JP6364719B2 - Curable resin composition, cured product, laminate, hard coat film and film laminate - Google Patents

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.

  Some thermoplastic resin films represented by polyethylene terephthalate (PET) film have a hard coating with excellent hardness and slipperiness. A film on which such a hard coating has been performed may be wound into a roll during storage because of its simplicity in forming and processing into a final product. Thus, when it rolls in roll shape, there exists a problem that the overlapping surfaces block.

  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, a resin that is separately contained with respect to the solubility parameter (SP value) of a specific unsaturated double bond-containing monomer containing an alkylene oxide unit having 2 to 4 carbon atoms. By setting the solubility parameter (SP value) of the resin low, 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 as follows.

[1] The following components (A), (B), and (C) are included, and the content of the resin of component (A) is 0. 0 with respect to a total of 100 parts by weight of component (A) and component (B). 5 parts by weight or more and 25 parts by weight or less, and the content of component (C) is 0.001 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight in total of component (A) and component (B), A curable resin composition, wherein the solubility parameter (SP value) of the component (A) is 5.7 or more higher than the solubility parameter (SP value) of the component (B).
Component (A): The weight average molecular weight (Mw) is 5,000 or more, and one or more resin components (B) having a (meth) acryloyl group: the weight average molecular weight (Mw) is less than 5,000, It has two or more unsaturated double bonds in one molecule and a polyfunctional monomer and / or oligomer component having two or more (meth) acryloyl group (C): a silicon atom-containing and / or fluorine atom and, and the amount of the reactive group containing active hydrogen is at 0.9 mmol / g or more and a weight average molecular weight (Mw) of 14, compound is 000～40,000

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

[ 3 ] The curable resin composition according to [ 2 ], wherein the hydrogen bonding group is a hydroxyl group.

[ 4 ] The curable resin according to any one of [1] to [ 3 ], wherein the component (B) is a polyfunctional (meth) acrylate having two or more unsaturated double bonds in one molecule. Composition.

[ 5 ] The curable resin composition according to [ 4 ], including a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule as the polyfunctional (meth) acrylate.

[ 6 ] The curable resin composition according to any one of [1] to [ 5 ], including a polyether-modified silicone oil and / or a polyester-modified silicone oil as the component (C).

[ 7 ] The curable resin composition according to any one of [1] to [ 6 ], including the compound containing a fluorine atom as the component (C).

[ 8 ] The solubility parameter (SP value) of the component (A) is from 14.0 to 20.0, and the solubility parameter (SP value) of the component (B) is from 8.0 to 14.0. The curable resin composition according to any one of [1] to [ 7 ], which is:

[ 9 ] The curable resin composition according to any one of [1] to [ 8 ], wherein the component (C) is a polyether-modified hydroxyl group-containing polydimethylsiloxane.

[ 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.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

  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 includes the following components (A), (B) and (C), and the solubility parameter (SP value) of the component (A) is the solubility parameter of the component (B). It is characterized by being higher than (SP value). The following component (A) may include those corresponding to the component (C), but such a component is regarded as the component (C).
Component (A): One or more resins having a weight average molecular weight (Mw) of 5,000 or more Component (B): Weight average molecular weight (Mw) of less than 5,000, and one or more (meth) Monomer and / or oligomer having acryloyl group Component (C): a reactive group containing a silicon atom and / or a fluorine atom and containing active hydrogen (hereinafter sometimes referred to as “active hydrogen-containing reactive group”) Compound whose amount is 0.9 mmol / g or more

<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, for example, when the compound of component (C) has both a low polarity silicon atom and / or fluorine atom and a high polarity active hydrogen-containing reactive group, component (C) and component (A) It segregates on the coating surface without hindering phase separation with the component (B). Thereby, since the surface energy of a coating film can be reduced and slipperiness can be imparted in addition to surface irregularities, it is presumed that the antiblocking property is 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). When the solubility parameter cannot be obtained by the above method, for example, the sample does not dissolve in acetone, the estimation is performed by the method proposed by Fedors et al. 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 composition of the present invention, the SP value of the component (A) is higher than the SP value of the component (B), more preferably the SP value of the component (A) is less than the SP value of the component (B). It is preferably 5 or more, particularly preferably 1.0 or more. Further, the SP value of the resin of the component (A) used in the present invention is preferably 14.0 or more, more preferably 16.0 or more, and preferably 20.0 or less, 18. More preferably, it is 0 or less. On the other hand, the SP value of the monomer and / or oligomer containing one or more (meth) acryloyl groups of the component (B) used in the present invention is preferably 8.0 or more, and 10.0 or more. Is more preferable, 14.0 or less is preferable, and 13.0 or less is more preferable.

