.

Examples of the photo radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ] 2-Methyl-propan-1-one is more preferred.

  In addition, when the curable resin composition contains a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group, a photocationic polymerization initiator is used as a polymerization initiator together with the above-mentioned photoradical polymerization initiator. It may be included. Any known cationic photopolymerization initiator may be used as long as it does not significantly impair the effects of the present invention.

  The content of these polymerization initiators in the curable resin composition of the present invention is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components, and is preferably 5 parts by weight or less. It is more preferable that It is preferable for the content of the photopolymerization initiator to be equal to or lower than the above upper limit value because the mechanical strength is not easily lowered by the initiator decomposition product.

  The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types. As the photosensitizer, any known photosensitizer can be used as long as the effects of the present invention are obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, And 4-dimethylaminoacetophenone.

  In the curable resin composition of the present invention, the content of the photosensitizer is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components. The following is more preferable. It is preferable for the content of the photosensitizer to be not more than the above upper limit value because it is difficult for the mechanical strength to decrease due to a decrease in the crosslinking density.

The additive is optional within the range where the effects of the present invention can be achieved, and various materials added to the composition used for the same application can be used as the additive. An additive may be used individually by 1 type, and 2 or more types may be mixed and used for it. Examples of such additives include glass fiber, glass beads, silica particles (except those corresponding to the component (B)), alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc. , Fillers such as kaolin, metal oxide, metal fiber, iron, lead, metal powder; carbon materials such as carbon fiber, carbon black, graphite, carbon nanotubes, fullerenes such as C60 (fillers, carbon materials (Sometimes collectively referred to as “inorganic components”); antioxidants, heat stabilizers, UV absorbers, hindered amine light stabilizers (HALS), anti-fingerprint agents, surface hydrophilizing agents, antistatic agents, imparting slipperiness Agent, plasticizer, mold release agent, antifoaming agent, leveling agent, anti-settling agent, surfactant, thixotropy imparting agent, lubricant, flame retardant, flame retardant aid, polymerization inhibitor, filler, silane Modifiers such as pulling agents; colorants such as pigments, dyes, hue modifiers; and curing agents, catalysts, curing accelerators necessary for the synthesis of monomers or / and oligomers thereof, or inorganic components; etc. Is mentioned.

  In the curable resin composition of the present invention, the content of the additive is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components, and is 5 parts by weight or less. More preferably. It is preferable for the content of the additive to be equal to or less than the above upper limit value because it is difficult for the mechanical strength to decrease due to a decrease in the crosslinking density.

  There are no particular limitations on the method for incorporating the optional components such as the above-mentioned additives into the curable resin composition of the present invention, and conventionally known mixing and dispersing methods may be mentioned. In addition, in order to disperse | distribute the said arbitrary component more reliably, it is preferable to perform a dispersion | distribution process using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill , A kneader, a homogenizer, an ultrasonic disperser and the like.

<Physical properties of curable resin composition>
The curable resin composition of the present invention preferably has a molecular weight between calculated network crosslinking points of 1,000 to 15,000. In the present invention, the “molecular weight between calculated network cross-linking points” is an average value of molecular weights between active energy ray reactive groups (hereinafter sometimes referred to as “cross-linking points”) that form a network structure in the entire composition. Means. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction of curing the curable resin composition with active energy rays, when a compound having only one active energy ray reactive group (hereinafter sometimes referred to as “monofunctional compound”) is reacted, On the other hand, when a compound having two or more active energy ray reactive groups (hereinafter sometimes referred to as “polyfunctional compound”) reacts, a network structure is formed.

  Therefore, the active energy ray reactive group possessed by the polyfunctional compound is the crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound is the crosslinking possessed by the polyfunctional compound. The molecular weight between points of calculation network cross-linking points is calculated as the effect of extending the molecular weight between points, and the calculation of the molecular weight between cross-linking points of calculation network is the same reactivity of all active energy ray reactive groups. It is calculated on the assumption that all active energy ray reactive groups react by irradiation with active energy rays.

  In a polyfunctional compound single system in which only one kind of polyfunctional compound reacts, the molecular weight between calculated network crosslinking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1,000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.

  On the other hand, in the mixed system of polyfunctional compounds in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition Is the molecular weight between the calculated network cross-linking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1,000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of reactive energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × (2/20) = 520.

