JP2015071666A - Curable resin composition, cured product, laminate, hard coat film, and film laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition from which such a hard coat layer can be formed that has the sufficient antiblocking property and high hardness, gives a good appearance of a coating film, and has high transparency.SOLUTION: A curable resin composition comprises the following components (A), (B), and (C), in which a solubility parameter (SP) of the component (A) is higher than a solubility parameter (SP) of the component (B). The components are: (A) a resin having a weight average molecular weight (Mw) of over 13,000; (B) a monomer and/or oligomer having a weight average molecular weight (Mw) of less than 2,000 and at least one (meth)acryloyl group; and (C) a resin which is obtained by polymerizing a radical polymerizable monomer having an alkyl group having 1 to 24 carbon atoms in a side chain via an atom excluding at least carbon, and which has a weight average molecular weight (Mw) ranging from 2,000 to 13,000.

Description

  The present invention relates to a curable resin composition that can provide a cured product having good antiblocking properties. The present invention also provides a cured product obtained by curing the curable resin composition, a laminate having a cured layer, a hard coat film, and a film laminate obtained by laminating the hard coat film with another resin film. About.

  The surface of a thermoplastic resin film typified by a polyethylene terephthalate (PET) film is provided with a hard coating having excellent hardness and slipperiness. A film on which such a hard coating has been performed may be wound into a roll during storage for the purpose of securing a storage location, operability during molding, preventing contamination, and the like.

  As a method for preventing this blocking, a method for preventing blocking by mixing inorganic fine particles in the hard coat layer on the surface so that the hard coating surface has a specific surface roughness is disclosed (see Patent Document 1). Moreover, it is contained in the resin composition by containing a resin and a specific unsaturated double bond-containing monomer containing an alkylene oxide unit having 2 to 4 carbon atoms in the resin composition for forming the hard coat layer. A method is disclosed in which blocking is prevented by depositing resin by phase separation after application of the composition and forming irregularities on the surface (see Patent Document 2).

JP 2004-42653 A JP 2010-163535 A

  In the technique disclosed in Patent Document 1, in order to form irregularities on the surface of the hard coat layer by particles mixed in the hard coat layer, it is necessary to reduce the thickness of the hard coat layer. For this reason, the hardness of a hard-coat layer falls and there exists a tendency for abrasion resistance not to be enough. On the other hand, in the technique disclosed in Patent Document 2, the SP value of the resin separately contained is lower than the SP value of the specific unsaturated double bond-containing monomer containing an alkylene oxide unit having 2 to 4 carbon atoms. By setting, the resin is precipitated by phase separation after coating. However, when the present inventors examined, in the technique currently disclosed by patent document 2, since the unsaturated double bond containing monomer contains an alkylene oxide unit, the hardness of the formed hard coat layer is low, It was found that antiblocking and scratch resistance were not sufficient.

  The present invention solves such problems of the prior art, and forms a hard coating layer having sufficient anti-blocking performance, high hardness, good coating film appearance, and high transparency. An object of the present invention is to provide a curable resin composition that can be used.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by adding a specific compound to the curable resin composition. That is, the gist of the present invention is the following [1] to [16].

[1] The following component (A), component (B) and component (C) are included, and the solubility parameter (SP _A ) of the component ( _A ) is higher than the solubility parameter (SP _B ) of the component (B). A curable resin composition.
Component (A): Resin having a weight average molecular weight (Mw) of more than 13,000 Component (B): Weight average molecular weight (Mw) of less than 2,000 and having one or more (meth) acryloyl groups Monomer and / or oligomer Component (C): A radically polymerizable monomer having an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least an atom other than carbon in the side chain is polymerized. Resin obtained and having a weight average molecular weight (Mw) of 2,000 to 13,000

[2] The curable resin composition according to [1], including 0.5 to 25% by weight of component (A) with respect to the total amount of component (A) and component (B).

[3] The curable resin composition according to [1] or [2], comprising 0.001 to 20 parts by weight of the component (C) with respect to 100 parts by weight of the total of the component (A) and the component (B). .

[4] The curable resin composition according to any one of [1] to [3], wherein the component (A) is a resin having a hydrogen bonding group and a (meth) acryloyl group.

[5] The curable resin composition according to [4], wherein the hydrogen bonding group is a hydroxyl group.

[6] The curable resin composition according to any one of [1] to [5], wherein the component (B) is a polyfunctional (meth) acrylate having two or more unsaturated double bonds in one molecule. object.

[7] The curable resin composition according to [6], including a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule as the polyfunctional (meth) acrylate.

[8] The curable resin composition according to any one of [1] to [7], including a compound represented by the following formula (1) as the radical polymerizable monomer.
^{_{CH 2 = C (R 1)}} -C (O) -X-R 2 (1)
(In the above formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent, X is —O— or —NH—.

[9] The component (C) has a reactive group having active hydrogen, and the amount of the reactive group is 0.1 to 8.0 mmol / g, according to any one of [1] to [8] Curable resin composition.

[10] The curable resin composition according to any one of [1] to [9], further comprising the following component (D).
Component (D): inorganic particles having an average primary particle size of 1 μm or less

[11] The curable resin composition according to [10], including 0.05 to 30 parts by weight of the component (D) with respect to 100 parts by weight of the total of the component (A) and the component (B).

[12] The curable resin composition according to any one of [1] to [11], wherein the component (A) is based on a ring-opening / addition reaction of a compound having an oxirane structure.

[13] A cured product obtained by curing the curable resin composition according to any one of [1] to [12].

[14] A laminate obtained by forming a cured layer on the substrate by curing the curable resin composition according to any one of [1] to [12].

[15] A hard coat film obtained by curing the curable resin composition according to any one of [1] to [12].

[16] A film laminate obtained by laminating the hard coat film according to [15] with another resin film.

  According to the curable resin composition of the present invention, even if the hard coat layers or the hard coat layer and another resin film are in close contact with each other, blocking does not occur, the hardness is high, and the coating film appearance is good. A hard coat layer with high transparency can be formed. Moreover, this hard coat layer can be made thin.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description described below is an example of the embodiments of the present invention, and the present invention is limited to the following descriptions as long as the gist thereof is not exceeded. It is not a thing. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.

  In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means either one or both. Similarly, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, meaning either one or both, and “(meth) acryloyl group” is a generic term for acryloyl group and methacryloyl group, Means either or both. The same applies to “(meth) acrylic monomer” and “(meth) acrylic resin”. “(Poly) propylene glycol” means either or both of “propylene glycol” and “polypropylene glycol”. The same applies to “(poly) ethylene glycol”.

[Curable resin composition]
The curable resin composition of the present invention comprises the following component (A), component (B) and component (C), and the solubility parameter (SP _A ) of component ( _A ) is the solubility parameter of component (B). It is higher than (SP _B ).
Component (A): Resin having a weight average molecular weight (Mw) of more than 13,000 Component (B): Weight average molecular weight (Mw) of less than 2,000 and having one or more (meth) acryloyl groups Monomer and / or oligomer Component (C): A radically polymerizable monomer having an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least an atom other than carbon in the side chain is polymerized. Resin obtained and having a weight average molecular weight (Mw) of 2,000 to 13,000

<Reason why the present invention is effective>
The details of the mechanism of action of the curable resin composition of the present invention that provides a hard coat layer with high hardness, excellent antiblocking performance, and further excellent transparency and coating film appearance are not clear, but are presumed as follows. . That is, when the curable resin composition of the present invention is applied and dried, the component (A), for example, a resin such as a (meth) acryloyl polymer having a hydrogen bonding group in the side chain described later is a component ( It precipitates on the coating film surface by phase separation with B) to form fine irregularities. At this time, since the resin of the component (C) has a low polarity alkyl group having 1 to 24 carbon atoms in the side chain, the surface energy of the coating film can be reduced and slipperiness can be imparted. It is presumed that it will be further improved.

<SP value>
The solubility parameter (SP value) is a solubility parameter, which is a measure of solubility. The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller. In the present invention, the SP value is a value measured by the following method. 0.5 g of sample is weighed into a 100 ml Erlenmeyer flask, and 10 ml of acetone is added to dissolve the resin. Here, hexane is dropped while stirring with a magnetic stirrer, and the dripping amount (vh) of hexane at the point where the solution becomes cloudy (turbid point) is determined. Next, when deionized water is used instead of hexane, the dripping amount (vd) of deionized water at the cloud point is obtained. From vh and vd, the SP value is given in References: SUH, CLARKE, J. P. S. A-1, 5, 1671-1681 (1967). Further, when the solubility parameter cannot be obtained by the above method, for example, the sample does not dissolve in acetone, it is estimated by the method proposed by Fedors et al. (Hereinafter sometimes referred to as “Federals method”). . Specifically, it can be obtained by referring to “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”.