  In the present invention, the SP value of the resin of component (A) is higher than the SP value of the monomer and / or oligomer containing one or more (meth) acryloyl groups of component (B), thereby causing phase separation. It becomes easy. In order to make the SP value of the resin of component (A) higher than the SP value of the monomer and / or oligomer containing one or more (meth) acryloyl groups of component (B), for example, component (A) It is sufficient to design the resin so that it contains a large number of highly polar functional groups in the side chain of the resin, and more specifically, as described later, by opening a monomer having an oxirane skeleton by addition of (meth) acrylic acid. And a method for preparing a copolymer. In addition, 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 higher having an alicyclic skeleton 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 composition of the present invention can be enhanced. As a combination of such functional groups, for example, a functional group having active hydrogen (hydroxyl group, amino group, thiol group, carboxyl group, etc.) and an epoxy group, a functional group having active hydrogen and an isocyanate group, and an ethylenically unsaturated group 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, functional group having active hydrogen and functional group having active hydrogen 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)>
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. These resins may be polymers having a relatively low molecular weight, so-called oligomers. 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.
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. Furthermore, a (meth) acryloyl polymer having a hydrogen bonding group in the side chain is preferred because it is easier 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 (Meth) acrylates containing hydroxyl groups such as glycol mono (meth) acrylate, (poly) butylene glycol- (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol- (poly) butylene glycol mono (meth) acrylate, etc. A polymer obtained by polymerizing a monomer having an oxirane structure, 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 method of ring-opening / addition reaction of a monomer having a hydroxyl group such as lactic acid, a polymer having a reactive group that undergoes a ring-opening / addition reaction with an oxirane structure such as a carboxyl group or an amino group, and producing a polymer. Examples include a method of ring-opening / addition reaction of a monomer having an oxirane structure.

  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 (1) to (3).

(Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p represents an integer of 1 to 8).

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

(Here, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 8)

In formula (1), preferred as R ¹ and R ² are each independently a hydrogen atom or a methyl group. Specific examples of the monomer represented by the formula (1) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (GMA) is available. From the viewpoint of

In the formula (2), preferred as R ³ and R ⁵ are each independently a hydrogen atom or a methyl group, and preferred as R ⁴ is a —CH ₂ O— group. Specific examples of the monomer represented by the formula (2) 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 (3), R ⁶ is preferably a hydrogen atom or a methyl group. Examples of the monomer represented by the formula (3) include 3,4-epoxycyclohexylmethyl (meth) acrylate. 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) of 5,000 or more. The weight average molecular weight (Mw) of the component (A) is preferably 8,000 or more, and more preferably 10,000 or more. Moreover, it is preferable that it is 100,000 or less, It is more preferable that it is 70,000 or less, It is still more preferable that it is 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 mmol / g or more from the viewpoint of improving scratch resistance of the cured product to be formed. Is preferable, more preferably 2 mmol / g or more, and particularly preferably 3 mmol / g or more. From the viewpoint of preventing gelation, the (meth) acryloyl equivalent is preferably 10 mmol / g or less, more preferably 8 mmol / g or less, and particularly preferably 6 mmol / g or less.

  In addition, the resin of the component (A) used in the present invention preferably has a secondary hydroxyl group equivalent (introduced amount of secondary hydroxyl group) of 1 mmol / g or more from the viewpoint of improving antiblocking properties, and is 2 mmol / g or more. More preferably, it is more preferably 3 mmol / g or more. Further, 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 mmol / g or less, and preferably 8 mmol / g or less. More preferably, it is particularly preferably 6 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 1 part by weight or more, more preferably 3 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)>
As the monomer and / or oligomer containing one or more (meth) acryloyl groups of the component (B), a polyfunctional monomer, for example, a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate may be used. it can. 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 5,000 from the viewpoint of good handling properties and coating properties of the curable resin composition. From the viewpoint of making this effect better, the component (B) preferably has a weight average molecular weight of 3,000 or less, and more preferably 2,000 or less.