When the curable resin composition contains a monofunctional compound, it is calculated to form an equimolar amount of each active energy ray reactive group (that is, a crosslinking point) of the polyfunctional compound and the monofunctional compound linked to the crosslinking point. Assuming that the reaction is carried out so as to be located in the middle of the formed molecular chain, the extension of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, and the total activity of the polyfunctional compound in the composition It is half of the value divided by the number of energy ray reaction radix. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition.

  For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1,000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the calculated network cross-linking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinks of the composition is 1000 + 500 = 1500.

From the above, in the mixture of monofunctional compounds M _A molar molecular weight W _A, and f _B functional compound M _B mol molecular weight W _B, and f _C functional compound M _C mol molecular weight W _C, the composition The molecular weight between the calculated network cross-linking points of the product can be expressed by the following formula.

  The molecular weight between the calculated network crosslinking points of the curable resin composition of the present invention thus calculated is preferably 1,000 or more, more preferably 2,000 or more, and 3,000 or more. More preferably, it is particularly preferably 4,000 or more, on the other hand, preferably 15,000 or less, more preferably 12,000 or less, and particularly preferably 10,000 or less. .

  When the molecular weight between the calculated network crosslinking points is not more than the above upper limit, the stain resistance of the cured product obtained from the curable resin composition tends to be good. Further, when the molecular weight between the calculated network cross-linking points is not less than the above lower limit value, the three-dimensional workability of the obtained cured product tends to be good. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the three-dimensional processability is excellent. It is presumed that this is because the structure becomes a strong structure and is excellent in stain resistance.

  The molecular weight between the calculation network cross-linking points can be controlled, for example, by adding a monomer for forming a molecular weight of the urethane (meth) acrylate oligomer or a cross-linked structure. For example, when the number average molecular weight of the urethane (meth) acrylate oligomer is lowered or the polyfunctional acrylate is added, the value of the molecular weight between calculated network crosslinking points tends to be lowered.

The viscosity of the curable resin composition of the present invention can be appropriately adjusted according to the use and usage of the curable composition, but from the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc., E The viscosity at 25 ° C. in a type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 mPa · s or more, more preferably 30 mPa · s or more, while 50,000 mPa · s or less. It is preferably 10,000 mPa · s or less, more preferably 5,000 mPa · s or less, and particularly preferably 2,000 mPa · s or less. The viscosity of the curable resin composition can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer according to the present invention, the type of the optional component, the blending ratio thereof, and the like.

  The curable resin composition of the present invention preferably has a tensile modulus measured by the following method of 2,500 or more with respect to a cured film formed by the following method. It is more preferably 800 or more, and further preferably 3,000 or more. It is preferable from the viewpoints of scratch resistance, contamination resistance, wear resistance and the like that the tensile elastic modulus is not less than the above lower limit. On the other hand, the upper limit is not particularly limited, but is usually 5,000 MPa or less. In addition, the film forming method and measuring method at the time of measuring this tensile elastic modulus are as follows.

(Film forming method)
A curable resin composition is coated on a polyethylene terephthalate film with a bar coater to form a coating film, and then dried at 60 ° C. for 1 minute, and accelerated using an electron beam irradiation device (CB175, manufactured by Eyegraphic). After irradiating the dried coating film with an electron beam under the conditions of a voltage of 165 kV and an irradiation dose of 5 Mrad, and further curing at 23 ° C. for 1 day to form a cured film, the cured film is peeled off from the polyethylene terephthalate film to have a film thickness of about 20 μm. A cured film is obtained.

(Tensile modulus measurement method)
The cured film is cut to a width of 10 mm, and using a Tensilon tensile tester (“RTC-1210A” manufactured by Orientec Co., Ltd.), the temperature is 23 ° C., the humidity is 55% RH, the tensile speed is 50 mm / min, and the distance between chucks is 50 mm. The tensile modulus is measured by performing a tensile test under the conditions. More specifically, a straight line connecting the stress at 0% elongation and the stress at 0.5% elongation of the stress-strain curve (SS curve) obtained by conducting the tensile test under the above conditions is extended to 100 The stress converted at% elongation is taken as the tensile modulus.