In the curable resin composition of the present invention, the solubility parameter (SP _A ) of the component ( _A ) is higher than the solubility parameter (SP _B ) of the component (B). Furthermore, it is preferable that SP _A is 0.5 or more higher than SP _B of the component (B), and it is particularly preferable that SP _A is 1.0 or more higher. Further, the SP _A of the resin of the component (A) used in the present invention is preferably 14.0 or more, more preferably 15.0 or more, more preferably 16.0 or more, It is preferably 22.0 or less, and preferably 20.0 or less. On the other hand, the SP _B of the monomer and / or oligomer containing one or more (meth) acryloyl groups of the component (B) used in the present invention is preferably 10.5 or more, and 11.0 or more. Is more preferably 15.0 or less, and more preferably 14.0 or less. SP _A and SP _B are preferably in the above ranges from the viewpoints of compatibility and phase separation.

In addition, the solubility parameter (SP _C ) of the component (C) is preferably 13.0 or less from the viewpoint of imparting slipperiness by lowering the surface energy when the curable composition is cured. It is more preferably 5 or less, and further preferably 11.5 or less. On the other hand, the solubility parameter (SP _C ) of the component (C) is usually 8.0 or more, preferably 9.0 or more. Furthermore, it is preferable that SP _B is larger than SP _C from the viewpoint of increasing the effect of imparting slipperiness by lowering the surface energy when curing the curable resin composition.

In the present invention, SP _A is higher than SP _B , so that phase separation is likely to occur. In order to make SP _A higher than SP _B , for example, the side chain of the resin of component (A) may be designed to include many functional groups having high polarity. Thus, a method of preparing a copolymer by ring-opening a monomer having an oxirane skeleton by addition of (meth) acrylic acid can be mentioned. In addition, a component having a low SP value may be selected as a monomer and / or oligomer containing one or more (meth) acryloyl groups of component (B). For example, bifunctional or more having an alicyclic structure as component (B) And a method using acrylate.

<Functional groups that react with each other>
The resin of component (A) included in the present invention and the monomer and / or oligomer containing one or more (meth) acryloyl groups of component (B) each have a functional group that reacts with each other. Is preferred. By reacting such a functional group, the hardness, solvent resistance, etc. of the cured product obtained by curing the curable resin composition of the present invention can be enhanced. Examples of combinations of such functional groups include, for example, reactive groups having an active hydrogen (hydroxyl group, amino group, thiol group, carboxyl group, etc.) and an epoxy group, reactive groups having an active hydrogen and an isocyanate group, and ethylenic unsaturation. Group and ethylenically unsaturated group (polymerization of ethylenically unsaturated group occurs), silanol group and silanol group (condensation polymerization of silanol group occurs), silanol group and epoxy group, reactive group having active hydrogen and active hydrogen And reactive groups having active groups, active methylene and acryloyl groups, oxazoline groups and carboxyl groups, and the like.

  As used herein, “functional groups that react with each other” can be obtained by mixing only the monomer and / or oligomer containing the resin of component (A) and one or more (meth) acryloyl groups of component (B). Although reaction does not advance, what reacts mutually by mixing a polymerization initiator together is also contained. Examples of the polymerization initiator that can be used here include a photopolymerization initiator, which will be described in detail later.

<Component (A)>
Component (A) used in the present invention is a resin having a weight average molecular weight (Mw) exceeding 13,000. “Exceeding 13,000” means “greater than 13,000”. Examples of the resin of component (A) include resins such as (meth) acrylic resin, olefin resin, polyether resin, polyester resin, polyurethane resin, polysiloxane resin, polysilane resin, polyimide resin, and fluorine resin. Among these, from the viewpoint of SP value, a resin including a (meth) acrylic structure, a polyether structure, a polyester structure, a polyurethane structure, and a polyimide structure in the skeleton structure is preferable, and the SP value can be easily controlled. In addition, a resin containing a (meth) acrylic structure in the skeleton structure is particularly preferable because it can be easily polymerized. Here, the “resin containing a (meth) acrylic structure in the skeleton structure” means a resin obtained by polymerizing at least a monomer having a (meth) acryloyl group, that is, a resin having a (meth) acryloyl group (hereinafter, “ (It may be referred to as “(meth) acryloyl polymer”).

As a resin containing a (meth) acrylic structure in the skeleton structure, a resin obtained by polymerizing or copolymerizing a (meth) acrylic monomer, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond Etc.
Examples of the resin having an olefin structure in the skeleton structure include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene ionomer, ethylene / vinyl alcohol copolymer, ethylene / vinyl chloride copolymer, etc. Is mentioned. Among these, an ethylene / vinyl acetate copolymer, an ethylene ionomer, an ethylene / vinyl alcohol copolymer, an ethylene / vinyl chloride copolymer, and the like are preferable.
The resin including a polyether structure in the skeleton structure is a resin including an ether bond in a molecular chain, and examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
The resin containing a polyester structure in the skeleton structure is a resin containing an ester bond in the molecular chain, and examples thereof include unsaturated polyester resins, alkyd resins, and polyethylene terephthalate.
The resin containing a polyurethane structure in the skeleton structure is a resin containing a urethane bond in the molecular chain.
The resin containing a polysiloxane structure in the skeleton structure is a resin containing a siloxane bond in the molecular chain.
A resin containing a polysilane structure in the skeleton structure is a resin containing a silane bond in the molecular chain.
A resin including a polyimide structure in a skeleton structure is a resin including an imide bond in a molecular chain.
The resin including a fluorine structure in the skeleton structure is a resin including a structure in which part or all of the hydrogen atoms of polyethylene are replaced with fluorine atoms.
The resin of component (A) may be a copolymer containing two or more of the above skeleton structures, or may be a copolymer composed of the above skeleton structures and other skeleton structures.

  Of the above-mentioned resins, a resin having a (meth) acryloyl group is preferable from the viewpoint of high SP value, easy control of the SP value, and easy polymerization. Further, a resin having a hydrogen bonding group and a (meth) acryloyl group is preferable because it is easy to make the SP value higher than the later-described polyfunctional (meth) acrylate suitable as the component (B).

  Here, the hydrogen bonding group means a functional group capable of hydrogen bonding with other functional groups, specifically a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, an amide group, a phosphoric acid group. And are preferably hydroxyl groups, amino groups, amide groups, and carboxyl groups, more preferably hydroxyl groups, and particularly preferably secondary hydroxyl groups. The amount of hydrogen bonding group possessed by the (meth) acryloyl polymer is not particularly limited, but is preferably 1.0 mmol / g or more.

The method for introducing a hydroxyl group as a hydrogen bonding group is not particularly limited, but hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (poly) propylene glycol- (poly) ethylene Glycol mono (meth) acrylate, (poly) butylene glycol- (poly)
A method of polymerizing by using as a raw material a hydroxyl group-containing (meth) acrylate such as ethylene glycol mono (meth) acrylate and (poly) propylene glycol- (poly) butylene glycol mono (meth) acrylate, and a monomer having an oxirane structure Method for producing polymerized polymer, ring-opening / addition reaction of this, Method for producing polymer polymerized with monomer having oxirane structure, and ring-opening / addition reaction of monomer having hydroxyl group such as lactic acid, carboxyl group And a method of polymerizing a monomer having a reactive group that undergoes a ring-opening / addition reaction with an oxirane structure such as an amino group, followed by a method of subjecting the monomer having an oxirane structure to a ring-opening / addition reaction.

  In addition, it is preferable that the (meth) acryloyl polymer has an unsaturated double bond because the resulting cured product has high hardness. Such a (meth) acryloyl polymer having an unsaturated double bond includes, for example, a resin copolymerized with a (meth) acryloyl monomer, a (meth) acryloyl monomer and another monomer having an ethylenically unsaturated double bond. Copolymerized resin, resin obtained by reacting (meth) acryloyl monomer with another ethylenically unsaturated double bond and a monomer having an epoxy group, (meth) acryloyl monomer and other ethylenically unsaturated double bond and isocyanate Examples thereof include a resin obtained by reacting a monomer having a group.