  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. In addition, "substantially not containing" here means that it is 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 determined according to the above-mentioned component in the curable resin composition of the present invention ( 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). Moreover, it is preferable that it is 99.5 weight part or less, It is more preferable that it is 97 weight part or less, It is still more preferable that it is 95 weight part or less. When the content of the component (B) is less than the above lower limit, the performance such as hardness and antiblocking property is lowered, and when it exceeds the upper limit, the antiblocking property tends to be lowered.

<Ingredient (C)>
Component (C) is a compound containing a silicon atom and / or a fluorine atom and having an active hydrogen-containing reactive group (active hydrogen-containing reactive group) in an amount of 0.9 mmol / g or more. The active hydrogen-containing reactive group contained in the component (C) is not particularly limited as long as it is a group capable of reacting with an NCO group, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and a thiol group. Preferred are those having a hydroxyl group, an amino group, and a carboxyl group in terms of good compatibility with the component (A), and those having a hydroxyl group are particularly preferred. The compound of component (C) may contain two or more of these active hydrogen-containing reactive groups. By containing such an active hydrogen-containing reactive group, the surface energy can be lowered without breaking the surface uneven structure generated by phase separation of the component (A) and the component (B), and the anti-blocking property is improved. The effect of improving is produced.

  In the present invention, the amount of the active hydrogen-containing reactive group in the component (C) is 1.3 mmol / g or more from the viewpoint of improving the anti-blocking property by making the affinity with the component (A) good. Is preferable, and it is more preferable that it is 1.5 mmol / g or more. From the viewpoint of reducing the surface energy of the component (C), the amount of the active hydrogen-containing reactive group is preferably 30 mmol / g or less, more preferably 20 mmol / g or less, and 10 mmol / g or less. More preferably it is.

  Here, the active hydrogen-containing reactive group amount of the component (C) is specifically a value calculated by measurement by the following method. More specific measurement examples will be shown in the following examples.

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. Into an Erlenmeyer flask, 1 to 2 g of the reaction product and 20 mL of 0.5 mol / L dibutylamine toluene solution are added, diluted with 100 mL of acetone, and reacted at 25 ° C. for 30 minutes. Then, the amount of hydroxyl groups is titrated with 0.5 mol / L hydrochloric acid aqueous solution. In addition, except that IPDI was not added to the Erlenmeyer flask, titration is performed in the same manner to obtain a blank. Then, the amount of active hydrogen-containing reactive group is calculated by the following formula. When the sample is dissolved in the solvent having an active hydrogen-containing reactive group, the amount of the active hydrogen-containing reactive group in the solvent is obtained by calculation and subtracted from the following value.
(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)

  As long as the component (C) satisfies the amount of the active hydrogen-containing reactive group, it may contain only a silicon atom or a fluorine atom. And a compound containing a silicon atom and / or a fluorine atom is preferable from the viewpoint of reducing the surface energy. In each case, the number of silicon atoms and / or fluorine atoms contained in the compound is not particularly limited.

  In the case where the component (C) is a compound containing a silicon atom (hereinafter sometimes referred to as “Si-containing compound”), as the Si-containing compound, a polyether-modified silicone oil and / or a polyester-modified silicone oil may be used. The compatibility with (A) is improved, and the surface energy can be lowered without breaking the surface uneven structure formed by the phase separation of the component (A), which is preferable in terms of improving the antiblocking property.

  The polyether-modified silicone oil is obtained by modifying a part of the side chain of a linear polymer composed of siloxane bonds with a polyether. Examples of the linear polymer composed of siloxane bonds include those in which a part of the side chain is a methyl group, those in which all of the side chain and both ends or one end are methyl groups, and a part of the side chain is a phenyl group. Some, some of the side chains are hydrogen-bonding groups, and some of the side chains are hydrogen atoms. Among these, all of the side chain and both ends or one end is a methyl group, a part of the side chain is a hydrogen bonding group, and a part of the side chain is a hydrogen atom, The resulting cured product is preferred from the viewpoint of good antiblocking properties and good optical properties, and those in which all side chains and both ends or one end are methyl groups are particularly preferred from the viewpoint of easy surface segregation. Moreover, various organic groups can be introduced into silicone oil, and the properties differ depending on the type of organic group. An organic group may be further introduced into the polyether-modified silicone oil. Examples of the organic group include an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group, a fluoro group, an amino group, an epoxy group, Examples include thiol groups. Among these, alkyl group, aralkyl group, hydroxyl group, amino group, acryloyl group, carboxyl group, carbonyl group, and epoxy group are preferable because of good antiblocking property, and alkyl group, aralkyl group, hydroxyl group, amino group, carboxyl group are preferable. And the acryloyl group is particularly preferred.