[Cured product]
A cured product can be obtained by irradiating the curable resin composition of the present invention with active energy rays (hereinafter sometimes referred to as “cured product of the present invention”). Although the form of the hardened | cured material of this invention is not restrict | limited in particular, For example, it can obtain with the form of a cured film.

  Examples of active energy rays that can be used when the curable resin composition is cured include infrared rays, visible rays, ultraviolet rays, X rays, electron beams, α rays, β rays, and γ rays. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar A laser, a He—Cd laser, a solid laser, a xenon lamp, a high frequency induction mercury lamp, sunlight, or the like is suitable.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when it hardens | cures by electron beam irradiation, it is preferable that the irradiation amount is 1-15 Mrad. Moreover, when hardening by ultraviolet irradiation, it is preferable that it is 50-1,500 mJ / cm < ² >.

  When curing, any atmosphere of air, inert gas such as nitrogen or argon may be used. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

[Laminate]
A layered product can be obtained by forming a layer made of the cured product of the present invention on a substrate (hereinafter sometimes referred to as “the layered product of the present invention”). The laminate of the present invention is not particularly limited as long as it has a layer made of the cured product of the present invention on the substrate, and a layer other than the substrate and the layer composed of the cured product of the present invention is used as the substrate and the present invention. You may have between the layers which consist of this hardened | cured material, and you may have on the outer side. Moreover, the laminated body of this invention may have multiple layers which consist of a base material or the hardened | cured material of this invention.

  Although the manufacturing method in particular of the laminated body of this invention is not restrict | limited, It can obtain by apply | coating the curable resin composition of this invention on a base material, and hardening this curable resin composition. Coating methods for the curable resin composition include bar coater method, applicator method, curtain flow coater method, roll coater method, spray method, gravure coater method, comma coater method, reverse roll coater method, lip coater method, and die coater. Known methods such as a method, a slot die coater method, an air knife coater method and a dip coater method can be applied, and among them, a bar coater method and a gravure coater method are preferable. The method for curing the curable resin composition is as described above in the description of the cured product of the present invention.

  As a method of obtaining a laminate having a plurality of layers of cured products, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured. A known method such as a method in which the upper layer is applied after curing with active energy rays, and a method in which each layer is applied to a release film or a base film, and then the layers are bonded together in an uncured or semi-cured state. However, from the viewpoint of enhancing the adhesion between the layers, a method of curing with active energy rays after laminating in an uncured state is preferable. As a method of laminating in an uncured state, a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.

  Examples of the base material include polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polyolefin resins such as polypropylene resin and polyethylene resin, nylon resins, polycarbonate resins, (meth) acrylic resins, acrylonitrile-butadiene-styrene resins, and the like. Examples include various shapes of articles such as plates made of various plastics or metals. Among these, polyethylene terephthalate resin, acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin are preferable.

  In the laminate of the present invention, the thickness of the layer comprising the cured product of the present invention is appropriately determined according to the intended use, but is preferably 1 μm or more, more preferably 3 μm or more, and preferably Is 100 μm or less, more preferably 50 μm or less, and particularly preferably 20 μm. If the thickness of the layer made of the cured product of the present invention is not less than the above lower limit value, the appearance of design and functionality after three-dimensional processing tends to be favorable, while the film thickness is not more than the above upper limit value. In addition, the internal curability and the three-dimensional workability tend to be good.

[Use]
A cured product obtained from the curable resin composition of the present invention and a laminate obtained by forming the cured product on a substrate can be suitably used as a film for coating replacement. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. In particular, the cured product obtained from the curable resin composition of the present invention is useful as a decorative film using this as a top coat layer.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Measurement method of physical properties]
The measurement / evaluation method of the physical properties of the urethane (meth) acrylate oligomer and the cured film in the following Examples and Comparative Examples is as follows.

<Physical properties of urethane (meth) acrylate oligomer>
1-1) Number average molecular weight (Mn) of urethane (meth) acrylate oligomer
The number average molecular weight (Mn) of the urethane (meth) acrylate oligomer was measured by the GPC measurement method under the following conditions.
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel superH1000 + H2000 + H3000” manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / internal)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 0.5 mL / min Injection volume: 10 μL
Concentration: 0.2% by weight
Calibration sample: Monodisperse polystyrene calibration method: Polystyrene conversion

1-2) Urethane bond amount of urethane (meth) acrylate oligomer Total amount of urethane bond in the total amount of components of urethane (meth) acrylate oligomer (sum of the product of the number of moles of each raw material component and the molecular weight of each component) The amount of urethane bonds was calculated from the ratio of the total number of moles of isocyanate, the number of isocyanate groups of polyisocyanate, and the molecular weight of urethane bonds (59)).