  When the (meth) acryloyl polymer has a hydroxyl group as a hydrogen-bonding group, the origin of the hydroxyl group is due to the ring-opening / addition reaction of a monomer having an oxirane structure. It is preferable from the point which can improve the hardness of hardened | cured material and can prevent bleed out. Examples of the monomer having an oxirane structure include those represented by the following formulas (2) to (4).

In (formula (2), ^{R 2} represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, ^{R 3} represents a hydrogen atom or an alkyl group having a carbon number of 1 to 2, p is an integer of 1-8 .)

In the formula (2), preferred as R ² and R ³ are each independently a hydrogen atom or a methyl group. Specific examples of the monomer represented by the formula (2) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (GMA) is available. From the viewpoint of

(In Formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ represents a —CH ₂ O— group or —CH ₂ — group, and R ⁶ represents a hydrogen atom or carbon number. And represents an alkyl group of 1 to 2, q represents an integer of 0 to 7.)

In the formula (3), preferred as R ⁴ and R ⁶ are each independently a hydrogen atom or a methyl group, and preferred as R ⁵ is a —CH ₂ O— group. Specific examples of the monomer represented by the formula (3) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether can be exemplified, among which o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Is preferable from the viewpoint of availability.

(In Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 8)

In the formula (4), R ⁷ is preferably a hydrogen atom or a methyl group. Formula (4)
As a monomer represented by 3,4-epoxycyclohexylmethyl (meth) acrylate can be exemplified. Among them, 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of physical properties of a cured product of the curable resin composition such as hardness.

  The monomer having an oxirane structure used for the production of the (meth) acryloyl polymer is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of monomers constituting the (meth) acryloyl polymer. Preferably, it is 90% by weight or more. A large proportion of the monomer having an oxirane structure in the total amount of monomers constituting the (meth) acryloyl polymer is preferred because the amount of hydroxyl groups that can be introduced and the amount of unsaturated double bonds increase.

  The ring opening / addition reaction of the monomer having an oxirane structure is preferably an addition reaction of a carboxyxyl group, particularly preferably an addition reaction of acrylic acid. Due to the addition reaction of acrylic acid, a resin having a high SP value can be obtained by introducing a hydroxyl group, and an unsaturated double bond can be introduced, so that the curability of the curable resin composition is also improved. This is preferable because it can be performed.

  The resin of component (A) used in the present invention has a weight average molecular weight (Mw) exceeding 13,000. When the weight average molecular weight (Mw) is more than 13,000, phase separation is likely to occur between the component (A) and the component (B), and the uneven structure after the phase separation is increased, resulting in anti-blocking. This is because the properties are improved. From the viewpoint of further enhancing this effect, the weight average molecular weight (Mw) of the component (A) is preferably 15,000 or more. The weight average molecular weight (Mw) of the component (A) is preferably 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less. When the weight average molecular weight of the component (A) resin is within this range, the anti-blocking property tends to be good. In addition, the weight average molecular weight (Mw) of resin can be determined as a conversion value by a polystyrene standard using GPC (gel permeation chromatography). A specific method for measuring the weight average molecular weight of the component (A) is shown in the Examples section below.

  The resin of component (A) used in the present invention has a (meth) acryloyl equivalent (introduced amount of (meth) acryloyl group) of 1.0 mmol / g or more from the viewpoint of improving scratch resistance of the cured product to be formed. Preferably, it is 2.0 mmol / g or more, more preferably 3.0 mmol / g or more. From the viewpoint of preventing gelation, the (meth) acryloyl equivalent is preferably 10.0 mmol / g or less, more preferably 8.0 mmol / g or less, and 6.0 mmol / g or less. Particularly preferred.

  In addition, the component (A) resin used in the present invention preferably has a secondary hydroxyl group equivalent (introduced amount of secondary hydroxyl group) of 1.0 mmol / g or more from the viewpoint of improving antiblocking properties. It is more preferably 0 mmol / g or more, and particularly preferably 3.0 mmol / g or more. In addition, from the viewpoint of compatibility with the later-described polyfunctional (meth) acrylate suitably used as the component (B), the secondary hydroxyl group equivalent is preferably 10.0 mmol / g or less, and 8.0 mmol / g or less. It is more preferable that it is 6.0 mmol / g or less.

  The curable resin composition of the present invention may contain one kind of resin alone as the resin of the component (A), or two or more kinds having different resin types or different functional group equivalents. May be included.

The resin content of the component (A) of the curable resin composition of the present invention is 100 parts by weight in total of the component (A) and the component (B) described later in the curable resin composition of the present invention. 0.5 parts by weight or more, preferably 2 parts by weight or more, more preferably 3 parts by weight or more, and particularly preferably 5 parts by weight or more. Further, it is preferably 25 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less. It is preferable from the viewpoint of developing antiblocking properties when the content of the resin of the component (A) is at least the above lower limit. Moreover, it is preferable that it is below the said upper limit from a viewpoint of making transparency and antiblocking property of a coating liquid or a coating film favorable.

<Component (B)>
Component (B) used in the present invention is a monomer and / or oligomer having a weight average molecular weight (Mw) of less than 2,000 and having one or more (meth) acryloyl groups. As the monomer and / or oligomer of the component (B), a polyfunctional monomer such as a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate can be used. Examples of the oligomer include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and low molecular weight products of the resins mentioned in the above component (A). Among these, a polyfunctional monomer, a urethane (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer are preferable from the viewpoint of high hardness of the obtained cured product or good curability, and polyfunctional (meth) acrylate is particularly preferable. .

  Component (B) has a weight average molecular weight (Mw) of less than 2,000 from the viewpoint of improving the handling property and coating property of the curable resin composition. From the viewpoint of making this effect better, the component (B) preferably has a weight average molecular weight of 1,500 or less, more preferably 1,000 or less, and 800 or less. More preferably. On the other hand, the weight average molecular weight of component (B) is usually 100 or more.

  The polyfunctional (meth) acrylate is a compound having a (meth) acryloyl group and having two or more unsaturated double bonds in one molecule. As such a polyfunctional (meth) acrylate, for example, a polyfunctional (meta) having two or more unsaturated double bonds in one molecule, which is a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate. ) Acrylates. Of the polyfunctional (meth) acrylates, preferably, it has three or more (meth) acryloyl groups in one molecule from the viewpoint of improving the hardness of the resulting cured product and the curability of the curable resin composition. Polyfunctional (meth) acrylates are preferred, and specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate And trimethylolpropane tri (meth) acrylate. Among these, from the viewpoint of improving the hardness of the obtained cured product and the curability of the curable resin composition, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate is preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  Further, the monomer and / or oligomer containing one or more (meth) acryloyl groups of the component (B) used in the present invention preferably contains almost no monomer containing an ethylene oxide (EO) unit in the molecule, More preferably, it does not contain substantially. By not containing a monomer containing an ethylene oxide (EO) unit in the molecule, sufficient hardness can be ensured when a cured product is obtained. Here, “substantially free” means less than 3 parts by weight with respect to 100 parts by weight of the whole component (B).

  The curable resin composition of the present invention may contain only one type of monomer and / or oligomer containing one or more (meth) acryloyl groups as described above as component (B), Moreover, 2 or more types may be included.

  The content of one or more (meth) acryloyl group-containing monomers and / or oligomers, which is the component (B) of the curable resin composition of the present invention, is the above-described component ( It is preferably 75 parts by weight or more, more preferably 85 parts by weight or more, and still more preferably 90 parts by weight or more based on 100 parts by weight of the total of A) and the component (B). Further, it is preferably 99.5 parts by weight or less, more preferably 98 parts by weight or less, still more preferably 97 parts by weight or less, and particularly preferably 95 parts by weight or less. When the content of the component (B) is less than the above lower limit, the performance such as hardness and antiblocking property tends to decrease, and when the content exceeds the above upper limit, the antiblocking property tends to decrease.