  Specific examples of the polyether-modified silicone oil include BYK300, BYK302, BYK306, BYK307, BYK320, BYK325, BYK330, BYK331, BYK333, BYK337, BYK342, BYK345, BYK347, Y375, K375, K375, BYK3510, BYK3530 (above, manufactured by BYK Chemie), Silface SAG001, Silface SAG005 (above, Nissin Chemical Industry Co., Ltd.) FZ-2191, FZ-2166, FZ-2154, FZ-2120, L-720, SH8700 , L-7002, L-7001, SF8410, FZ-2123, SH8400, FZ-2164, FZ-77 FZ-2105, FZ-2208 (manufactured by Dow Corning Toray Co., Ltd.), SILWETL-8500, SILWETL-8610, SILWETL-8620, SILWETL-77, SILWETL-7280, SILWETL-7608 , SILWETL-7001, SILWETL-7002, SILWETL-7087, SILWETL-7210, SILWETL-7220, SILWETL-7230, SILWETL-7500, SILWETL-7510, SILWETL-7602, SILWETL-7622, SILWETL-776 , Momentive Performance Materials Japan). Among these, from the viewpoint of good antiblocking properties, BYK306, BYK307, BYK325, BYK331, BYK333, BYK342, BYK375, BYK377, BYK378, BYKUV3500, BYKUV3510, and Sylface SAG001 are more preferable. To BYK325, BYK331, BYK375, BYK377, BYKUV3500, BYKUV3510, and Sylface SAG001 are particularly preferable.

  The polyester-modified silicone oil is one in which a part of the side chain of a linear polymer composed of a siloxane bond is modified with polyester. A part of the side chain may be modified with polyether. Examples of the linear polymer composed of siloxane bonds include those in which a part of the side chain is a methyl group, those in which all of the side chain and both ends or one end are methyl groups, and a part of the side chain is a phenyl group. Some, some of the side chains are hydrogen-bonding groups, and some of the side chains are hydrogen atoms. Among these, all of the side chain and both ends or one end is a methyl group, a part of the side chain is a hydrogen bonding group, and a part of the side chain is a hydrogen atom, The resulting cured product has good anti-blocking properties and good optical properties, and is preferred because all of the side chains and both ends or one end are methyl groups, that is, polydimethylsiloxane tends to segregate on the surface. Is particularly preferred. Moreover, various organic groups can be introduced into silicone oil, and the properties differ depending on the type of organic group. An organic group may be further introduced into the polyether-modified silicone oil. Examples of the organic group include an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group, a fluoro group, an amino group, an epoxy group, Examples include thiol groups. Among these, alkyl group, aralkyl group, hydroxyl group, amino group, acryloyl group, carboxyl group, carbonyl group, and epoxy group are preferable because of good antiblocking property, and alkyl group, aralkyl group, hydroxyl group, amino group, carboxyl group are preferable. And the acryloyl group is particularly preferred.

  Specific examples of the polyester-modified silicone oil include BYK-310, BYK-313, BYK-315, BYK-370, BYK-371, BYK-375, BYK-3570 (manufactured by BYK Chemie), and the like. BYK370 and BYK375 are preferable in that they have an active hydrogen-containing reactive group.

  When component (C) is a compound containing a fluorine atom (hereinafter sometimes referred to as “F-containing compound”), the F-containing compound contains a fluorine atom and has a weight average molecular weight (Mw) of 2 , 40,000 to 40,000 compounds are preferred. The weight average molecular weight of the F-containing compound is more preferably 5,000 to 30,000, and particularly preferably 5,000 to 20,000. When the weight average molecular weight of the F-containing compound is within this range, bleeding out is difficult, which is preferable. A specific method for measuring the weight average molecular weight of the F-containing compound is shown in the Examples section below.