<Physical properties of cured film>
2-1) Evaluation of appearance of cured film The obtained cured film was visually evaluated as follows.
○: Transparent with no turbidity or foreign matter seen.
X: Turbidity and foreign matter are confirmed.

2-2) The scratch resistance evaluation described later film forming method cured film laminated on a polyethylene terephthalate obtained in I, the haze value measured before the scratch test and H _1. On the other hand, in an atmosphere of 23 ° C. and 55% RH, 200 gf (per area of 4 cm ² ) was placed on steel wool (steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd.), and the polyethylene obtained by the above-mentioned film forming method I terephthalate Gakushin abrasion tester laminated cured film surface on rubbed 15 round trips (manufactured by Toyo Seiki), and the haze value measured immediately after the H _2. ΔH (ΔH = H ₂ −H ₁ ) was determined from the values of H ₁ and H ₂ . It is evaluated that the smaller the value of ΔH, the better the scratch resistance. In the above, the haze value is a haze meter ("HAZE" manufactured by Murakami Color Research Laboratory Co., Ltd.).
METER HM-65W "), and measured according to JIS K7105.

2-3) Evaluation of surface hardness About the cured film laminated | stacked on the polyethylene terephthalate obtained by the film forming method I mentioned later using a Fischer scope HM200 (made by Fisher Instruments company), it is 5 mN / mm < ² > with a Vickers indenter. The indentation hardness (Vickers hardness) of the surface protective layer was measured with a test force of. The higher the value of Vickers hardness, the better the surface hardness.

2-4) Evaluation of elastic modulus A cured film of the film forming method II described later is cut into a width of 10 mm, and a temperature of 23 ° C. and a humidity of 55% is obtained using a Tensilon tensile tester (“RTC-1210A” manufactured by Orientec Co., Ltd.). A tensile test was performed under the conditions of RH, a tensile speed of 50 mm / min, and a distance between chucks of 50 mm, and the tensile elastic modulus was measured. More specifically, a straight line connecting the stress at 0% elongation and the stress at 0.5% elongation of the stress-strain curve (SS curve) obtained by conducting the tensile test under the above conditions is extended to 100 The stress converted at% elongation was taken as the tensile modulus. It is evaluated that the larger the value of the tensile elastic modulus, the better the elastic modulus.

2-5) Evaluation of stretchability A cured film of the film formation method II described later is cut into a width of 10 mm, and a temperature of 100 ° C. and a tensile speed are measured using a Tensilon tensile tester (“MX2-500N” manufactured by Imada Co., Ltd.). The breaking elongation was measured under the conditions of 40 mm / min and a distance between chucks of 40 mm. If the elongation at break was 50% or more, it was evaluated that the three-dimensional formability was good.

[Raw materials / solvents]
The raw materials and solvents used in Examples and Comparative Examples below and their abbreviations are as follows.

<Raw material of component (A)>
((A-1) Polyisocyanate)
・ IPDI: Isophorone diisocyanate (Evonik Degussa Japan, trade name “VESTANAT IPDI”)
((A-2) C2-C14 aliphatic diol)
EG: ethylene glycol 1,4-CHDM: 1,4-cyclohexanedimethanol 1,12-DD: 1,12-dodecanediol (trade name “1,12-dodecanediol” manufactured by Ube Industries)
((A-3) hydroxyalkyl (meth) acrylate)
V-300: A mixture of 40 to 45% by weight of pentaerythritol triacrylate and 35 to 40% by weight of pentaerythritol tetraacrylate (catalog value) (trade name Biscoat 300 manufactured by Osaka Organic Chemical Co., Ltd.)