<Ingredient (C)>
Component (C) is obtained by reacting a radically polymerizable monomer having an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least an atom other than carbon in the side chain, and A resin having a weight average molecular weight (Mw) of 2,000 to 13,000. When the weight average molecular weight of the component (C) resin is 2,000 or more, the component (C) can be suppressed from bleeding out from the surface after the curable resin composition is cured, , 13,000 or less, it becomes easier to segregate on the surface when the curable resin composition is cured than the component (A), and the slipperiness is improved. The resin of component (C) is obtained by reacting a radically polymerizable monomer having an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least atoms other than carbon in the side chain. Therefore, the resin obtained is derived from this radical polymerizable monomer and has an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least atoms other than carbon in the side chain. Have. Here, the atoms other than carbon in the side chain are not particularly limited, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Among these, an oxygen atom and a nitrogen atom are preferable, and in particular, in the side chain. It preferably has an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least one of an ester bond, an amide bond and an ether bond. A C1-C24 alkyl group has the effect | action which reduces the polarity of resin of a component (C), reduces the surface energy of the hardened | cured material obtained by hardening a curable resin composition, slipperiness, antiblocking Sex can be imparted.

  In the resin of component (C), the alkyl group in the side chain preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms, and preferably 22 or less carbon atoms. It is more preferably 18 or less, still more preferably 12 or less carbon atoms, and particularly preferably 8 or less carbon atoms. This is because when the side chain alkyl group is a long chain, it tends to segregate on the surface of the coating when cured, and the slipperiness tends to improve, but the formation of irregularities due to phase separation is hindered by steric hindrance. In addition, when a short-chain alkyl group is included, it is difficult to segregate the surface, but it is difficult to inhibit phase separation, and the balance between them is obtained.

  The weight average molecular weight of the resin of the component (C) is preferably 2,200 or more from the viewpoint of enhancing the above effect, and is preferably 11,000 or less, more preferably 10,000 or less. Moreover, the weight average molecular weight of resin of a component (C) can be measured by using GPC so that it may mention later.

As the radically polymerizable monomer used as a raw material for the resin of component (C), it is preferable to use a compound having a structure represented by the following formula (1) from the viewpoint of slipperiness and antiblocking property. In addition, by using a compound having the structure represented by the formula (1) as a raw material, the obtained resin can easily introduce the alkyl group having 1 to 24 carbon atoms and can be easily polymerized. It is preferable from the viewpoint that
^{_{CH 2 = C (R 1)}} -C (O) -X-R 2 (1)
(In the above formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent, X is —O— or —NH—.

In the above formula (1), R ¹ is more preferably a hydrogen atom or a methyl group. In Formula (1), R ² is more preferably an alkyl group having 2 or more carbon atoms, more preferably an alkyl group having 4 or more carbon atoms, and an alkyl group having 22 or less carbon atoms. More preferably, it is more preferably an alkyl group having 18 or less carbon atoms, particularly preferably an alkyl group having 12 or less carbon atoms, and most preferably an alkyl group having 8 or less carbon atoms. This is because when the alkyl group of R ² is a long chain, it tends to segregate on the surface of the coating film when the cured product is formed, and the slipping property tends to improve, but it inhibits the formation of irregularities due to phase separation due to steric hindrance. In addition, when a short-chain alkyl group is included, surface segregation is difficult but phase separation is hardly inhibited, and these are balanced. Further, when R ² in the formula (1) has a hydroxyl group, this hydroxyl group is preferable because it acts as a reactive group having active hydrogen, and by introducing this hydroxyl group, the component (C) is made hydrophilic. It is also possible to control the solubility parameter (SP _c ) of the component (C). Further, in the formula (1), X is preferably —O—.

The compound having the structure represented by the above formula (1) may contain a plurality of types at the time of preparing the resin of the component (C). That is, in order to produce the resin of component (C), a plurality of monomers having different portions corresponding to R ¹ and R ² may be used.

  As an example of the compound represented by the formula (1), as the (meth) acrylate monomer in which X in the formula (1) is —O—, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meta ) Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) ) Acrylate, alkyl (meth) acrylate such as behenyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin (meth) acrylate, etc. Hydroxyalkyl (meth) acryl Over doors and the like. Examples of the compound represented by the formula (1) include (meth) acrylamide monomers in which X in the formula (1) is —NH—, such as ethyl (meth) acrylamide, n-butyl (meth) acrylamide, i Alkyl (meth) acrylamides such as butyl (meth) acrylamide and t-butyl (meth) acrylamide; N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N, N-dihydroxyethyl (meth) acrylamide And N-hydroxyalkyl (meth) acrylamide.

The component (C) resin may be copolymerized with a radical polymerizable monomer other than the compound represented by the formula (1). Examples of such monomers include methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, and methoxytetramethylene. Glycol (meth) acrylate, octoxy (poly) ethylene glycol (meth) acrylate, octoxy (poly) propylene glycol (meth) acrylate, octoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, octoxytetramethylene glycol ( Such as meth) acrylate, lauroxy (poly) ethylene glycol (meth) acrylate, stearoxy (poly) ethylene glycol (meth) acrylate, etc. Glycol (meth) acrylic monomer having an alkyl group at the end of (meth) acrylic monomer having a bulky substituent such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Body, (meth) acrylic monomer having carboxyl group such as (meth) acrylic acid, (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, (poly) ethylene glycol / (poly) (Poly) alkylene glycol (meth) acrylate such as propylene glycol (meth) acrylate and tetramethylene glycol (meth) acrylate; 2- (meth) acryloyloxyethyl phosphate having a phosphate group in the molecule (meth) Acrylate, glycy (Meth) acrylate having an epoxy group such as ru (meth) acrylate and methylglycidyl (meth) acrylate; having an oxolane group such as tetrahydrofurfuryl (meth) acrylate and (meth) acryloyloxypropyl-1,3-dioxolane (Meth) acrylic monomer; (meth) acrylic monomer having ethylene urea group such as N- (2- (meth) acryloyloxyethyl) ethyleneurea, dicyclopentyl such as dicyclopentenyloxyethyl (meth) acrylate (Meth) acrylic monomer having a group, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth) acryloyloxyethyltrimethyl Ammonium Examples include amino group-containing (meth) acrylic monomers such as chloride and (meth) acryloyloxyethyldimethylbenzylammonium chloride; styrene monomers such as styrene, p-chlorostyrene, and p-bromostyrene. In the resin of component (C) used in the present invention, the above raw material monomers may be used alone or in a mixture of two or more.

  The reaction time for the radical polymerization reaction is usually 1 to 20 hours, preferably 3 to 12 hours. Moreover, reaction temperature is 40-120 degreeC normally, Preferably it is 50-100 degreeC.

  Examples of the organic solvent that can be used for the radical polymerization reaction include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ethylene glycol dimethyl ether and propylene. Examples include ether solvents such as glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

As the radical polymerization initiator, known radical polymerization initiators can be used. For example, organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyronitrile Azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is usually used in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight as a total of the raw material radical polymerizable monomers.

  Component (C) can be produced by using a radical polymerizable monomer as described above and using a known radical polymerization reaction. The radical polymerization reaction can usually be carried out in an organic solvent in the presence of a radical polymerization initiator. In order to make the weight average molecular weight of the resin of component (C) fall within the above range, for example, polymerization conditions such as polymerization temperature, polymerization initiator amount, chain transfer agent amount, solid content concentration, monomer addition method, etc. Can take a way to control.

  When obtaining the resin of the component (C), it is preferable to use a chain transfer agent because it is easy to control the weight average molecular weight. The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably based on 100 parts by weight of the total amount of radical polymerizable monomers used as raw materials. Is 1.0 to 15 parts by weight.

  As the chain transfer agent, known ones can be used, for example, butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2 -Octyl mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decane Lithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, And thiol compounds such as mercaptosuccinic acid and 2-mercaptoethanesulfonic acid.

  The component (C) resin preferably has a reactive group having active hydrogen. Here, the reactive group having active hydrogen means a functional group containing hydrogen capable of hydrogen bonding with an atom present in another functional group, specifically a hydroxyl group, an amino group, a thiol group, a carboxyl group, Examples thereof include a sulfonic acid group, an amide group, and a phosphoric acid group, and are preferably a hydroxyl group, an amino group, an amide group, and a carboxyl group, and more preferably a hydroxyl group, because they are easily phase-separated (anti-blocking properties are easily exhibited) Particularly preferred is a secondary hydroxyl group. The amount of the reactive group having an active hydrogen that the (meth) acryloyl polymer has is not particularly limited, but is 0.1 or more from the viewpoint of improving the anti-blocking property with good affinity with the component (A). It is preferable that it is 0.3 mmol / g or more, and it is still more preferable that it is 0.5 mmol / g or more. On the other hand, from the viewpoint of reducing the surface energy of the component (A), it is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, and particularly preferably 4.0 mmol / g. preferable.