  Specific examples of F-containing compounds include Megafuck F-477, Megafuck F-554, Megafuck F-556, Megafuck F-555, Megafuck F-444, Megafuck F-557, and Megafuck F-552. , Mega Fuck F-558, Mega Fuck F-562, Mega Fuck F-568, Mega Fuck F-559, Mega Fuck F-561, Mega Fuck F-563, Mega Fuck R-40, Mega Fuck RS-922, Mega Fuck RS-537, Mega Fuck RS-507, Mega Fuck RS-903-3, Mega Fuck RS-75, Mega Fuck RS-76E (manufactured by DIC), Aftergent 710FM, Aftergent 710FL, Aftergent 730FL, Aftergent 730LM, aftergent 710FS, aftergent 601 D, Aftergent 602A, Aftergent 650A, Aftergent 100, Aftergent 150, Aftergent 300, Aftergent 320, Aftergent 400SW, Aftergent 212P, Aftergent 208G, Aftergent 215M, Aftergent 251, Aftergent 250, Aftergent 240G, Aftergent 245F, Aftergent 228P, Aftergent 220P, Aftergent 212M (Neos), DSN-403N, NS-9013 (Daikin), LE-604, Floren AO-82, Floren AO- 98, Florene AO-106, Florene AO-108, Florene NAF-250 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. LE-604, MegaFace F-556, NS-9013, Aftergent 730FL, Aftergent 730LM, Aftergent 602A, and Aftergent 650A are preferred, and particularly contain active hydrogen-containing reactive groups. From the viewpoint of improving the anti-blocking property, LE-604, Megafac F-556, and NS-9013 are particularly preferable.

  In this invention, these components (C) may be used individually by 1 type, and 2 or more types may be mixed and used for them. Furthermore, you may use together the thing containing only another silicon atom, the thing containing only a fluorine atom, and the thing containing a silicon atom and a fluorine atom.

  The content of the compound containing a silicon atom and / or a fluorine atom as the component (C) of the curable resin composition of the present invention and having an active hydrogen-containing reactive group amount of 0.9 mmol / g or more is It is preferably 0.001 part by weight or more, and 0.05 part by weight or more 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 invention. Is more preferable, and it is still more preferable that it is 0.1 weight part or more. Further, it is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5.0 parts by weight or less, and particularly preferably 3.0 parts by weight or less. If content of a component (C) is this range, since the antiblocking property and surface property of the hard-coat layer obtained are favorable, it is preferable.

<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. Use of inorganic particles having an average primary particle diameter exceeding 1 μm is not preferable because sedimentation occurs due to the weight of the particles and storage stability of the coating liquid of the curable resin composition tends to decrease.

  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, and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and 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 liquid having a solid content of 20 to 100% by weight, particularly 30 to 80% by weight, using the above-mentioned solvent. 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 laminate of the present invention is formed by forming a cured layer of 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 or the like. It can be a body. 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 polyester film. Polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film and the like can be used. Also, as the resin plate, for example, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyether sulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate, polyether plate , Polymethylpentene plate, polyetherketone plate, (meth) acrylonitrile plate and the like. 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, the thing of about 25-1000 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. The light irradiation for curing, it is preferred that the cumulative amount of light is irradiated so as to be 100 mJ / cm ² or more 20,000mJ / 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 ( It can be measured according to JIS B-0601-2001 using a color 3D laser microscope manufactured by Keyence Corporation.

  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, for a hard coat film formed with a film thickness of 3 μm by the curable resin composition of the present invention, the pencil hardness measured according to JIS K-5600 is preferably H or more, and preferably 2H or more. 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, a TN (Twisted Nematic) type liquid crystal cell, an STN (Super Twisted Nematic) type liquid crystal cell, a HAN (Hybrid Alignment Nematic) type liquid crystal cell, an IPS (In Plane Switching) type liquid crystal cell, and a VA (vertical type liquid crystal cell). Examples thereof include an MVA (Multiple Vertical Alignment) type liquid crystal cell, an OCB (Optical Compensated Bend) type liquid crystal cell, and the like. 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, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Component (C)]
In the following Examples and Comparative Examples, details of the compounds used as the component (C) are as follows.

<Calculation of active hydrogen-containing reactive group amount>
The amount of reactive hydrogen-containing reactive group 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. In addition, the detailed usage-amount of each component used for reaction is as Table 2 below.
(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 F-containing compound>
About the F containing compound used as a component (C), 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: 0.02% by weight
Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion

[Evaluation method]
The evaluation methods of the coating liquid (curable resin composition) prepared in Examples and Comparative Examples and the manufactured cured film (hard coat film) are 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 shifted ○: Can be shifted and no sound is produced △: Can be displaced, but sound is sounded ×: The cured film surfaces are in close contact with each other and the cured film surfaces are What can not be shifted

<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.

<Synthesis Example 1: Synthesis of acryloyl copolymer (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 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. 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, whereby an acryloyl equivalent having an acryloyl group and a methoxysilyl group and a weight average molecular weight of 20,000 ( The amount of acryloyl group introduced) was 4.47 mmol / g, the amount of secondary hydroxyl group equivalent (the amount of secondary hydroxyl group introduced) was 4.47 mmol / g, and an acryloyl copolymer (A-1) was obtained. The SP value of this acryloyl copolymer (A-1) was 17.8. Hereinafter, this is referred to as “resin (A-1)”.

The weight average molecular weight of the acryloyl copolymer (A-1) is a value measured by the GPC method under the following conditions.
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: 0.02% by weight
Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion

<Synthesis Example 2: Colloidal silica (D-1) surface-modified with resin (A-1)>
In a four-necked flask, 3.75 parts by weight of the resin (A-1) obtained in Synthesis Example 1 and (D-1) colloidal silica (manufactured by Nissan Chemical: MEK-ST (average primary particle size of 10 to 15 nm (catalog value) )) 1.25 parts by weight is added, 0.005 part by weight of acetylacetone aluminum is added as a catalyst for the silane coupling reaction, the reaction is performed at 70 ° C. for 4 hours, and the surface of the colloidal silica is modified with the resin (A-1). (D-1) was prepared, which is hereinafter referred to as “resin (A-2)”.

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

[Examples and comparative examples using Si-containing compounds as component (C)]
<Example I-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 4.

<Examples I-2 to I-4 and Comparative Examples I-1 to I-4>
A curable resin composition was obtained in the same manner as in Example I-1 except that the formulation shown in Table 3 was used, and a cured film was formed and evaluated in the same manner. The results are shown in Table 4.

[Examples and comparative examples using F-containing compounds as component (C)]
<Examples II-1 to II-4 and Comparative Example II-1>
A curable resin composition was obtained in the same manner as in Example I-1 except that the formulation shown in Table 3 was used, and a cured film was formed and evaluated in the same manner. The results are shown in Table 4.

[Other comparative examples]
<Comparative Examples III-1 to III-4>
A curable resin composition was obtained in the same manner as in Example I-1 except that the formulation shown in Table 3 was used, and a cured film was formed and evaluated in the same manner. The results are shown in Table 4.

  In addition, when the coating-film external appearance of the cured film of the film laminated body obtained in Example I-1-4 and II-1-4 was visually observed, there were almost no defects and it was very excellent.

[Evaluation results]
From the above results, according to the present invention, by adding the specific component (C), a cured film having high hardness and excellent antiblocking property, and further excellent coating film appearance and transparency is formed. I can see that

Claims (13)

The following components (A), (B) and (C) are included, and the resin content of component (A) is 0.5 parts by weight with respect to 100 parts by weight as a total of component (A) and component (B). 25 parts by weight or less, and the content of the component (C) is 0.001 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight in total of the component (A) and the component (B). A curable resin composition, wherein the solubility parameter (SP value) of A) is 5.7 or more higher than the solubility parameter (SP value) of the component (B).
Component (A): The weight average molecular weight (Mw) is 5,000 or more, and one or more resin components (B) having a (meth) acryloyl group: the weight average molecular weight (Mw) is less than 5,000, polyfunctional monomer and / or oligomer component having two or more unsaturated double bonds, and two or more (meth) acryloyl groups in a molecule (C): it contains the full Tsu atom, and Compound having an active hydrogen-containing reactive group amount of 0.9 mmol / g or more and a weight average molecular weight (Mw) of 2,000 to 40,000   The curable resin composition according to claim 1, wherein the component (A) is a resin having a hydrogen bonding group and a (meth) acryloyl group.   The curable resin composition according to claim 2, wherein the hydrogen bonding group is a hydroxyl group.   The curable resin composition according to any one of claims 1 to 3, 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 4, comprising a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule as the polyfunctional (meth) acrylate. The solubility parameter (SP value) of the component (A) is 14.0 or more and 20.0 or less, and the solubility parameter (SP value) of the component (B) is 8.0 or more and 14.0 or less. The curable resin composition according to any one of claims 1 to 5 . Furthermore, the curable resin composition of any one of Claims 1 thru | or 6 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 7 , 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 8 , 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 9 . 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 9 on a base material. Hard coat film formed by curing a curable resin composition according to any one of claims 1 to 9. The film laminated body formed by laminating | stacking the hard coat film of Claim 12 with another resin film.