<Raw material of component (B)>
(Silica particles dispersed in a solvent)
MEK-ST: methyl ethyl ketone (MEK) -dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, trade name MEK-ST, average primary particle size: 15 nm (catalog value), silica solid content: 30% by mass)
(Silane compound having (meth) acryloyl group)
KBM5103: γ- (meth) acryloyloxypropyltrimethoxysilane (trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Organic solvent>
MEK: methyl ethyl ketone (SP value: 9.0)

[Synthesis Example A-1]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 179 g of IPDI, 148 g of 1,12-dodecanediol, 327 g of methyl ethyl ketone, and 0.02 g of dioctyltin dilaurate are added and oiled. The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After cooling to 60 ° C. after completion of the reaction, 0.1 g of dioctyltin dilaurate, 0.2 g of methyl hydroquinone and 73 g of methyl ethyl ketone were further added, and 73 g of V-300 was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and after confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 200 g of methyl ethyl ketone was added, and the urethane acrylate oligomer (A-1) was obtained. About the obtained urethane acrylate oligomer (A-1), the number average molecular weight was measured by the method of said 1-1). The obtained results are shown in Table-1.

[Synthesis Example A-2]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 189 g of IPDI, 162 g of 1,12-dodecanediol, and 351 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate are added and oiled. The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After cooling to 60 ° C. after completion of the reaction, 0.1 g of dioctyltin dilaurate, 0.2 g of methyl hydroquinone and 49 g of methyl ethyl ketone were added, and 49 g of V-300 was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and after confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 200 g of methyl ethyl ketone was added, and the urethane acrylate oligomer (A-2) was obtained. About the obtained urethane acrylate oligomer (A-2), the number average molecular weight was measured by the method of said 1-1). The obtained results are shown in Table-1.

[Synthesis Example A-3]
Into a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 245 g of IPDI and 61 g of ethylene glycol were added, and 309 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate were further added in an oil bath. The reaction was allowed to proceed for 9 hours while heating to 0 ° C. After cooling to 60 ° C. after completion of the reaction, 0.1 g of dioctyltin dilaurate, 0.2 g of methyl hydroquinone and 90 g of methyl ethyl ketone were further added, and 76 g of HEA 14 g and V-300 were added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and after confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 200 g of methyl ethyl ketone was added, and the urethane acrylate oligomer (A-3) was obtained. About the obtained urethane acrylate oligomer (A-3), the number average molecular weight was measured by the method of said 1-1). The obtained results are shown in Table-1.

[Synthesis Example A-4]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 204 g of IPDI and 122 g of 1,4-cyclohexanedimethanol were added, and 326 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate were added. The reaction was conducted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the reaction, the reaction mixture was cooled to 60 ° C., and further 0.1 g of dioctyltin dilaurate, 0.2 g of methyl hydroquinone and 74 g of methyl ethyl ketone were added, and 73 g of V-300 was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and after confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 200 g of methyl ethyl ketone was added, and the urethane acrylate oligomer (A-4) was obtained. About the obtained urethane acrylate oligomer (A-4), the number average molecular weight was measured by the method of said 1-1). The obtained results are shown in Table-1.

[Synthesis Example B-1]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 904 g of MEK-ST (solid content 30%) and 37 g of KBM-5103 are added, and 54 g of methyl ethyl ketone and 0.15 g of methyl hydroquinone are added. Silica particles formed by adding 3.1 g of water and 1.5 g of acetylacetone aluminum and reacting for 4 hours while heating to 70 ° C. in an oil bath and modified with a compound having a (meth) acryloyl group on the surface (B-1 ) The amount of (meth) acryloyl groups modified on the surface of the silica particles was 0.51 mmol / g.

[Example 1]
The silica particles (B-1) obtained by modifying the urethane acrylate oligomer (A-1) obtained in Synthesis Example A-1 and the surface obtained in Synthesis Example B-1 with a compound having a (meth) acryloyl group. It mix | blended as shown in Table-2 and mixed uniformly, and the curable resin composition was obtained.

(Film forming method I)
A curable resin composition is coated on a polyethylene terephthalate film with a bar coater to form a coating film, and then dried at 60 ° C. for 1 minute, and accelerated using an electron beam irradiation device (CB175, manufactured by Eyegraphic). Curing by irradiating the dried coating film with an electron beam under the conditions of a voltage of 165 kV and an irradiation dose of 5 Mrad, and further curing at 23 ° C. for one day to form a cured film, and a cured film having a thickness of about 5 μm is laminated on polyethylene terephthalate. A membrane was obtained. About the obtained cured film, the physical-property evaluation of said 2-1)-2-3) was performed. These results are shown in Table-2.