The method for introducing a hydroxyl group as a reactive group having active hydrogen is not particularly limited, but hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (poly) propylene glycol- ( (Meth) acrylates having hydroxyl groups such as poly) ethylene glycol mono (meth) acrylate, tetramethylene glycol- (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol- (poly) butylene glycol mono (meth) acrylate A method of polymerizing using a monomer as a raw material, a method of producing a polymer obtained by polymerizing a monomer having an oxirane structure, a ring-opening / addition reaction of the polymer, and a polymer obtained by polymerizing a monomer having an oxirane structure. A polymer is produced by polymerizing a monomer having a ring opening / addition reaction with an oxirane structure such as a carboxyl group or an amino group, and a method in which a monomer having a hydroxyl group such as lactic acid is subjected to a ring opening / addition reaction. In addition, examples thereof include a method in which a monomer having an oxirane structure undergoes ring-opening / addition reaction.

Component (C) can be produced by the method described above, but commercially available products can also be used as they are. Examples of commercially available products include “Polyflow No.75”, “Polyflow No.77”, “Polyflow No.90”, “Polyflow No.50EHF”, “Polyflow No.85HF”, “Polyflow No.95”, “Polyflow No.99C”, “Polyflow”. "No. 7""Polyflow No. 54N""PolyflowKL-800" (all manufactured by Kyoeisha Chemical Co., Ltd.), "LF1984""LF1983""LHP90""LHP95""UVX-271""UVX-272""UVX-" 190 "" UVX-36 "" UVX-35 "" UVX-3750 "" UVX-189 "(all manufactured by Enomoto Kasei)," BYK-350 "" BYK-352 "" BYK-354 "" BYK-356 ""BYK-361N""BYK-381""BYK-392""BYK-394""BY -3441 "," BYK-3440 "(both BYK Co., Ltd.), and the like. Among these, “Polyflow No. 75”, “Polyflow No. 77”, “BYK-361N”, and “BYK-3441” are preferable, and “Polyflow No. 75” and “Polyflow No. 77” are more preferable.

  In the curable resin composition of the present invention, the content of the component (C) is preferably 0.001 part by weight or more with respect to 100 parts by weight of the total amount of the component (A) and the component (B). More preferably 0.01 parts by weight or more, still more preferably 0.1 parts by weight or more, while preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight. Or less. When the content of the component (C) is not less than the above lower limit value, it is preferable from the viewpoint of imparting slipperiness necessary for improving the antiblocking property, and on the other hand, when it is not more than the above upper limit value, the surface hardness is reduced. It is preferable from the viewpoint that it can be suppressed.

<Component (D)>
The curable resin composition of the present invention further comprises a hard coat layer having good antiblocking properties while maintaining high hardness, containing inorganic particles having an average primary particle size of 1 μm or less as the component (D). It is preferable at the point which can provide the curable resin composition which can be formed.

  That is, in addition to being capable of phase separation by containing a highly polar resin of component (A) and one or more (meth) acryloyl group-containing monomers and / or oligomers of component (B), inorganic By adding the particles together, when cured, inorganic particles are also present near the surface together with the phase separated resin. The presence of the resin and inorganic particles allows the curable resin composition of the present invention to form moderate irregularities on the surface when it is used as a hard coat layer, and to exhibit excellent antiblocking properties.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. Among these, silica is preferable. Moreover, the inorganic particle mentioned above may use only 1 type, and may be used in combination of 2 or more type.

  The average primary particle diameter of the inorganic particles is 1 μm or less, preferably 200 nm or less, and more preferably 100 nm or less. The lower limit of the average primary particle diameter of the inorganic particles is not particularly limited, but is usually 5 nm or more, preferably 10 nm or more. It is preferable to use inorganic particles having an average primary particle size of the upper limit or less from the viewpoint of preventing sedimentation due to the weight of the particles and maintaining the storage stability of the coating liquid of the curable resin composition.

  On the other hand, the movement of the inorganic particles having an average primary particle diameter in the above range in the coating liquid of the curable resin composition is governed by thermal diffusion rather than sedimentation by gravity, so the inorganic particles are coated with the curable resin composition. It can be stably dispersed in the liquid, and is effectively present on the surface when a hard coat layer is formed. Moreover, there exists a tendency for an optical characteristic to become favorable, so that the average primary particle diameter of an inorganic particle is small.

  In addition, the average primary particle diameter of the inorganic particle in this invention says the value which averaged the magnitude | size of the particle | grains observed with electron microscopes, such as TEM.

The inorganic particles of the component (D) are curable resin of the present invention as inorganic particles surface-modified with the resin of the component (A) as shown in the examples described later in terms of improving antiblocking properties and hardness. It is preferable to mix | blend with a composition. In order to produce inorganic particles surface-modified with such a resin, for example, the resin and the inorganic particles are mixed in the presence of a silane coupling reaction catalyst such as acid, base, and acetylacetone aluminum at 25 to 120 ° C. for 1 to 24. The method of making it react for about hours is mentioned.

  The content of the component (D) in the curable resin composition of the present invention is 0. 0 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) in the curable resin composition of the present invention. It is preferably 05 parts by weight or more, more preferably 0.5 parts by weight or more, still more preferably 0.7 parts by weight or more, and particularly preferably 1 part by weight or more. Further, it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, further preferably 5 parts by weight or less, particularly preferably 3 parts by weight or less, and 2 parts by weight or less. It is particularly preferred that there is. It is preferable that the content of the component (D) is not less than the above lower limit value because the effect of using inorganic particles can be sufficiently obtained, and it is preferably not more than the above upper limit value from the viewpoint of transparency.

<Polymerization initiator>
The curable resin composition of the present invention preferably contains a polymerization initiator in order to be cured by active energy rays. The polymerization initiator is usually 0.01 parts by weight or more, preferably 0.1 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B) in the curable resin composition of the present invention. Part or more, more preferably 1 part by weight or more, and usually 20 parts by weight or less, preferably 10 parts by weight or less.

  As the polymerization initiator, a photopolymerization initiator is preferable. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [ 4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) -butanone-1. These polymerization initiators may be used alone or in a combination of two or more.

<Other ingredients>
The curable resin composition of the present invention may contain components other than the aforementioned components (A) to (D) and the polymerization initiator as long as the effects of the present invention are not impaired. Other components that can be contained in the curable resin composition of the present invention include a solvent for uniformly mixing each component, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, and the like. Various conventional additives and the like can be mentioned.

  The solvent is not particularly limited, and is appropriately selected in consideration of the components (A), (B), (C), the material of the base material serving as the base, the coating method of the composition, and the like. Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol. Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol; and the like; dichloromethane, halogenated solvents such as chloroform.

These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  There is no restriction | limiting in particular in the usage-amount of a solvent, It considers the applicability | paintability of the curable resin composition prepared, the viscosity and surface tension of a liquid, the compatibility of solid content, etc. suitably. Usually, the curable resin composition of the present invention is prepared as a coating solution having a solid content of 20 to 99.9% by weight, particularly 30 to 80% by weight, using the solvent described above. In addition, here, solid content in the curable resin composition of this invention refers to the sum total of components other than the solvent contained in the curable resin composition of this invention.

<Method for preparing curable resin composition>
The preparation method of the curable resin composition of this invention is not specifically limited, For example, it combines with a component (D), a solvent, a polymerization initiator, an additive, etc. further as needed by component (A)-(C). It can be prepared by mixing. As described above, when component (D) is used, component (D) is preferably used in a form that is surface-modified with the resin of component (A).

[Hardened product / Laminate]
A cured product can be obtained by curing the curable resin composition of the present invention. In particular, the present invention comprises a cured layer formed by curing the curable resin composition of the present invention on the substrate by applying and curing the curable resin composition of the present invention on the substrate. It can be set as the laminated body of invention. Moreover, the hard coat film (hard coat layer) of this invention can be obtained by apply | coating the curable resin composition of this invention on a base material etc. in this way, and making it harden | cure in a film form. In addition, the hard coat film of the present invention is laminated on the other resin film by applying the curable resin composition of the present invention on the other resin film as a substrate and curing it to form a hard coat film. A film laminate is obtained.

  As the base material for molding the hard coat film, various resin films and resin plates can be used. Examples of resin films include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, and polycarbonate film. Polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film and the like can be used. Examples of resin plates include acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate butyrate cellulose plates, polyether sulfone plates, polyurethane plates, polycarbonate plates, polysulfone plates, polyether plates, polymethyl. Examples include a pentene plate, a polyether ketone plate, and a (meth) acrylonitrile plate. Moreover, glass etc. can also be used as needed. These base materials are all excellent in transparency and are preferable for application to a display device described later. In addition, although the thickness of a base material can be selected timely according to a use, a thing of about 25-1,000 micrometers is generally used.

  The coating method of the curable resin composition of the present invention is not particularly limited. For example, dip coating method, air knife coating method, curtain coating method, spin coating method, roller coating method, bar coating method, wire bar coating method, gravure coating method, extrusion coating method (US Pat. No. 2,681,294) It can apply by the method of.

  The thickness of the hard coat film (hard coat layer) is not particularly limited and can be appropriately set in consideration of various factors so that the film thickness after drying is usually 0.01 to 20 μm. A curable resin composition can be applied.

  The coating film applied and formed on the substrate may be phase-separated at room temperature, or may be phase-separated in advance by drying the composition before curing. When drying or heating before hardening the applied coating film, it is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, preferably 0.01 to 30 minutes, more preferably 0.1 to 10%. The components (A) and (B) can be phase-separated by drying for a minute. Drying before curing and phase separation in advance is preferable because the solvent in the coating film having fine irregularities can be effectively removed and irregularities of a desired size can be provided on the cured film.

As another method of phase separation before curing, a method of irradiating the coating film with active energy rays to cause phase separation can also be used. As the active energy ray to be irradiated, for example, light having an exposure amount of 0.1 to 3.5 J / cm ² , preferably 0.5 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. For example, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or the like is used as the polymerization initiator, the irradiation light is irradiated with light having a wavelength near 310 nm or 360 nm. It is preferable to irradiate light having a wavelength near 360 nm. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing occur. Irradiating light to cause phase separation is preferable because unevenness of the surface shape due to drying unevenness of the solvent contained in the curable resin composition can be avoided.

A hard coat film having fine irregularities is formed by curing a coating film obtained by application of the curable resin composition or a coating film dried after application. Curing can be performed by irradiating the coating film with light using a light source that emits an active energy ray having a wavelength as required. In addition, the light irradiation for hardening has an integrated light quantity of 100 mJ / cm ² or more and 20
It is preferable to irradiate with 2,000 mJ / cm ² or less. As the light source, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.

<Physical properties>
The hard coat film of the present invention has good antiblocking properties. The good antiblocking property of the hard coat film of the present invention is due to imparting good irregularities to the surface by phase separation of the component (A) and the component (B) in the hard coat layer.

Therefore, for example, the surface roughness (Ra) of a hard coat film formed with a film thickness of 3 μm by the curable resin composition of the present invention is preferably 1 nm or more, and more preferably 3 nm or more. The upper limit of the surface roughness Ra is not particularly limited, but is usually 200 nm or less. The surface roughness (Ra) means arithmetic average roughness (Ra), and is a parameter defined in JIS B-0601-2001. For example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratory, or ( Using a color 3D laser microscope manufactured by Keyence Corporation, JIS
It can be measured according to B-0601-2001.

  Moreover, Sm of the hard coat film formed with the film thickness of 3 μm by the curable resin composition of the present invention is preferably 0.001 μm or more and 10 μm or less, and more preferably 0.005 μm or more and 5 μm or less. Preferably, it is 0.01 μm or more and 3 μm or less. Here, Sm is the average length of the roughness curve elements on the surface, and is generally referred to as the average interval between the peaks and valleys of the roughness curve or the average interval between the irregularities. Sm can be measured in accordance with JIS B-0633 using, for example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratories or a color 3D laser microscope manufactured by Keyence Corporation.

  Moreover, the hard coat film obtained by the curable resin composition of this invention has favorable hardness. For example, the pencil hardness measured according to JIS K-5600 for a hard coat film formed with a film thickness of 3 μm by the curable resin composition of the present invention is preferably H or higher, and preferably 2H or higher. More preferred.

  In addition, the hard coat film obtained by the curable resin composition of the present invention has good transparency. For example, the total light transmittance of the hard coat film formed with a film thickness of 3 μm by the curable resin composition of the present invention is 85% or more, preferably 90% or more, and haze is 2%. 0.0% or less, preferably 1.8% or less, more preferably 1.5% or less, still more preferably less than 1.0%, and particularly preferably less than 0.5%.

The total light transmittance (Tt (%)) of the hard coat film is calculated by the following equation by measuring the incident light intensity (T0) to the hard coat film and the total transmitted light intensity (T1) transmitted through the hard coat film. The
Tt (%) = (T ₁ / T ₀ ) × 100
The total light transmittance can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).
The haze of the hard coat film can be calculated from the following formula in accordance with JIS K-7136 (2000).
H (%) = (Td / Tt) × 100
H: Haze (cloudiness value) (%)
Td: Diffuse light transmittance (%)
Tt: Total light transmittance (%)
The haze can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).

<Roll film laminate>
The film laminate of the present invention formed by forming the hard coat film of the present invention on another resin film exhibits good antiblocking properties when wound into a roll, and is preferable for such an embodiment. Applied. Such a roll-shaped film laminate is formed by applying and curing the curable resin composition of the present invention on a resin film as a base material to form the hard coat film of the present invention and winding it into a roll. Manufactured.

<Display device>
The laminate formed by forming a hard coat layer on a substrate with the curable resin composition of the present invention can be applied to a display device using this laminate together with a light source. In this case, it is preferable that the base material which forms a hard-coat layer is a translucent base material. As a translucent base material, what was mentioned above as a base material which forms a hard coat film can be used. The light source is preferably disposed on the back surface of the base material, that is, the surface opposite to the hard coat layer forming surface of the base material, and emits light toward the base material from there.

  The light source that can be combined with the laminate on which the hard coat layer is formed is not particularly limited as long as it can emit light, and examples thereof include a light emitting diode, a cold cathode tube, a hot cathode tube, and an EL element. However, a liquid crystal module, a backlight unit, or the like may be used.

The liquid crystal module includes the light source, and further has a configuration in which polarizing plates / liquid crystal cells / polarizing plates are arranged in this order. The liquid crystal cell is not particularly limited as long as it is generally used in a liquid crystal display device. For example, TN (Twisted Nematic) type liquid crystal cell, STN (Super Twisted Nematic) type liquid crystal cell, H
AN (Hybrid Alignment Nematic) type liquid crystal cell, IPS (In
Examples thereof include a plane switching (LCD) type liquid crystal cell, a VA (vertical alignment) type liquid crystal cell, an MVA (multiple vertical alignment) type liquid crystal cell, and an OCB (optically compensated bend) type liquid crystal cell. Such a display device may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusing plate, a light diffusing sheet, a light collecting sheet, a reflecting plate, and the like.

  The display device using the laminate of the present invention includes a liquid crystal display device (liquid crystal display), an LED (light emitting diode display), an ELD (electroluminescence display), a VFD (fluorescent display), a PDP (plasma display panel), and the like. It can be applied to flat panel displays. Moreover, since the curable resin composition of this invention used for preparation of a display apparatus also has a weather resistance in addition to antiblocking property, use of these display apparatuses outdoors is attained. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of posting information such as advertisements.

  In addition, the outdoor or semi-outdoor use of the display device using the laminate of the present invention includes a touch panel, which has a mechanism for operating the device by pressing the display on the screen, for example, Bank ATMs, vending machines, personal digital assistants (PDAs), photocopiers, facsimiles, game machines, information displays installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multiple installed in convenience stores) This is useful in a functional terminal), a mobile phone, a railway vehicle monitoring device, and the like.

  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.

[Evaluation method]
The evaluation method of the coating liquid (curable resin composition) prepared in the following Examples and Comparative Examples and the produced cured film (hard coat film) is as follows.

<Appearance of coating liquid>
The obtained coating liquid was visually observed and evaluated according to the following criteria.
○: The coating solution is transparent ×: The coating solution is cloudy

<Transparency (haze value)>
Transparency after leaving the obtained film laminate in a temperature-controlled room at 23 ° C. and 60% relative humidity for 12 hours was evaluated by haze value (H%) according to JIS K-7136 (2000). By subtracting the value (H%), the haze value (H%) of the cured film was obtained and evaluated according to the following criteria.
○: Haze value of cured film is less than 0.5% Δ: Haze value of cured film is 0.5% or more and less than 1.0% ×: Haze value of cured film is 1.0% or more

<Anti-blocking property>
Two film laminates are prepared, and the cured film surfaces are superposed at 23 ° C. and a relative humidity of 60%, and after the load of about 1 kg is applied by finger pressure, the cured film surfaces have slipperiness. The anti-blocking property was evaluated according to the following criteria.
◎: Can be easily slid ○: Can be slid and no sound is produced △: Can be slid but produces sound ×: Cured film surfaces are in close contact with each other Things that can't slide between surfaces

<Pencil hardness>
Pencil hardness was measured with respect to the cured film of the obtained film laminated body according to JIS K-5600.

[Component (A) and Component (D)]
The component (A) used in the following Examples and Comparative Examples and the component (D) inorganic particles surface-modified with the component (A) were synthesized by the following method.

A-1:
In a flask equipped with a thermometer, stirrer and reflux condenser, 157.3 g propylene glycol monomethyl ether, 98.0 g glycidyl methacrylate, 1.0 g methyl methacrylate, 1.0 g ethyl acrylate, 1.9 g mercaptopropyltrimethoxysilane, and Add 1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)
For 3 hours. Thereafter, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 138.1 g of propylene glycol monomethyl ether and 0.45 g of p-methoxyphenol were added and 100 ° C. Until heated. Next, 50.7 g of acrylic acid and 3.08 g of triphenylphosphine were added and reacted at 110 ° C. for 6 hours, thereby having an acryloyl group and a methoxysilyl group, and a weight average molecular weight (Mw) of 20,000. An acryloyl copolymer having an acryloyl equivalent (introduction amount of acryloyl group) of 4.47 mmol / g and a secondary hydroxyl group equivalent (introduction amount of secondary hydroxyl group) of 4.47 mmol / g was obtained. The SP value of this acryloyl copolymer was 17.8. Hereinafter, this acryloyl copolymer is referred to as “A-1”.

A-2:
In a four-necked flask, 3.75 parts by weight of the acryloyl copolymer resin (A-1) obtained in Synthesis Example 1 and (D-1) colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: MEK-ST (average primary particle size 10 -15 parts by weight (catalog value)) 1.25 parts by weight were added, 0.005 parts by weight of acetylacetone aluminum was added as a catalyst for the silane coupling reaction, and the reaction was carried out at 70 ° C. for 4 hours to obtain an acryloyl copolymer (A-1 The surface-modified colloidal silica (D-1) was prepared, hereinafter referred to as “A-2”.

<Weight average molecular weight of component (A)>
About A-1, the weight average molecular weight was measured on condition of the following by GPC method. The value of each weight average amount is as shown in Table 1.
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel Super H1000 + H2000 + H3000” manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / built-in)
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

[Component (B)]
In the following Examples and Comparative Examples, dipentaerythritol hexaacrylate (SP value 12.1) was used as the component (B).

[Component (C)]
In the following Examples and Comparative Examples, details of the compounds used as the component (C) are as follows. C-1 to C-6, c-3 and c-4 were synthesized, and c-1 and c-2 were used commercially. The abbreviations used below are as follows.
MEK: methyl ethyl ketone DT: dodecanethiol EA: ethyl acrylate (in the above formula (1), R ¹ is a hydrogen atom and R ² is an ethyl group)
BMA: butyl methacrylate (compound in which R ¹ is a methyl group and R ² is a butyl group in the formula (1))
HEA: hydroxyethyl acrylate (in the formula (1), R ¹ is a hydrogen atom and R ² is a hydroxyethyl group)
BA: butyl acrylate (in the above formula (1), R ¹ is a hydrogen atom and R ² is a butyl group)
LMA: Lauryl methacrylate (a compound in which R ¹ is a methyl group and R ² is a dodecyl group in the above formula (1))
HEMA: hydroxyethyl methacrylate (in the above formula (1), R ¹ is a methyl group, R ² is a hydroxyethyl group)
EHA: 2-ethylhexyl acrylate (compound in which R ¹ is a hydrogen atom and R ² is a 2-ethylhexyl group in the formula (1))

<C-1 to C-5 (for Examples)>
C-1:
In a flask equipped with a thermometer, stirrer and reflux condenser, put 250.33 g of MEK, 1.50 g of DT, 25.00 g of EA, 25.00 g of BMA, and 2.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile). , 25.00 g of EA, 25.00 g of BMA, and 10.40 g of MEK were added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 2.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 10.80 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. Thus, C-1 having an alkyl group (carbon number: 2 or 4) in the side chain, a weight average molecular weight of 7,800, and an SP value of 10.4 (calculated value by the federals method) was obtained.

C-2:
A flask equipped with a thermometer, a stirrer and a reflux condenser is charged with 243.33 g of MEK, 15.00 g of DT, 25.00 g of EA, 25.00 g of BMA and 1.20 g of 2,2′-azobis (2,4-dimethylvaleronitrile). , 25.00 g of EA, 25.00 g of BMA and 21.40 g of MEK were added dropwise over 1.5 hours, and the mixture was reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. Thus, C-2 having an alkyl group (carbon number: 2 or 4) in the side chain, a weight average molecular weight of 2,600, and an SP value of 10.2 (calculated value by the federals method) was obtained.

C-3:
In a flask equipped with a thermometer, stirrer and reflux condenser, MEK 243.33 g, DT 15.00 g, HEA 9.00 g, BA 20.00 g, EHA 21.00 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 1 .20 g was added, and a mixture of HEA 9.00 g, BA 20.00 g, EHA 21.00 g and MEK 21.40 g was added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.97 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. And having an alkyl group (carbon number: 2, 4 or 7), a weight average molecular weight of 3,400, an amount of active hydrogen-containing reactive group of 2.2 mmol / g, and an SP value of 10.8 (according to the federals method) C-3 of (calculated value) was obtained.

C-4:
In a flask equipped with a thermometer, stirrer and reflux condenser, MEK 131.67 g, DT 5.00 g, EA 20.00 g, BMA 20.00 g, HEMA 10.00 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 1 .20 g was added, and a mixture of EA 20.00 g, BMA 20.00 g, HEMA 10.00 g and MEK 21.40 g was added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. And having an alkyl group (carbon number: 2 or 4), a weight average molecular weight of 6,100, an active hydrogen-containing reactive group amount of 2.1 mmol / g, an SP value of 11.0 (calculated value by the federals method) C-4 was obtained.

C-5:
In a flask equipped with a thermometer, stirrer and reflux condenser, MEK 131.67 g, DT 5.00 g, EA 20.00 g, BMA 20.00 g, LMA 10.00 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 1 .20 g was added, and a mixture of EA 20.00 g, BMA 20.00 g, LMA 10.00 g, and MEK 21.40 g was added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. Thus, C-5 having an alkyl group (carbon number: 2, 4 or 12), a weight average molecular weight of 6,400, and an SP value of 10.2 (calculated value by the federals method) was obtained.

C-6:
In a flask equipped with a thermometer, stirrer and reflux condenser, MEK 131.67 g, DT 5.00 g, HEA 9.00 g, BA 31.00 g, LMA 10.00 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 1 .20 g was added, and a mixture of HEA 9.00 g, BA 31.00 g, LMA 10.00 g and MEK 21.40 g was added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. And having an alkyl group (carbon number: 2, 4 or 12), a weight-average molecular weight of 7,100 and an amount of reactive hydrogen-containing reactive group of 1.9 mmol / g, SP value of 11.1 (calculated value by Fedors method) C-6 was obtained.

<C-1 to c-4 (for comparative example)>
c-1:
Product name “DMH-20” manufactured by Nippon Emulsifier Co., Ltd.
Compound represented by the following formula (5)

分子量：２４０
ＳＰ値：１１．３（フェドアーズ法による算出値）
活性水素を有する反応性基量：８．５ｍｍｏｌ／ｇ

Molecular weight: 240
SP value: 11.3 (calculated value by the federals method)
Amount of reactive group having active hydrogen: 8.5 mmol / g

c-2:
Butyl acrylate (monomer)
(In the formula (1), R ¹ is a hydrogen atom and R ² is a butyl group)
Molecular weight: 130
SP value: 9.2 (calculated value by the Fedodors method)

c-3:
A flask equipped with a thermometer, stirrer and reflux condenser was charged with 131.67 g of MEK, 9.00 g of HEA, 20.00 g of BA, 21.00 g of EHA and 1.20 g of 2,2′-azobis (2,4-dimethylvaleronitrile). , HEA 9.00 g, BA 20.00 g, EHA 21.00 g and MEK 21.40 g were reacted at 65 ° C. for 3 hours while dropping over 1.5 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. And having an alkyl group (carbon number: 2, 4, 7, or 12) in the side chain, a weight average molecular weight of 21,600, an amount of active hydrogen-containing reactive group of 2.3 mmol / g, SP value of 11.1. C-3 of (calculated value by the feder's method) was obtained.

c-4:
A flask equipped with a thermometer, stirrer and reflux condenser was charged with 131.67 g of MEK, 25.00 g of EA, 25.00 g of BA and 1.20 g of 2,2′-azobis (2,4-dimethylvaleronitrile), and 25.00 g of EA. , 25.00 g of BA and 21.40 g of MEK were added dropwise over 1.5 hours, and reacted at 65 ° C. for 3 hours. Thereafter, 0.62 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is further added and reacted for 3 hours, and then 8.90 g of MEK and 0.50 g of p-methoxyphenol are added and heated to 100 ° C. Thus, c-4 having an alkyl group (carbon number: 2 or 4) in the side chain and a weight average molecular weight of 19,900 and an SP value of 10.4 (calculated value by the federals method) was obtained.

<Calculation of functional group amount having active hydrogen>
The amount of reactive groups having active hydrogen of the above compound used as component (C) was determined by the following method.
2 to 6 g of isophorone diisocyanate (IPDI), 0.5 to 10 g of sample, 0.01 to 0.05 g of dioctyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-810) are thoroughly mixed and mixed at 70 ° C. For 1 hour. An Erlenmeyer flask was charged with 1 to 2 g of the reaction product and 20 mL of a 0.5 mol / L dibutylamine toluene solution, diluted with 100 mL of acetone, and reacted at 25 ° C. for 30 minutes. Then, the amount of hydroxyl groups was titrated with 0.5 mol / L hydrochloric acid aqueous solution. Moreover, except having not put IPDI in the Erlenmeyer flask, it titrated similarly and calculated | required the blank. And the quantity of the active hydrogen containing reactive group was computed by the following formula | equation. Table 1 shows the amounts of active hydrogen-containing reactive groups determined. Moreover, it shows in Table-2 about the quantity of the reaction material of IPDI, the sample, dioctyltin dilaurate, and IPDI used for the measurement.
(NCO% after treatment)
= {(B1-A1) × 0.5 × 42.02} / (1 × 1000) × 100
A1: Amount of hydrochloric acid aqueous solution required for titration of IPDI-containing solution (mL)
B1: Amount of hydrochloric acid aqueous solution required for titration of blank solution containing no IPDI (mL)
(Active hydrogen-containing reactive group amount (mmol / g))
= 1000 / sample amount × (4202 × (IPDI amount) /111.14
-(NCO% after treatment) x (total charge)) / 4202 / (sample solid content) x 100
42.02 = (NCO molecular weight)
111.14 = (NCO equivalent of IPDI)
When the sample was dissolved in the solvent having an active hydrogen-containing reactive group, the amount of the active hydrogen-containing reactive group in the solvent was obtained by calculation and subtracted from the above value.

<Weight average molecular weight of component (C)>
The weight average molecular weights of C-1 to C-6, c-3 and c-4 were measured by the same method as the weight average molecular weight of A-1.

<Example 1>
(Manufacture of curable resin composition)
In a four-necked flask, the component (A) containing the component (D) is 5.0 parts by weight of the resin (A-2), the component (B) is 95.0 parts by weight of dipentaerythritol hexaacrylate, (C) After adding 0.5 parts by weight of BYK377, 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure 184” manufactured by BASF) is added as a polymerization initiator, and further 157.5 parts by weight of methyl ethyl ketone. Was added to obtain a curable resin composition. Table 3 shows parts by weight of each component based on a total of 100 parts by weight of the weight of the component (A) and the weight of the component (B).

(Coating process)
A bar coater was used for the obtained curable resin composition on a transparent biaxially stretched PET film having a thickness of 188 μm (haze value 0.8%; manufactured by Mitsubishi Plastics, Inc., trade name: Diafoil (registered trademark) O321E). The coating film thickness after drying was 2 to 3 μm and dried by heating at 80 ° C. for 1 minute.

(Curing process)
EYE UV METER UVPF-A1, PD365 made by Eye Graphic Co., Ltd. is used at a position of 15 cm under the light source, using a high pressure mercury lamp with a power density of 120 W / cm as a light source. Then, the cured film was obtained by irradiating with ultraviolet rays so as to obtain an integrated light quantity of 200 mJ / cm ² .

(Evaluation)
The prepared curable resin composition (coating liquid) and the formed cured film (hard coat film) were evaluated as described above, and the results are shown in Table-3.

<Examples 2-7, Comparative Examples 1-6>
A curable resin composition was obtained in the same manner as in Example 1 except that the blending composition was changed as shown in Table-3. Various evaluations were performed in the same manner as in Example 1.

  In addition, when the coating-film external appearance of the cured film of the film laminated body obtained in Examples 1-7 and Comparative Examples 1-6 was visually observed, there were few defects and it was very excellent.

[Evaluation results]
From Table-3, Examples 1-7 which correspond to this invention have the anti-blocking property superior to Comparative Examples 1-6, having the coating liquid external appearance, transparency, and hardness equivalent to Comparative Examples 1-6. It can be seen that That is, according to the present invention, it can be seen that a cured film having high hardness and excellent antiblocking property, and further excellent coating film appearance and transparency can be formed.

Claims (16)

The following component (A), component (B) and component (C) are included, and the solubility parameter (SP _A ) of the component ( _A ) is higher than the solubility parameter (SP _B ) of the component (B). Curable resin composition.
Component (A): Resin having a weight average molecular weight (Mw) of more than 13,000 Component (B): Weight average molecular weight (Mw) of less than 2,000 and having one or more (meth) acryloyl groups Monomer and / or oligomer Component (C): A radically polymerizable monomer having an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent via at least an atom other than carbon in the side chain is polymerized. Resin obtained and having a weight average molecular weight (Mw) of 2,000 to 13,000   The curable resin composition according to claim 1, comprising 0.5 to 25% by weight of component (A) with respect to the total amount of component (A) and component (B).   The curable resin composition of Claim 1 or 2 which contains 0.001-20 weight part of components (C) with respect to a total of 100 weight part of a component (A) and a component (B).   The curable resin composition according to any one of claims 1 to 3, wherein the component (A) is a resin having a hydrogen bonding group and a (meth) acryloyl group.   The curable resin composition according to claim 4, wherein the hydrogen bonding group is a hydroxyl group.   The curable resin composition according to any one of claims 1 to 5, wherein the component (B) is a polyfunctional (meth) acrylate having two or more unsaturated double bonds in one molecule.   The curable resin composition according to claim 6, comprising a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule as the polyfunctional (meth) acrylate. The curable resin composition according to any one of claims 1 to 7, comprising a compound represented by the following formula (1) as the radical polymerizable monomer.
^{_{CH 2 = C (R 1)}} -C (O) -X-R 2 (1)
(In the above formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 24 carbon atoms which may have a hydroxyl group as a substituent, X is —O— or —NH—.   The curing according to any one of claims 1 to 8, wherein the component (C) has a reactive group having active hydrogen, and the amount of the reactive group is 0.1 to 8.0 mmol / g. Resin composition. Furthermore, the curable resin composition of any one of Claims 1 thru | or 9 containing the following component (D).
Component (D): inorganic particles having an average primary particle size of 1 μm or less   The curable resin composition according to claim 10, comprising 0.05 to 30 parts by weight of the component (D) with respect to 100 parts by weight of the total of the component (A) and the component (B).   The curable resin composition according to any one of claims 1 to 11, wherein the component (A) is obtained by a ring-opening / addition reaction of a compound having an oxirane structure.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 12.   The laminated body formed by forming the hardened layer formed by hardening | curing the curable resin composition of any one of Claims 1 thru | or 12 on a base material.   A hard coat film obtained by curing the curable resin composition according to claim 1.   The film laminated body formed by laminating | stacking the hard coat film of Claim 15 with another resin film.