(Film Formation Method II)
A curable resin composition is coated on a polyethylene terephthalate film with a bar coater to form a coating film, and then dried at 60 ° C. for 1 minute, and accelerated using an electron beam irradiation device (CB175, manufactured by Eyegraphic). After irradiating the dried coating film with an electron beam under the conditions of a voltage of 165 kV and an irradiation dose of 5 Mrad, and further curing at 23 ° C. for 1 day to form a cured film, the cured film is peeled off from the polyethylene terephthalate film to have a film thickness of about 20 μm. A cured film was obtained. About the obtained cured film, the physical-property evaluation of said 2-4) and 2-5) was performed. These results are shown in Table-2.

[Examples 2 to 5, Reference Example 1 and Comparative Examples 1 to 8]
As shown in Table-2 or Table-3, a curable resin composition was obtained in the same manner as in Example 1 except that the blending composition was changed. In Comparative Examples 4 and 5, “MEK-ST” used as a raw material of Synthesis Example B-1 was used as a comparison target for Synthesis Example B-1. Each curable resin composition was evaluated in the same manner as in Example 1. The obtained results are shown in Table-2 or Table-3.

[Evaluation results]
Table 2 and Table 3 show the following. First, compared with Examples 1-3, Comparative Examples 1 and 2 are examples in which the amount of component (B) is small, and Comparative Example 3 is an example in which the amount of component (B) is large. From comparison between Examples 1 to 3 and Comparative Examples 1 and 2, it can be seen that the scratch resistance, surface hardness and elastic modulus are remarkably improved when the blending amount of the component (B) is within the range of the present invention. Moreover, it turns out from the comparison with Examples 1-3 and Comparative Example 3 that a cured film external appearance and stretchability are remarkably excellent in the compounding quantity of a component (B) being the range of this invention. That is, it can be seen that the present invention improves the scratch resistance, surface hardness, elastic modulus, cured film appearance, and stretchability in a well-balanced manner.

  Next, with respect to each of Examples 1 and 3, Comparative Examples 4 and 5 are examples in which MEK-ST was used instead of component (B). From the comparison between Example 1 and Comparative Example 4 and Example 3 and Comparative Example 5, it can be seen that the scratch resistance is remarkably improved by using the component (B).

In contrast to Examples 4 to 5 , Comparative Examples 6 to 8 are examples in which the component (B) was not used. It can be seen that the corresponding Examples 4 to 5 using the same kind of component (A) for each of Comparative Examples 6 to 8 significantly improve the scratch resistance, surface hardness and elastic modulus.

  A cured product obtained from the curable resin composition of the present invention and a laminate obtained by forming the cured product on a substrate can be suitably used as a film for coating replacement. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. In particular, the cured product obtained from the curable resin composition of the present invention is useful as a decorative film using this as a top coat layer.

Claims (7)

A curable resin composition comprising the following component (A) and component (B), and comprising 18.5 to 45% by weight of component (B) relative to the total amount of component (A) and component (B).
Component (A): Reaction of at least (a-1) polyisocyanate, (a-2) a diol having 2 to 14 carbon atoms and a chain structure, and (a-3) hydroxyalkyl (meth) acrylate Urethane (meth) acrylate oligomer component (B) having a urethane bond amount of 24% by weight or more obtained in this manner: silica particles whose surface is modified with a compound having a (meth) acryloyl group   The curable resin composition according to claim 1, wherein the urethane (meth) acrylate oligomer of component (A) has a number average molecular weight (Mn) of 500 to 15,000.   The urethane (meth) acrylate oligomer of component (A) is a (a-1) polyisocyanate and (a-2) aliphatic having 2 to 14 carbon atoms and reacting with a chain structure diol to form a urethane prepolymer. The curable resin composition according to claim 1 or 2, which is obtained by reacting (a-3) hydroxy (meth) acrylate with the resulting product.   The curable resin composition according to any one of claims 1 to 3, wherein the (a-1) polyisocyanate is a polyisocyanate having an alicyclic structure.   Hardened | cured material formed by irradiating an active energy ray to the curable resin composition of any one of Claims 1 thru | or 4.   The laminated body formed by forming the layer which consists of hardened | cured material of Claim 5 on a base material.   The laminate according to claim 6, wherein the substrate is at least one selected from polyethylene terephthalate resin, acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin.