JP5568832B2 - Curable resin composition and hard coat film - Google Patents

Description

  The present invention relates to a curable resin composition and a hard coat film for protecting the surface of a display or the like using the same.

  An image display surface in an image display device such as a liquid crystal display, a CRT display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged during handling. Therefore, an image display surface is obtained by using a hard coat film in which a hard coat (HC) layer is formed on a base film or a hard coat film (optical laminate) having optical functions such as antireflection and antiglare properties. In general, the scratch resistance is improved.

  The hard coat layer is usually formed as a thin coating film of about 3 to 50 μm on a light-transmitting substrate using a photopolymerizable resin such as a thermosetting resin or an ultraviolet curable resin. However, when the coating film thickness is thin, a film having sufficiently high mechanical strength (pencil hardness) cannot be obtained due to the influence of deformation of the underlying base material. For example, when a thin coating film having a thickness of about 3 to 50 μm is formed on a triacetyl cellulose film having a thickness of 80 μm, it is difficult to achieve a mechanical strength of 4H or higher in pencil hardness.

As a method for improving the hardness of the hard coat layer, it is conceivable to simply increase the thickness of the hard coat layer. However, when the thickness is increased, the hardness is improved, but the hard coat layer is liable to be cracked or the entire laminate is warped (so-called curl) due to curing shrinkage of the components of the hard coat layer. Thus, there is a problem that workability is remarkably impaired when the laminate is attached to a display.
In addition, as a method for improving the hardness of the hard coat layer, there is a method of adding silica fine particles, but the fine particles are likely to aggregate, and irregularities of aggregates may occur on the surface.

In order to cope with these problems, Patent Document 1 discloses that even when a plastic film substrate is used, film peeling and cracking hardly occur, a curling problem is avoided, and a hard coat film having sufficient hardness is ethylenic. Contains both a crosslinkable compound having a ring-opening polymerizable group in the side chain of a polymer obtained by polymerizing a monomer having a double bond and a compound having two or more ethylenically unsaturated groups in the same molecule. It has been shown that a curable composition that polymerizes both the ring-opening polymerizable group and the ethylenically unsaturated group in the crosslinkable compound is applied and cured on a substrate.
However, although the hard coat layer of Patent Document 1 is effective with a thick substrate such as polyethylene terephthalate having a thickness of 188 μm as shown in the Examples, the thin substrate shown in Comparative Example 7 was used. In such a case, sufficient hardness cannot be obtained, and curling is difficult to suppress. In addition, the hard coat film cannot be cut cleanly and has poor restoration properties.

In Patent Document 2, as a hard coat film having high hardness and suppressing cracking and curling, the hard coat layer has urethane acrylate (A), isocyanuric acid acrylate (B), and inorganic ultrafine particles (C). A hard coat film is shown which is a cured coating layer containing.
However, in the hard coat layer of Patent Document 2, inorganic ultrafine particles are not crosslinkable. In addition, as described in the examples, the amount of light irradiation at the time of photocuring must be increased, and if a substrate that is susceptible to thermal damage such as a triacetyl cellulose film is used, the hard coat film is polymerized. Due to the heat of polymerization, the base material is damaged by heat, and there is a problem that wrinkles that are apparent even when visually observed. Further, even the hard coat layer of Patent Document 2 cannot suppress the occurrence of curling and cracking while maintaining the hardness.

With the recent increase in demand for display devices, the demand for hard coat films is increasing, and it is required to produce high-quality hard coat films with high productivity. However, a long light irradiation time is required in the curing step of the curable resin composition, which is rate-limiting and it is difficult to improve productivity.
Thus, it is possible to obtain a hard coat film that has sufficient scratch resistance, does not cause cracks, curls are suppressed, does not easily cause shrinkage of the substrate during curing, and can be manufactured at a high production rate. could not.
JP 2003-147017 A JP 2006-106427 A

  The present invention solves the above problems, has a sufficient scratch resistance, does not cause cracks, curls are suppressed, hardly causes shrinkage of the base material during curing, and is a hard coat film at a high production rate. Is provided, and a hard coat film using the same is provided.

（式中、Ａは炭素原子を含む環状構造と炭素原子数が４以上の鎖状構造の組合せ、Ｘ、ＹはＮＣＯ、水素または炭化水素基を示す）
で表され、末端に２つ以上の反応性官能基を有する分子量が３,０００以上の化合物、
（Ｂ）２つ以上の反応性官能基を有する分子量が１０,０００未満の化合物、及び、
（Ｃ）少なくとも表面の一部に有機成分が被覆され、当該有機成分により導入された反応性官能基を表面に有する無機微粒子からなる硬化性樹脂組成物を提供する。 In order to solve the above problems, the present invention provides:
(A) Formula (1):

(In the formula, A represents a combination of a cyclic structure containing carbon atoms and a chain structure having 4 or more carbon atoms, and X and Y represent NCO, hydrogen, or a hydrocarbon group)
A compound having a molecular weight of 3,000 or more and having two or more reactive functional groups at its ends,
(B) a compound having two or more reactive functional groups and a molecular weight of less than 10,000, and
(C) Provided is a curable resin composition comprising inorganic fine particles having a reactive functional group introduced on the surface thereof, the organic component being coated on at least a part of the surface, and having a reactive functional group introduced on the surface.

  According to the present invention, the compound (A) having a molecular weight of 3,000 or more having two or more reactive functional groups at the terminal, and a compound having a molecular weight of less than 10,000 having two or more reactive functional groups ( B) and inorganic fine particles (C) having reactive functional groups on the surface, and the compound (A), the compound (B), and the inorganic fine particles (C) are sufficiently reacted with each other. It is possible to obtain a hard coat layer that has scratch resistance, does not cause cracks, and curl is suppressed.

  In the curable resin composition of the present invention, the compound (A), the compound (B), and the inorganic fine particles (C) have a polymerizable unsaturated group as a reactive functional group, thereby improving the hardness of the cured film. From the point of view, it is preferable.

  In the curable resin composition of the present invention, the content of the compound (A) is 5 to 100 parts by weight with respect to 100 parts by weight of the compound (B), and the content of the inorganic fine particles (C). Is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B) from the viewpoint of balancing the hardness and cracks of the cured film.

  In the curable resin composition of the present invention, the average particle size of the inorganic fine particles (C) is preferably 20 to 500 nm from the viewpoint of improving the hardness of the cured film.

In the curable resin composition of the present invention, the organic component covering the inorganic fine particles (C) is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating. Is preferable from the viewpoint of improving the hardness of the cured film.

In the curable resin composition of the present invention, the inorganic fine particles (C) are saturated or unsaturated carboxylic acids, acid anhydrides, acid chlorides, esters and acid amides corresponding to the carboxylic acids, amino acids, imines, nitriles, In the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of isonitriles, epoxy compounds, amines, β-dicarbonyl compounds, silanes, and functional metal compounds, water as a dispersion medium and It is preferable that it is obtained by dispersing inorganic fine particles in an organic solvent because the film strength can be improved even if the organic component content is small.
In addition, it is preferable that the surface modification compound is a compound having at least one hydrogen bond forming group from the viewpoint that the organic component can be surface modified efficiently.
Furthermore, the surface modification compound preferably has a polymerizable unsaturated group. In this case, since the introduced inorganic fine particles (C) are easy to form a cross-linked bond, the hardness of the cured film can be improved.

  In the curable resin composition of the present invention, the inorganic fine particles (C) are formed by discharging a monomer in which inorganic fine particles having a particle diameter of 500 nm or less are dispersed in a hydrophobic vinyl monomer into water through a hydrophilicized porous film. It is preferable to obtain an aqueous dispersion of monomer droplets in which fine particles are dispersed, followed by polymerization from the viewpoint of narrowing the particle size distribution and improving monodispersibility.

In the curable resin composition of the present invention, the inorganic fine particle (C) is a reactive functional group introduced into the surface of the inorganic fine particle, formula (2):
^{-Q 1 -C (= Q 2)} -NH- (2)
(Wherein Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S).
And a compound containing a silanol group or a group that generates a silanol group by hydrolysis, and the metal oxide fine particles can be obtained, thereby improving dispersibility in organic components and film strength. It is preferable from the point.

  The curable resin composition of the present invention is a triacetylcellulose base material having a hard coat layer surface hardness of 80 μm by a pencil hardness test specified in JIS 5600-5-4 (1999) when a cured film is formed. From the viewpoint of scratch resistance and scratch prevention, 4H or more is preferable.

  Moreover, in order to solve the said subject, this invention provides a hard-coat film provided with the hard-coat layer which consists of hardened | cured material of the curable resin composition as described above on a light-transmitting resin base material.

  The hard coat film of the present invention is provided with a hard coat layer made of a cured product of the curable resin composition on the base material, so that it has sufficient scratch resistance and does not cause cracks and curling can be suppressed. It is difficult to cause shrinkage of the base material at the time of curing, and it can be produced at a high production rate.

In the hard coat film of the present invention, the hard coat layer may contain an antistatic agent and / or an antiglare agent.
Further, the hard coat film of the present invention is an antistatic layer, an antiglare layer, a low refractive index layer, and / or between the light transmissive resin substrate and the hard coat layer and / or on the hard coat layer. It may be formed by forming one or more layers selected from the group consisting of antifouling layers.

The curable resin composition of the present invention has sufficient scratch resistance, does not cause cracks, curls are suppressed, does not easily cause shrinkage of the base material during curing, and can produce a hard coat film at a high production rate. It can be formed.
Therefore, the hard coat film using the curable resin composition of the present invention has sufficient scratch resistance, does not generate cracks, curl is suppressed, and does not easily cause shrinkage of the substrate during curing, and There is an effect that it can be manufactured at a high production speed.

  The present invention relates to a curable resin composition and a hard coat film using the same. Hereinafter, the curable resin composition and the hard coat film will be described in order.

（式中、Ａは炭素原子を含む 環状構造と炭素原子数が４以上の鎖状構造の組合せ、Ｘ、ＹはＮＣＯ、水素または炭化水素基を示す）
で表され、末端に２つ以上の反応性官能基を有する分子量が３,０００以上の化合物、
（Ｂ）２つ以上の反応性官能基を有する分子量が１０,０００未満の化合物、及び、
（Ｃ）少なくとも表面の一部に有機成分が被覆され、当該有機成分により導入された反応性官能基を表面に有する無機微粒子を含有し、
前記化合物（Ａ）、前記化合物（Ｂ）、及び前記無機微粒子（Ｃ）が互いに反応することが可能であることを特徴とする。 I. Curable resin composition The curable resin composition of the present invention,
(A) Formula (1):

(In the formula, A is a combination of a cyclic structure containing a carbon atom and a chain structure having 4 or more carbon atoms, and X and Y are NCO, hydrogen or a hydrocarbon group)
A compound having a molecular weight of 3,000 or more and having two or more reactive functional groups at its ends,
(B) a compound having two or more reactive functional groups and a molecular weight of less than 10,000, and
(C) containing inorganic fine particles having a reactive functional group on the surface thereof, the organic component being coated on at least a part of the surface and introduced by the organic component;
The compound (A), the compound (B), and the inorganic fine particles (C) can react with each other.

  The curable resin composition of the present invention has a compound (A) having a molecular weight of 3,000 or more having two or more reactive functional groups at the terminal and a molecular weight of 10,000 or more having two or more reactive functional groups. Less than the compound (B) and inorganic fine particles (C) having reactive functional groups on the surface, the compound (A), the compound (B), and the inorganic fine particles (C) can react with each other. As a result, it is possible to obtain a hard coat layer that has sufficient scratch resistance, does not cause cracks, and curl is suppressed.

In the present invention, in order to achieve sufficient hardness in the thin film, in addition to the compound (B) having a molecular weight of less than 10,000 and having two or more reactive functional groups that function as hard segment components in the hard coat layer. The inorganic fine particles (C) that can react with the compound (B) and function as a hard segment component harder than the compound (B) are used in combination.
However, when only the compound (B) and the inorganic fine particles (C) are combined, the hardness is increased, but cracking occurs only by bending a little, and the adhesion is lowered, which causes a practical problem. In addition, when a soft segment component is added so as to give more flexibility in order to prevent cracks from occurring, the hardness decreases as it becomes a problem in use.
Further, when a crosslinkable compound having a polymerizable group is combined with a side chain of a polymer obtained by polymerizing a monomer having an ethylenic double bond as in Patent Document 1, a relatively hard main chain structure of the polymer is obtained. As a result, even if flexibility is imparted, the restoration does not occur, so that it is not possible to prevent the occurrence of cracks during cutting.
On the other hand, in the present invention, the compound (B) and the inorganic fine particles (C) further have two or more reactive functional groups at the terminal capable of reacting with the compound (B) and the inorganic fine particles (C). Since a compound (A) having a molecular weight of 3,000 or more is used in combination, flexibility and resilience can be imparted while maintaining the desired hardness even in a thin film, so cracks when bending or cutting Occurrence can be prevented.
That is, the compound (A) is bulky in the molecule, and can have flexibility and resilience by having a cyclic structure of a hard segment component. On the other hand, the compound (A) can be crosslinked with both the compound (B) and the inorganic fine particles (C), which are the hard segment components, by the reactive functional group at the terminal, and thus achieves a desired hardness even in a thin film. It becomes possible.

Further, the curable resin composition of the present invention contains the specific compound (A), the compound (B), and the inorganic fine particles (C), all of which are capable of reacting with each other, thereby reducing low irradiation. It can be cured in a short amount of time. Therefore, the curable resin composition of the present invention reduces heat damage to the base material due to the heat of polymerization at the time of curing, hardly causes shrinkage of the base material, can further suppress curling of the hard coat layer, and is high. A hard coat film can be formed at a production rate.
Therefore, according to the present invention, it has sufficient scratch resistance, does not cause cracking, curl is suppressed, it is difficult to cause shrinkage of the base material during curing, and a hard coat film can be formed at a high production rate. A curable resin composition can be obtained.

Hereinafter, each structure of the curable resin composition of this invention is demonstrated in order.
In the present specification, (meth) acryloyl represents acryloyl and methacryloyl, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl. In addition, the light in this specification includes not only electromagnetic waves having wavelengths in the visible and non-visible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

The reactive functional group in this specification includes a photocurable functional group and a thermosetting functional group. The photo-curable functional group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation, such as photo radical polymerization, photo cation polymerization, and photo anion polymerization. And a reaction that proceeds by a reaction method such as addition polymerization or condensation polymerization that proceeds via photodimerization.
In addition, the thermosetting functional group in the present specification is a functional group capable of curing a coating film by causing a polymerization reaction or a crosslinking reaction to proceed between the same functional groups or other functional groups by heating. And examples thereof include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and an isocyanate group.
As the reactive functional group used in the present invention, (meth) acryloyl group, (meth) acryloyloxy group, vinyl group (CH ₂ ═CH—), CH ₂ ═CR— (here, particularly from the viewpoint of reactivity) And R is a hydrocarbon group), a polymerizable unsaturated group such as a cinnamoyl group, a maleate group, an acrylamide group, and an ethynyl group is preferably used.

  In addition, the reactive functional groups of the compound (A), the compound (B), and the inorganic fine particles (C) can react with each other means a combination of those in which the reactive functional groups can directly react with each other. In addition to the case where it has, an embodiment in which the three components of the reactive functional group of the compound (A), the compound (B), and the inorganic fine particles (C) can react with each other via another crosslinking component is also included. Since the three components of the compound (A), the compound (B), and the inorganic fine particles (C) can react with each other, in the cured film formed by the resin composition of the present invention, the compound ( A network structure in which the three components of A), the compound (B), and the inorganic fine particles (C) are crosslinked can be formed.

  In addition, in the present specification, the molecular weight means a weight average molecular weight which is a polystyrene conversion value measured by gel permeation chromatography when having a molecular weight distribution, and when there is no molecular weight distribution, the molecular weight of the compound itself. Say.

（式中、Ａは炭素原子を含む環状構造と炭素原子数が４以上の鎖状構造の組合せ、Ｘ、ＹはＮＣＯ、水素または炭化水素基を示す）
で表され、末端に２つ以上の反応性官能基を有する分子量が３,０００以上の化合物である。分子量が３,０００より小さい化合物であると、得られた樹脂に充分な柔軟性が与えられず、クラック発生の原因となることから好ましくない。 <Compound (A) Represented by Formula (1)>
The compound (A) used in the present invention has the formula (1):

(In the formula, A represents a combination of a cyclic structure containing carbon atoms and a chain structure having 4 or more carbon atoms, and X and Y represent NCO, hydrogen, or a hydrocarbon group)
And a compound having a molecular weight of 3,000 or more having two or more reactive functional groups at its ends. A compound having a molecular weight smaller than 3,000 is not preferable because the obtained resin is not sufficiently flexible and causes cracks.

  Preferable examples of the cyclic structure of the compound A include xylylene diisocyanate, isophorone diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate. , Isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, 1,3-adamantanediol, 1,6-hexane diisocyanate, etc. Is mentioned.

  Preferred examples of the chain structure of the compound A having 4 or more carbon atoms include 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,4-butanediisocyanate, 1,5-heptane isocyanate, 1,6-hexane isocyanate, 1,6-heptane diisocyanate and the like.

  Examining the number of carbon atoms in the main chain of the chain structure, if the number of atoms in the main chain is less than 4, the flexibility of the finally obtained hard coat layer becomes insufficient.

  Combining a ring structure and a chain structure prevents curling without reducing the film hardness due to the bulky structure of the hard segment, and further reduces the steric hindrance of the ring structure via the chain structure. Is done. As a result, the reactivity is excellent and the film hardness of the hard coat film is improved.

  As a method for introducing a reactive functional group into the compound represented by the formula (1), a method of forming a urethane polymer of an isocyanate in the compound and a (meth) acrylate containing a reactive hydroxyl group is effective.

  Specific examples of the (meth) acrylate bonded to the compound represented by the above formula (1) include pentaerythritol triacrylate, dipentaerythritol triacrylate, 2-hydroxy-1-acryloxy-3-methacrylate, 4-hydroxy Examples include butyl acrylate and 4-acryloyloxybutyl isocyanate.

  The molecular weight of the compound (A) used in the present invention is 3,000 or more, more preferably 4,000 or more, from the viewpoint of imparting flexibility to the cured film and preventing cracks.

  As a commercial item containing the compound (A) represented by the said Formula (1), brand name KRM7804, KRM8321 (made by Daicel Cytec), brand name A-6M (made by Negami Kogyo), brand name HMP-, for example. 2M (manufactured by Negami Kogyo) and the like.

The content of the compound (A) is preferably 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the compound (B). If the content of the compound (A) is 5 parts by weight or more with respect to 100 parts by weight of the compound (B), the cured film can be given flexibility and restorability, and if it is 100 parts by weight or less, it is cured. The film hardness can be maintained.
In addition, the content of the inorganic fine particles (C) is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B), and further 20 to 40 parts by weight. Part is desirable. If the content of the component (C) is 10 parts by weight or less, sufficient hardness cannot be obtained in the hard coat layer, and if it is 60 parts by weight or more, the amount of inorganic fine particles in the hard coat layer is too large and brittle. As a result, it causes a decrease in hardness and occurrence of cracks, which is not desirable.

<Compound (B) having two or more reactive functional groups and a molecular weight of less than 10,000>
In the curable resin composition of the present invention, the compound (B) having two or more reactive functional groups and a molecular weight of less than 10,000 is combined with the inorganic fine particles (C) to cure the resin composition. The film hardness is improved and sufficient scratch resistance is imparted. In addition, what has the structure of the said compound (A) is remove | excluded from the compound (B) which has a molecular weight less than 10,000 which has a 2 or more reactive functional group.

  In the present invention, the compound (B) has reactive functional groups that can react with each other in the combination of the compound (A) and the reactive inorganic fine particles (C). And it has enough scratch resistance, no cracks, curling is suppressed, it is difficult to cause shrinkage of the base material during curing, and a hard coat film can be formed at a high production rate. It can be used by appropriately selecting from compounds. Although the said compound (B) may be used individually by 1 type, you may mix and use 2 or more types.

  The compound (B) preferably has 3 or more reactive functional groups in one molecule from the viewpoint of imparting hardness by increasing the crosslinking density of the cured film. Here, when the compound (B) is a compound having a molecular weight distribution, the number of reactive functional groups is represented by an average number.

  Further, the molecular weight of the compound (B) is preferably less than 10,000, and if it is 10,000 or more, the obtained resin becomes too soft and sufficient hardness cannot be obtained. And from a viewpoint of a hardness improvement, it is preferable that the molecular weight of a compound (B) is less than 5,000.

Specific examples are given below, but the compound (B) used in the present invention is not limited thereto.
As specific examples having a polymerizable unsaturated group, polyfunctional (meth) acrylate monomers having two or more polymerizable unsaturated groups in one molecule include 1,6-hexanediol di (meth) acrylate, neopentyl. Bifunctional (meth) acrylate compounds such as glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate; trimethylolpropane tri (meth) acrylate, and EO (ethylene oxide) , Hereinafter referred to as EO), PO (propylene oxide, hereinafter referred to as PO), epichlorohydrin modified product, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, and EO, PO, epichlorohydrin modified product, isocyanur Luric acid EO-modified tri (meth) acrylate (Aronix M-315 manufactured by Toagosei Co., Ltd.), tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) Trifunctional (meth) acrylate compounds such as ethyl, glycerol tri (meth) acrylate and its EO, PO, and epichlorohydrin modified products; pentaerythritol tetra (meth) acrylate and its EO, PO, epichlorohydrin modified products, ditrimethylolpropane tetra Tetrafunctional (meth) acrylate compounds such as (meth) acrylates; Dipentaerythritol penta (meth) acrylates and pentafunctional (meth) acrylate compounds such as EO, PO, epichlorohydrin, fatty acids, alkyls, urethane modified products; Intererythritol hexa (meth) acrylate and its EO, PO, epichlorohydrin, fatty acid, alkyl, urethane modified product, sorbitol hexa (meth) acrylate and its EO, PO, epichlorohydrin, fatty acid, alkyl, urethane modified product, etc. A (meth) acrylate compound is mentioned.

  As (meth) acrylate compounds (or pre-compounds), epoxy (meth) acrylates obtained by addition reaction of glycidyl ether and a monomer having (meth) acrylic acid or carboxylic acid group; reaction of polyol and polyisocyanate (Meth) acrylates obtained by addition reaction of a product with a hydroxyl group-containing (meth) acrylate; polyester acrylates obtained by esterification of a polyester polyol composed of a polyol and a polybasic acid and (meth) acrylic acid A polybutadiene (meth) acrylate which is a (meth) acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton. When the reactive functional group of the essential component in the present invention is a polymerizable unsaturated group, urethane (meth) acrylate is preferably used from the viewpoint of imparting hardness and flexibility to the cured film.

As the glycidyl ether used in the above epoxy (meth) acrylates, 1,6-hexane diglycidyl ether, polyethylene glycol glycidyl ether, bisphenol A type epoxy resin, naphthalene type epoxy resin, cardo epoxy resin, glycerol triglycidyl ether, phenol novolac Type epoxy resin and the like.
Examples of the polyol used in the urethane (meth) acrylates include 1,6-hexanediglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and polyester diol. It is done. Examples of the polyisocyanate used in the urethane (meth) acrylates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamelletin diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like. Examples of the (meth) acrylate containing a hydroxyl group used in the urethane (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol. (Meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like.
Examples of the polyol for forming the polyester polyol used in the polyester acrylates include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, trimethylolpropane, and pentaerythritol. Examples of the polybasic acid include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

（式中、Ｌは炭素数１〜１０の連結基を表し、ｑは０又は１を表す。Ｒは水素原子又はメチル基を表す。Ａは任意のビニルモノマーの重合単位を表し、単一成分であっても複数の成分で構成されていてもよい。ｏ、ｐは各重合単位のモル％である。ｐは０であっても良い）
で表される重合体を用いることもできる。 The compound (B) used in the present invention has the following general formula (3) having a molecular weight of less than 10,000:

(In the formula, L represents a linking group having 1 to 10 carbon atoms, q represents 0 or 1, R represents a hydrogen atom or a methyl group, A represents a polymerization unit of any vinyl monomer, and a single component. Or o and p are mol% of each polymer unit. P may be 0)
It is also possible to use a polymer represented by

L in the general formula (3) represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. Alternatively, it may have a branched chain structure, may have a cyclic structure, or may have a heteroatom selected from O, N, and S.
Preferable examples of the linking group L in the general formula (3) include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —. O — **, * — (CH ₂ ) ₆ —O — **, * — (CH ₂ ) ₂ —O— (CH) ₂ —O — **, * —CONH— (CH ₂ ) ₃ —O— **, * —CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — **, and the like. Here, * represents a linking site on the compound main chain side, and ** represents a linking site on the (meth) acryloyl group side.

  In general formula (3), R represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.

  In the general formula (3), o may be 100 mol%, that is, a single polymer. Moreover, even if o is 100 mol%, the copolymer in which 2 or more types of polymerization units containing the (meth) acryloyl group represented by o mol% were used may be used. The ratio of o and p can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency.

  In the general formula (3), A represents a polymerization unit of any vinyl monomer, and is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, transparency, and the like. It may be composed of a single or a plurality of vinyl monomers.

  For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, etc. (Meth) acrylates such as vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, Styrene derivatives such as styrene and p-hydroxymethyl styrene, and unsaturated hydrocarbons such as crotonic acid, maleic acid and itaconic acid. Mention may be made of carbon acids and derivatives thereof.

  Moreover, the reactive compound which has an ethylenic double bond group in the terminal and side chain whose weight average molecular weight is 10,000 terminal can also be used. As the reactive compound, the skeleton component is poly (meth) acrylate methyl, polystyrene, poly (meth) acrylate butyl, poly (acrylonitrile / styrene), poly ((meth) acrylate 2-hydroxymethyl / (meth) acrylic Acid methyl), poly (2-hydroxymethyl (meth) acrylate / butyl (meth) acrylate), and copolymers of these resins and silicone resins.

Commercially available products can be used for the above compounds. As urethane acrylates having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade names AH-600, AT-600, UA-306H, UA-306T, UA- manufactured by Kyoeisha 306I, etc .; manufactured by Nippon Synthetic Chemical Co., Ltd. Product names UV-1700B, UV-3000B, UV-3200B, UV-6300B, UV-6330B, UV-7000B, etc .; Arakawa Chemical Industries, Ltd. Product name Beam Set 500 series (502H, 504H, 550B) Etc.); Shin-Nakamura Chemical Co., Ltd. trade names U-6HA, U-15HA, UA-32P, U-324A, etc .; Toagosei Co., Ltd. trade names M-9050 and the like.
Among them, as urethane (meth) acrylate suitably used in combination with the compound (A) of the present invention, a monomer or multimer of isophorone diisocyanate, pentaerythritol polyfunctional acrylate, and dipentaerythritol polyfunctional acrylate are reacted. The urethane (meth) acrylate obtained by doing this. As a commercial item of the said urethane (meth) acrylate, brand name UV-1700B (made by Nippon Synthetic Chemical) is mentioned, for example.

  Moreover, as epoxy acrylates having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade names SP series (SP-4060, 1450, etc.), VR series ( VR-60, 1950; VR-90, 1100, etc.); manufactured by Nippon Synthetic Chemical Co., Ltd., trade names UV-9100B, UV-9170B, etc .; manufactured by Shin-Nakamura Chemical Co., Ltd., trade names EA-6320 / PGMAc, EA-6340 / PGMAc, etc. Can be mentioned.

  In addition, as a reactive compound having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, Toagosei's product name Macromonomer Series AA-6, AS-6, AB-6 , AA-714SK and the like.

On the other hand, among reactive functional groups, cyclic ether groups such as an epoxy group and an oxetanyl group are preferable in that the shrinkage caused by the polymerization reaction is small and the curl property of the cured film is low.
Epoxidation of polyglycidyl ether of polyhydric alcohol having alicyclic ring or cyclohexene ring or cyclopentene ring-containing compound as a resin having two or more epoxy groups with an appropriate oxidizing agent such as hydrogen peroxide or peracid Aliphatic polyhydric alcohol or polyglycidyl ether of an alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, homo compound of glycidyl (meth) acrylate, co-compound Aliphatic epoxy resins such as bisphenol A, bisphenols such as bisphenol F and hydrogenated bisphenol A, or derivatives thereof such as alkylene oxide adducts and caprolactone adducts, and glycidyl ethers produced by the reaction of epichlorohydrin, and Novola Epoxy resins and are glycidyl ether type epoxy resins derived from bisphenols are exemplified.

<Inorganic fine particles (C) having a reactive functional group on the surface>
In the present invention, for the primary purpose of remarkably improving the hardness so as to have sufficient scratch resistance, at least a part of the surface is coated with an organic component, and the reactive functional group introduced by the organic component. Inorganic fine particles (C) having a surface thereof. The inorganic fine particles (C) may further impart functions to the hard coat layer, and are appropriately selected and used according to the purpose.

  Examples of the inorganic fine particles include metal oxide fine particles such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and fluoride. Examples thereof include metal fluoride fine particles such as magnesium and sodium fluoride. Metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.

  From the viewpoint of high hardness, silica and aluminum oxide are preferable. In addition, in order to form a high refractive index layer in phase, fine particles having a high refractive index when a film such as zirconia, titania or antimony oxide is formed can be appropriately selected and used. Similarly, in order to obtain a relatively low refractive index layer, metal fluoride fine particles such as magnesium fluoride and sodium fluoride, and fine particles having a low refractive index during film formation such as hollow silica fine particles are appropriately selected. Can be used. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.

  The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, a metal oxide has a hydroxyl group and an oxy group, such as a metal sulfide, a thiol group and a thio group, or a nitride such as an amino group, an amide group, and an imide group.

  The inorganic fine particles (C) used in the present invention are coated with an organic component on at least a part of the surface, and have a reactive functional group introduced by the organic component on the surface. Here, the organic component is a component containing carbon. Further, as an aspect in which at least a part of the surface is coated with an organic component, for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, thereby In addition to the mode in which the organic component is bonded to the part, for example, the mode in which the organic component is adhered to the hydroxyl group present on the surface of the metal oxide fine particles by an interaction such as hydrogen bonding, or one or two or more in the compound particle An embodiment containing inorganic fine particles is included.

The coating organic component covers almost the entire particle surface from the viewpoint of suppressing aggregation of the inorganic fine particles and increasing the number of reactive functional groups on the surface of the inorganic fine particles to improve the hardness of the film. It is preferable. From such a viewpoint, the organic component covering the inorganic fine particles (C) is 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating in the inorganic fine particles (C). It is preferably included. In an embodiment in which an organic component is attached to or bonded to the surface of the inorganic fine particles, the organic component covering the inorganic fine particles (C) is 2. 2. per unit area of the inorganic fine particles before coating in the inorganic fine particles (C). More preferably, it is contained in an amount of 00 × 10 ⁻³ g / m ² or more, and particularly preferably 3.50 × 10 ⁻³ g / m ² or more. In the embodiment in which the inorganic fine particles are contained in the compound particles, the organic component covering the inorganic fine particles (C) is 3.50 × 10 5 per unit area of the inorganic fine particles before coating in the inorganic fine particles (C). ^-3 g / m ² or more is more preferable, and 5.50 × 10 ⁻³ g / m ² or more is particularly preferable.

The ratio of the organic component to be coated is usually determined by a thermogravimetric analysis in the air from room temperature to usually 800 ° C., for example, as a constant weight value when the dry powder is completely burned in the air. Can be sought.
The amount of organic component per unit area is determined by the following method. First, the organic component weight / inorganic component weight is measured by differential thermogravimetric analysis (TGA). Next, the volume of the entire inorganic component is calculated from the weight and the specific gravity of the used inorganic fine particles. Further, assuming that the inorganic fine particles before coating are spherical, the volume per inorganic fine particle before coating is calculated from the average particle diameter of the inorganic fine particles before coating. From the volume of the whole inorganic component and the volume per inorganic fine particle before coating, the number of inorganic fine particles before coating is obtained. Next, by dividing the organic component weight per inorganic fine particle (C) by the surface area per inorganic fine particle before coating, the amount of organic component per unit area of the inorganic fine particle before coating can be obtained. .

  In the present invention, by defining the particle size and content of the inorganic fine particles (C), an organic component (reactive functional group) is appropriately introduced into the inorganic fine particles (C), and the compatibility with the binder. Will also be excellent. If it is out of this range, the compatibility between the inorganic fine particles (C) and the binder is lowered, the optical properties (haze value, etc.) of the film are deteriorated, and the hardness is lowered because a crosslinking point is not formed with the binder. Will occur.

The average particle size of the inorganic fine particles (C) is preferably 20 to 500 nm from the viewpoint of hardness, more preferably 30 to 250 nm, and particularly preferably 30 to 150 nm. In addition, the inorganic fine particles (C) have a narrow particle size distribution and are monodispersed from the viewpoint of significantly improving the hardness while maintaining the restoration rate when only the resin is used without impairing the transparency. preferable.
The average particle diameter here is a 50% average particle diameter, and can be determined using, for example, a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

As a method for preparing inorganic fine particles (C) having an organic component coated on at least a part of the surface and having a reactive functional group introduced by the organic component on the surface, the kind of the inorganic fine particles and the reactive function to be introduced are used. A conventionally known method can be appropriately selected and used depending on the group.
Among them, in the present invention, the organic component to be coated can be contained in the inorganic fine particles (C) at least 1.00 × 10 ⁻³ g / m ² per unit area of the inorganic fine particles before coating, From the viewpoint of suppressing aggregation of inorganic fine particles and improving the hardness of the film, it is preferable to select and use any of the following inorganic fine particles (i), (ii) and (iii).
(I) Saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group on the surface.
(Ii) A monomer in which inorganic fine particles having a particle diameter of 500 nm or less are dispersed in a hydrophobic vinyl monomer is discharged into water through a hydrophilicized porous membrane to obtain an aqueous dispersion of monomer droplets in which inorganic fine particles are dispersed. Inorganic fine particles having reactive functional groups on the surface, obtained by polymerization.
(Iii) Reactive functional group to be introduced into the inorganic fine particles, formula (2):
^{-Q 1 -C (= Q 2)} -NH- (2)
(Wherein Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S).
And inorganic fine particles having a reactive functional group on the surface, obtained by bonding a compound containing a group shown in 1) and a compound containing a silanol group or a group that generates a silanol group by hydrolysis with metal oxide fine particles.

Hereinafter, the inorganic fine particles suitably used in the present invention will be described in order.
(I) Saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group on the surface.
When the inorganic fine particles (i) are used, there is an advantage that the film strength can be improved even if the organic component content is small.

  The surface modifying compound used for the inorganic fine particles of (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, a hydroxyl group, a thiol group, Dispersion conditions such as epoxy groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolysable residues of silanes, or C-H acid groups such as β-dicarbonyl compounds In the above-mentioned inorganic fine particles have a functional group capable of chemically bonding with a group present on the surface. The chemical bond here preferably includes a covalent bond, an ionic bond or a coordinate bond, but also includes a hydrogen bond. The coordination bond is considered to be complex formation. For example, acidic / base reaction, complex formation or esterification according to Bronsted or Lewis occurs between the functional group of the surface modifying compound and the group on the surface of the inorganic fine particle. The said surface modification compound used for the inorganic fine particle of said (i) can be used 1 type or in mixture of 2 or more types.

The surface modifying compound usually has a molecular residue in addition to at least one functional group (hereinafter referred to as a first functional group) that can participate in chemical bonding with a group on the surface of the inorganic fine particle. The molecular residue modifies the properties of the inorganic fine particles after being bound to the inorganic fine particles via the functional group capable of participating in the chemical bond. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates, or activates inorganic fine particles.
For example, examples of the hydrophobic molecular residue include an alkyl, aryl, alkaryl, aralkyl, or fluorine-containing alkyl group that causes inactivation or repulsion. Examples of the hydrophilic group include a hydroxy group, an alkoxy group, and a polyester group.

The reactive functional group introduced on the surface so that the inorganic fine particles (C) can react with the compound (A) or the compound (B) is appropriately selected according to the compound (A) or the compound (B). Is done. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.
When a reactive functional group capable of reacting with the compound (A) or the compound (B) is contained in the molecular residue of the surface modification compound, the first functional group contained in the surface modification compound It is possible to introduce a reactive functional group capable of reacting with the compound (A) or the compound (B) onto the surface of the inorganic fine particles of (i) above by reacting with the surface of the inorganic fine particles. For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.
On the other hand, in the molecular residue of the surface modification compound, a second reactive functional group is contained, and the second reactive functional group is used as a foothold to the surface of the inorganic fine particles of (i). A reactive functional group capable of reacting with the compound (A) or the compound (B) may be introduced. For example, a group capable of hydrogen bonding (hydrogen bond forming group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bond forming group introduced on the surface of the fine particles It is preferable that a reactive functional group capable of reacting with the compound (A) or the compound (B) is introduced by the reaction of the hydrogen bond forming group of the surface modification compound. That is, as a surface modification compound, a compound having a hydrogen bond forming group, a compound having a reactive functional group capable of reacting with the compound (A) such as a polymerizable unsaturated group or the compound (B), and a hydrogen bond forming group It is mentioned as a suitable example to use together. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond indicates that the bond unit contains —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound of the present invention, among them, a carboxyl group, a hydroxyl group, and an amide group are preferable.

The surface modifying compound used in the inorganic fine particles (i) has a molecular weight of 500 or less, more preferably 400, and particularly 200. Since it has such a low molecular weight, it is presumed that the surface of the inorganic fine particles can be rapidly occupied and aggregation of the inorganic fine particles can be prevented.
The surface modification compound used in the inorganic fine particles (i) is preferably a liquid under the reaction conditions for surface modification, and is preferably soluble or at least emulsifiable in a dispersion medium. Among these, it is preferable that the polymer is dissolved in the dispersion medium and uniformly distributed as discrete molecules or molecular ions in the dispersion medium.

  Saturated or unsaturated carboxylic acids have 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipine Examples include acids, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. The carboxylic acid includes those having a carbon chain blocked by an O-group, S-group or NH-group. Particularly preferred are carboxylic acid ethers such as carboxylic acid monoethers and carboxylic acid polyethers, and the corresponding acid hydrates, esters and amides (eg, methoxyacetic acid, 3,6-dioxaheptanoic acid and 3,6, 9-trioxadecanoic acid) and the like. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

Examples of preferred amines are those having the general formula Q _3-n NH _n (n = 0, 1 or 2), wherein the residues Q are independently 1 to 12, in particular 1 to 6, more preferably 1 to Alkyl having 4 carbon atoms (eg, methyl, ethyl, n-propyl, i-propyl and butyl) and aryl, alkaryl or aralkyl having 6-24 carbon atoms (eg, phenyl, naphthyl, tolyl and benzyl) Represents. Examples of preferred amines include polyalkyleneamines, and specific examples are methylamine, dimethylamine, trimethylamine, ethylamine, aniline, N-methylaniline, diphenylamine, triphenylamine, toluidine, ethylenediamine, and diethylenetriamine. .

Preferred β-dicarbonyl compounds are those having 4 to 12, especially 5 to 8 carbon atoms, such as diketones (such as acetylacetone), 2,3-hexanedione, 3,5-heptanedione, acetoacetic acid, acetoacetate. Examples include acetic acid-C ₁ -C ₄ -alkyl esters (such as ethyl acetoacetate), diacetyl and acetonyl acetone.
Examples of amino acids include β-alanine, glycine, valine, aminocaproic acid, leucine and isoleucine.

Preferred silanes are hydrolyzable organosilanes having at least one hydrolyzable group or hydroxy group and at least one non-hydrolyzable residue. Here, examples of the hydrolyzable group include a halogen, an alkoxy group, and an acyloxy group. As the non-hydrolyzable residue, a non-hydrolyzable residue having a reactive functional group and / or not having a reactive functional group is used. Silanes having at least partially organic residues substituted with fluorine may also be used.
As the silane used is not particularly limited, for _{example, CH 2 = CHSi (OOCCH 3} ) 3, CH 2 = CHSiCl 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (OC 2 H _{5) 3, CH 2 = CH} -Si (OC 2 H 4 OCH 3) 3, CH 2 = CH-CH 2 -Si (OC 2 H 5) 3, CH 2 = CH-CH 2 -Si (OC 2 H ₅ ) ₃ , CH ₂ ═CH—CH ₂ —Si (OOCCH ₃ ) ₃ , γ-glycidyloxypropyltrimethoxysilane (GPTS), γ-glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3aminopropyltrimethoxysilane, N- [N ′-(2′-aminoethyl)- -Aminoethyl] -3-aminopropyltrimethoxysilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N- Examples thereof include hydroxyethyl-N-methylaminopropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acryloxypropyltrimethoxysilane.

Examples of the metal compound having a functional group include metal compounds of metal M from the first group III to V and / or the second group II to IV of the periodic table. Zirconium and titanium alkoxides, M (OR) ₄ (M = Ti, Zr), wherein part of the OR group is replaced by a complexing agent such as a β-dicarbonyl compound or a monocarboxylic acid. Can be mentioned. When a compound having a polymerizable unsaturated group (such as methacrylic acid) is used as a complexing agent, a polymerizable unsaturated group can be introduced.

As the dispersion medium, water and / or an organic solvent is preferably used. A particularly preferred dispersion medium is distilled (pure) water. As the organic solvent, polar, nonpolar and aprotic solvents are preferred. Examples thereof include alcohols such as aliphatic alcohols having 1 to 6 carbon atoms (particularly methanol, ethanol, n- and i-propanol and butanol), ketones such as acetone and butanone, esters such as ethyl acetate; , Ethers such as tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethylsulfoxide; and aliphatic (optionally halogenated) such as pentane, hexane and cyclohexane And hydrocarbons. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation (optionally under reduced pressure), and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

  In preparing the inorganic fine particles (i), the concentration of the dispersion medium is usually 40 to 90, preferably 50 to 80, particularly 55 to 75% by weight. The rest of the dispersion is composed of untreated inorganic fine particles and the surface modifying compound. Here, the weight ratio of the inorganic fine particles / surface modification compound is preferably 100: 1 to 4: 1, more preferably 50: 1 to 8: 1, and even more preferably 25: 1 to 10: 1. .

  The inorganic fine particles (i) are preferably prepared at room temperature (about 20 ° C.) to the boiling point of the dispersion medium. Particularly preferably, the dispersion temperature is 50 to 100 ° C. The dispersion time depends in particular on the type of material used, but is generally from a few minutes to a few hours, for example 1 to 24 hours.

When the inorganic fine particles (i) are prepared, the inorganic fine particles are subjected to mechanical reaction pulverization in a dispersion medium in which the surface modifying compound is present, and at least partially chemically bonded to the colloidal inorganic fine particles obtained by pulverizing the surface modifying compound. This embodiment is also preferably used.
In this case, the mechanical pulverization is generally performed by a mill, a kneader (kneader), a cylinder mill or, for example, a high-speed disperser. Grinding machines suitable for machine grinding are homogenizer, turbo stirrer, mill with remote grinding tool (ball mill, rod mill, drum mill, cone mill, tube mill, self-pulverizing mill, planetary mill, vibration mill and stirrer mill), heavy roller Kneader, colloid mill and cylinder mill. Among them, a particularly preferable mill is a stirring ball mill having a motion stirrer and pulverized balls as pulverizing means.
Milling with grinding and homogenizing is preferably performed at room temperature. The required time is appropriately adjusted according to the type of mixing and the grinder used.

(Ii) A monomer in which inorganic fine particles having a particle diameter of 500 nm or less are dispersed in a hydrophobic vinyl monomer is discharged into water through a hydrophilicized porous membrane to obtain an aqueous dispersion of monomer droplets in which inorganic fine particles are dispersed. Inorganic fine particles having reactive functional groups on the surface, obtained by polymerization.
When the inorganic fine particles (ii) are used, there are merits that monodispersity is further enhanced from the viewpoint of particle size distribution, and irregular performance can be suppressed when coarse particles are included.

  The inorganic fine particles (C) used in the present invention are inorganic fine particles that have at least a part of the surface coated with an organic component and have reactive functional groups introduced by the organic component on the surface. The reactive vinyl monomer contains at least one having a reactive functional group or having another reactive functional group that allows a desired reactive functional group to be introduced later. For example, after using a hydrophobic vinyl monomer having a carboxyl group in advance and polymerizing it, the carboxyl group is reacted with glycidyl methacrylate to introduce a polymerizable unsaturated group.

  Specific examples of the hydrophobic vinyl monomer include aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene, divinylbenzene; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) T-butyl acrylate, n-hexyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Stearyl, benzyl (meth) acrylate, mono or di (meth) acrylate of (poly) ethylene glycol, mono or di (meth) acrylate of (poly) propylene glycol, mono- or di- (1,4-butanediol) (Meth) acrylate, trimethylolpropane mono- Unsaturated carboxylic acid esters such as di- or tri- (meth) acrylate; allyl compounds such as diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate; (poly) ethylene glycol di (meth) acrylate And (poly) oxyalkylene glycol di (meth) acrylates such as (poly) propylene glycol di (meth) acrylate. In addition, conjugated diene compounds such as butadiene, isoprene and chloroprene. Furthermore, reactive functional group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, glycidyl methacrylate, vinylpyridine, diethylaminoethyl acrylate, N-methylmethacrylamide, acrylonitrile and the like can be mentioned. Among these, highly water-soluble monomers such as acrylic acid, methacrylic acid, and itaconic acid can be used as long as the water solubility of the whole monomer is high and an oil-in-water monomer emulsion cannot be formed.

  The inorganic fine particles used in (ii) must have a small particle size and be well dispersed in the hydrophobic vinyl monomer. The particle size of the inorganic particles used here is 500 nm or less, preferably 300 nm or less, more preferably 150 nm or less. In addition, when the inorganic fine particles are not familiar with the hydrophobic vinyl monomer, it is preferable to previously surface the surface of the inorganic fine particles. For the surface treatment, a known method such as a dispersant treatment for adsorbing a pigment dispersant on the inorganic surface, a coupling agent treatment with a silane coupling agent, a titanate coupling agent, or a compound coating treatment by capsule polymerization may be applied. it can.

In (ii), in order to emulsify the hydrophobic vinyl monomer in which the inorganic fine particles are dispersed in water, the hydrophobic vinyl monomer is discharged into the water through the hydrophilicized porous membrane. These porous pores must have an average pore diameter of 0.01 to 5 μm, a uniform pore diameter, and must penetrate the front and back of the membrane. Glass is preferable as the material of the film. As a specific example, SiO ₂ —Al ₂ O ₃ —B ₂ O ₃ —CaO-based glass fired using volcanic ash shirasu as the main raw material is microphase-separated by heat treatment to be rich in boric acid. Porous glass (referred to as SPG) obtained by dissolving and removing the phase with an acid is preferred.

  In (ii), a surfactant or a water-soluble polymer needs to be present as a monomer droplet stabilizer in the aqueous phase for extruding the hydrophobic vinyl monomer containing inorganic fine particles through the porous membrane. Without the stabilizer, the monomer droplets ejected through the film merge with each other and have a wide particle size distribution. A preferable stabilizer is a water-soluble polymer stabilizer such as polyvinyl alcohol, hydroxypropylcellulose, polyvinylpyrrolidone or the like when the monomer droplets are about 1 μm or more, and a small amount of anionic surfactant or It is also preferable to add a nonionic emulsifier. For example, a combination of sodium lauryl sulfate as an emulsifier and 1-hexadecanol as a co-emulsifier is particularly preferable as the stabilizer in (ii) because it strongly adsorbs to the droplet surface and has a large stabilizing effect.

  In (ii), in order to polymerize the aqueous dispersion of monomer droplets containing emulsified inorganic fine particles, an oil-soluble radical initiator is mainly used. Examples of initiators that can be used as oil-soluble radical initiators include azo initiators such as azobisisobutyronitrile, aromatic peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, diisopropyl Examples thereof include aliphatic peroxides such as peroxydicarbonate and di (2-ethylhexylperoxy) dicarbonate. These can be used by dissolving in the monomer phase in advance before emulsification. Moreover, you may add water-soluble radical polymerization inhibitors, such as hydroquinone and iron chloride.

(Iii) Reactive functional group to be introduced into the inorganic fine particles, formula (2):
^{-Q 1 -C (= Q 2)} -NH- (2)
(Wherein Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S), and a silanol group or a silanol group is generated by hydrolysis. Inorganic fine particles having reactive functional groups on the surface, obtained by bonding a compound containing a group and metal oxide fine particles.
When the inorganic fine particles (iii) are used, there are merits that the amount of organic components is increased, dispersibility and film strength are further increased.

First, a compound containing a reactive functional group to be introduced into the inorganic fine particles, a group represented by the above formula (2), and a silanol group or a group that generates a silanol group by hydrolysis (hereinafter, reactive functional group-modified hydrolyzable silane Will be explained).
In the reactive functional group-modified hydrolyzable silane, the reactive functional group to be introduced into the inorganic fine particles is not particularly limited as long as it is appropriately selected so that it can react with the compound (A) and the compound (B). Suitable for introducing polymerizable unsaturated groups as described above.

In the reactive functional group-modified hydrolyzable silane, the group represented by the formula (2) [—Q ¹ —C (= Q ² ) —NH—] is specifically [—O—C (═O ) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [— NH-C (= S) -NH-] and [-S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use at least one NH-] group in combination. The group represented by the formula (2) [—Q ¹ —C (= Q ² ) —NH—] generates an appropriate cohesive force due to hydrogen bonding between molecules and has excellent mechanical strength when formed into a cured product. It is considered that properties such as adhesion to the substrate and heat resistance can be imparted.

  Examples of the group that generates a silanol group by hydrolysis include groups having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An oxysilyl group is preferred. A silanol group or a group that forms a silanol group by hydrolysis can be combined with the metal oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

に示す化合物を挙げることができる。 Preferable specific examples of the reactive functional group-modified hydrolyzable silane include, for example, the following formula (3):

The compound shown to can be mentioned.

式（４）中、Ｒ^a、Ｒ^bは同一でも異なっていてもよいが、水素原子又はＣ₁からＣ₈のアルキル基若しくはアリール基であり、例えば、メチル、エチル、プロピル、ブチル、オクチル、フェニル、キシリル基等を挙げることができる。ここでｍは１、２又は３である。
［（Ｒ^aＯ）_mＲ^b _3-mＳｉ−］で示される基としては、例えば、トリメトキシシリル基、トリエトキシシリル基、トリフェノキシシリル基、メチルジメトキシシリル基、ジメチルメトキシシリル基等を挙げることができる。このような基のうち、トリメトキシシリル基又はトリエトキシシリル基等が好ましい。

In formula (4), R ^a and R ^b may be the same or different, but are a hydrogen atom or a C ₁ to C ₈ alkyl group or aryl group, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, m is 1, 2 or 3.
Examples of the group represented by [(R ^a O) _m R ^b _3-m Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ^c is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may contain a chain, branched chain or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.
R ^d is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (2). Can also be included.

R ^e is an (n + 1) -valent organic group, and is preferably selected from a chain, branched chain, or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group.
Y ′ represents a monovalent organic group having a reactive functional group. The reactive functional group itself as described above may be used. For example, when the reactive functional group is selected from a polymerizable unsaturated group, (meth) acryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (Oxy) group, cinnamoyl (oxy) group, maleate group, (meth) acrylamide group and the like can be mentioned. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

  For the synthesis of the reactive functional group-modified hydrolyzable silane used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, for example, when it is desired to introduce a polymerizable unsaturated group, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group. . Further, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen group-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

For example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, or the like can be suitably used as the mercaptoalkoxysilane.
Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane, and the like. It can be used suitably.
Examples of the active hydrogen-containing polymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol. -Lutri (meth) acrylate, dipentaerythritol rupenta (meth) acrylate and the like. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used.

  In the production of the inorganic fine particles (C) in (iii), a reactive functional group-modified hydrolyzable silane is separately hydrolyzed and then mixed with the inorganic fine particles, followed by heating and stirring, or A method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles, and in the presence of other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of inorganic fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles is preferable. When the inorganic fine particles (C) (iii) are produced, the temperature is usually 20 ° C. or higher and 150 ° C. or lower, and the treatment time is in the range of 5 minutes to 24 hours.

  In order to accelerate the hydrolysis reaction, an acid, salt or base may be added as a catalyst. Preferable examples of the acid include organic acids and unsaturated organic acids; examples of the base include tertiary amines or quaternary ammonium hydroxides. The amount of the acid or base catalyst added is 0.001 to 1.0% by weight, preferably 0.01 to 0.1% by weight, based on the reactive functional group-modified hydrolyzable silane.

As the inorganic fine particles (C), powdery fine particles not containing a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent dispersion sol from the viewpoint of high productivity because the dispersion step can be omitted.
The content of the inorganic fine particles (C) is preferably 10 to 60 parts by weight, and more preferably 25 to 40 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B). If it is less than 10 parts by weight, the hardness of the hard coat layer surface may be insufficient, and if it exceeds 60 parts by weight, the adhesion at the interface between the hard coat layer and the substrate may be insufficient.

<Other ingredients>
The curable resin composition of the present invention may contain a polymerization initiator, an antistatic agent, an antiglare agent, and a solvent in addition to the above essential components. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. When it contains an antistatic agent and / or an antiglare agent, the curable resin composition of the present invention can further impart antistatic properties and / or antiglare properties.
(Polymerization initiator)
In the present invention, in order to initiate or promote the radical polymerizable functional group or the cationic polymerizable functional group, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator may be used as necessary. good. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization or cationic polymerization.

The radical polymerization initiator releases a substance that initiates radical polymerization by light irradiation and / or heating. Examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. Specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) ), 1-hydroxy-cyclohexyl-phenyl-ketone (quotient Name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 369, Ciba Specialty Chemicals) Manufactured by Co., Ltd.), bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name) Irgacure 784, Ciba Specialty Chemicals Co., Ltd.) and the like.

The cationic polymerization initiator releases a substance that initiates cationic polymerization by light irradiation and / or heating. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidi). Enyl) iron (II) and the like, and specific examples include benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosicphthalimide and the like.

  Examples of radical polymerization initiators that can be used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. More specifically, iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluorides, hexaf Sulfonium salts such as orophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, Examples include 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine and 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine.

(Antistatic agent (conductive agent))
Antistatic agents for forming the antistatic layer include quaternary ammonium salts, pyridinium salts, various cationic compounds having a cationic group such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, Anionic compounds having an anionic group such as phosphate ester base and phosphonate base, amphoteric compounds such as amino acid series and amino sulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. Further, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or compound that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.

Moreover, electroconductive ultrafine particles are mentioned. Examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation), often abbreviated as ITO ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The fine particles refer to those having a so-called submicron size of 1 micron or less, and preferably those having an average particle size of 0.1 nm to 0.1 μm.
The antistatic agent is contained in an amount of 1 to 30 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the total amount of the compound (A) and the compound (B).

(Anti-glare agent)
As an anti-glare agent, the thing similar to the anti-glare agent demonstrated by the term of the anti-glare layer mentioned later is 20-30 weight part with respect to 100 weight part of total amounts of the said compound (A) and the said compound (B). , Preferably 10 to 25 parts by weight.

(solvent)
Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Ketones; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide; diisopropyl ether, tetrahydrofuran, dioxane, dioxolane, etc. Ethers; halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, tetrachloroethane; dimethyl sulfoxide, Other materials such as propylene carbonate; or mixtures thereof. More preferred solvents include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone and the like.

<Preparation of resin composition>
The curable resin composition of the present invention is prepared by mixing and dispersing the above components according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing. When the inorganic fine particles (C) are obtained in a state of being dispersed in a solvent, the compound (A), the compound (B), and other components including the solvent are appropriately added, mixed and dispersed in the dispersed state. It is prepared by processing.

  The concentration of the solid content of the curable resin composition is not particularly limited, but it is usually preferably in the range of 5 to 40% by weight, particularly preferably in the range of 15 to 30% by weight.

II. Hard coat film The hard coat film of this invention is equipped with the hard-coat layer which consists of hardened | cured material of the said curable resin composition on a base material, Preferably a transparent resin base material.
The hard coat film of the present invention has sufficient scratch resistance by providing a hard coat layer comprising a cured product of the curable resin composition on a base material, preferably a light-transmitting resin base material. In addition, no cracks are generated, curling is suppressed, shrinkage of the base material hardly occurs during curing, and production is possible at a high production rate.
That is, in the present invention, the curable resin composition for forming the hard coat layer can react with the compound (B) and the inorganic fine particles (C), and further with the compound (B) and the inorganic fine particles (C). And a polyalkylene oxide chain-containing compound (A) having three or more reactive functional groups at the terminal. The polyalkylene oxide chain-containing compound (A) has a short main chain, and both the compound (B) and the inorganic fine particles (C) which are hard segment components due to the reactive functional group at the end of the comb-like polyalkylene oxide chain Since the hard coat layer of the present invention can provide flexibility and resilience while maintaining the desired hardness even if it is a thin film, it can prevent cracks from being generated during bending or cutting.

  Moreover, the curable resin composition forming the hard coat layer of the present invention contains the compound (A), the compound (B), and the inorganic fine particles (C), and these all react with each other, It can be cured in a low dose and in a short time. Therefore, the curable resin composition of the present invention reduces thermal damage to the substrate due to the heat of polymerization during curing, hardly causes shrinkage of the substrate during curing, can suppress curling of the hard coat layer, and Hard coat film can be manufactured at high production speed.

  FIG.1 and FIG.2 is sectional drawing which shows an example of the hard coat film of this invention. In the example shown in FIG. 1, a hard coat layer 2 made of a cured product of a curable resin composition is laminated on one surface side of a light transmissive resin substrate 1. In the example shown in FIG. 2, a hard coat layer 2 made of a cured product of the curable resin composition is laminated on one surface side of the light transmissive resin base material 1, and a lower refractive index is further formed on the hard coat layer 2. Layer 3 is laminated.

As shown in FIG. 2, the hard coat film of the present invention is added between the light-transmitting resin substrate and the hard coat layer and / or the hard coat film in consideration of the function or use as the hard coat film. Other layers, for example, one or more layers selected from the group consisting of an antistatic layer, an antiglare layer, a low refractive index layer, and an antifouling layer may be formed on the layer.
The hard coat film of the present invention may be provided with an antistatic function or an antiglare function when the hard coat layer contains an antistatic agent and / or an antiglare agent.
Hereinafter, each layer which comprises the hard coat film of this invention is demonstrated in order.

1. Base material The base material may be transparent, translucent, colorless or colored as long as it transmits light, but the average light transmittance in the visible light region of 380 to 780 nm is 50% or more, preferably 70% or more, More preferably, it is 85% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and the air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC). These light-transmitting resin substrates are excellent in terms of thinness, lightness, resistance to cracking, flexibility, and the like.

  Triacetate cellulose (TAC), diacetyl cellulose, acetate propionate cellulose, acetate butyrate cellulose, polyethylene terephthalate (PET), cyclic polyolefin, polyethersulfone, (meth) acrylic resin, polyurethane resin, polyester , A film or sheet formed of polycarbonate, polysulfone, polyether, trimethylpentene, polyetherketone, (meth) acrylonitrile, or the like.

  In the present invention, the substrate is appropriately selected depending on the mode in which the hard coat film is used. For example, when optical isotropy is required for the target hard coat film, a transparent substrate such as cellulose such as triacetate cellulose (TAC), diacetyl cellulose, acetate propionate cellulose, acetate butyrate cellulose, etc. Ester, polynorbornene-based transparent resin product name Arton (manufactured by JSR Co., Ltd.), ZEONOR (manufactured by Nippon Zeon Co., Ltd.), etc., easy adhesion treatment with cyclic polyolefin, polyester resin, acrylic resin, polyether resin PET or the like is used. When used for a liquid crystal display, triacetate cellulose (TAC) and cyclic polyolefin are preferable.

  In the present invention, the light-transmitting resin substrate may be subjected to surface treatment (eg, saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment), and primer layer (adhesive) Layer) may be formed. The light-transmitting resin substrate in the present invention refers to those including these surface treatments and primer layers.

  The thickness of the light-transmitting resin substrate is usually about 30 μm to 200 μm, preferably 40 μm to 200 μm. In the present invention, curl prevention is particularly excellent, so curling can be prevented even when the light-transmitting resin substrate is thin, and even a thickness of about 40 μm to 80 μm can be suitably used.

In the present invention, by having the specific hard coat layer, it is possible to suppress the occurrence of shrinkage wrinkles of the tatami pattern based on the thermal damage of the base material due to the heat of polymerization generated when the hard coat layer is cured. Therefore, even a base material having a relatively low heat resistance such as TAC does not cause such shrinkage wrinkles.
Moreover, it is preferable that the surface roughness (Ra) after laminating | stacking a hard-coat layer is 0.1 micrometer or less. Here, the surface roughness (Ra) is measured according to JIS B0601.

2. Hard coat layer The hard coat layer used in the present invention is a layer comprising a cured product of the curable resin composition.
In the present invention, the “hard coat layer” indicates a hardness of “H” or higher in the pencil hardness test specified in JIS 5600-5-4 (1999) as described above. The hardness is a value that depends on the type and thickness of the base material and is appropriately selected according to the use and required performance. The hard coat layer of the present invention is preferably 2H or more, more preferably in a pencil hardness test. Is 3H or more, particularly preferably 4H or more.

  Since the hard coat layer of the present invention is a layer composed of a cured product of the curable resin composition, an antiglare layer, a low refractive index layer, a high refractive index layer, a charging layer are added depending on the components added to the resin composition. It can also serve as a functional layer such as a preventive layer or an antifouling layer.

In the hard coat film of the present invention, the hard coat layer may be a single layer or a plurality of layers. The single layer in this case is a hard coat layer formed of the same composition, and may be formed by a plurality of coatings as long as the composition after coating and drying is the same composition. On the other hand, the term “multiple layers” means that the layers are formed from a plurality of compositions having different compositions. For example, a configuration in which the hard coat layer of the present invention that also functions as a low refractive index layer is further laminated on the hard coat layer of the present invention exclusively for the purpose of improving scratch resistance.
In the hard coat film of the present invention, the hard coat layer is essential, but may further include a hard coat layer made of another curable resin composition.

The film thickness (at the time of curing) of the hard coat layer can be appropriately selected according to the strength and required performance of the substrate. For example, it is 1-100 micrometers, Preferably it is 5-30 micrometers.
If the hard coat layer is too thin, the scratch resistance of the hard coat layer is insufficient. On the other hand, if the hard coat layer is too thick, the hardness is improved, but cracks and curls are likely to occur. Select appropriately according to strength and required performance.

  Further, when the surface of the hard coat layer is subjected to 10 reciprocating frictions with a predetermined friction load using # 0000 steel wool, and the presence or absence of subsequent peeling of the hard coat layer is visually observed, the friction load becomes 1000 g or more. It is preferable to withstand, and it is preferable to withstand a friction load of 1500 g or more.

  Further, the curl of the hard coat film is preferably 3 cm or less when a sample piece obtained by cutting the base material to 10 cm × 10 cm is placed on a horizontal base and the lift of the end portion is measured.

3. Other Layers The hard coat film according to the present invention is composed of a light-transmitting resin substrate and a hard coat layer. However, in consideration of the function or use as a hard coat film, in addition to the hard coat layer of the present invention, one or more layers as described below may be further contained. Furthermore, you may form including a middle refractive index layer and a high refractive index layer.

(1) Antistatic layer The antistatic layer contains an antistatic agent and a resin. The antistatic agent is the same as that described in the column of the hard coat layer. The thickness of the antistatic layer is preferably about 30 nm to 1 μm.

As the resin contained in the antistatic layer, a thermoplastic resin, a thermosetting resin, a photocurable resin, or a photocurable compound (including an organic reactive silicon compound) can be used. As the resin, a thermoplastic resin can be used, but a thermosetting resin is preferably used, and a photocurable composition containing a photocurable resin or a photocurable compound is more preferable.
As a photocurable composition, the pre-compound, compound, and / or monomer which have a polymerizable unsaturated group or an epoxy group in a molecule | numerator are mixed suitably.
As the pre-compound, compound and monomer in the photocurable composition, the same compounds as those mentioned for the compound (B) of the hard coat layer can be used.

  Usually, as a monomer in a photocurable composition, 1 type, or 2 or more types are mixed and used as needed, but in order to give a normal application | coating suitability to a photocurable composition, the said pre-compound Alternatively, the compound is preferably 5% by weight or more, and the monomer and / or polythiol compound is preferably 95% by weight or less.

(2) Antiglare layer The antiglare layer may be formed between the transparent resin substrate and the hard coat layer or the low refractive index layer. The antiglare layer comprises a resin and an antiglare agent, and the resin may be the same as that described in the section of the antistatic layer.

According to a preferred aspect of the present invention, the antiglare layer has an average particle diameter of R (μm), and the maximum value from the substrate surface in the vertical direction of the convex and concave portions of the antiglare layer is Hmax (μm). And the average interval between the irregularities of the antiglare layer is Sm (μm), and the average inclination angle of the irregularities is θa, the following formula:
8R ≦ Sm ≦ 30R
R <Hmax <3R
1.3 ≦ θa ≦ 2.5
1 ≦ R ≦ 8
What satisfies all simultaneously is preferable.

  According to another preferred embodiment of the present invention, when the refractive indexes of the fine particles and the transparent resin composition are n1 and n2, respectively, Δn = | n1-n2 | <0.1 is satisfied. And the anti-glare layer whose haze value inside an anti-glare layer is 55% or less is preferable.

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is about 2 to 30 parts by weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the resin composition.

It is preferable to add an antisettling agent when adjusting the composition for the antiglare layer. This is because, by adding an anti-settling agent, precipitation of the anti-glare agent can be suppressed and the anti-glare agent can be uniformly dispersed in the solvent. Specific examples of the anti-settling agent include silica beads having an average particle size of 0.5 μm or less, preferably about 0.1 to 0.25 μm.
The film thickness (when cured) of the antiglare layer is 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is within this range, the function as an antiglare layer can be sufficiently exhibited.

(3) Low refractive index layer The low refractive index layer is composed of a resin containing silica or magnesium fluoride, a fluorine resin which is a low refractive index resin, silica or a fluorine resin containing magnesium fluoride, It can be composed of a thin film having a refractive index of 1.46 or less, which is also about 30 nm to 1 μm, or a thin film formed by chemical vapor deposition or physical vapor deposition of silica or magnesium fluoride. The resin other than the fluororesin is the same as the resin used for constituting the antistatic layer.

  More preferably, the low refractive index layer can be composed of a silicone-containing vinylidene fluoride copolymer. This silicone-containing vinylidene fluoride copolymer is specifically a monomer containing 30 to 90% vinylidene fluoride and 5 to 50% hexafluoropropylene (including percentages below, all in terms of weight). It is obtained by copolymerization using the composition as a raw material, and comprises 100 parts of a fluorine-containing copolymer having a fluorine content of 60 to 70% and 80 to 150 parts of a polymerizable compound having an ethylenically unsaturated group. A low refractive index of less than 1.60 (preferably 1.46 or less) having a refractive index of less than 1.60 (preferably 1.46 or less) which is a thin film having a film thickness of 200 nm or less and is provided with scratch resistance. Form a layer.

In addition, the low refractive index layer also can be formed of a thin film made of SiO _2, an evaporation method, a sputtering method, or a plasma CVD method or the like, or to form a SiO ₂ gel film from the sol solution containing SiO ₂ sol It may be formed by a method. The low refractive index layer, in addition to SiO ₂ also, the or a thin film MgF _2, but may be configured in other materials, in terms of high adhesion to the lower layer, it is preferable to use a SiO ₂ thin film.

According to a preferred embodiment of the low refractive index layer of the present invention, it is preferable to use “fine particles having voids”.
The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the low refractive index layer. “Fine particles with voids” means a structure in which fine particles are filled with gas and / or a porous structure containing gas, and is inversely proportional to the gas occupancy in the fine particles compared to the original refractive index of the fine particles. Thus, it means a fine particle having a reduced refractive index. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

(4) Antifouling layer According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing contamination on the outermost surface of the low refractive index layer. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film.

  Specific examples of the antifouling agent include a fluorine-based compound and / or silicon that has low compatibility with a photocurable resin composition having a fluorine atom in the molecule and is difficult to add to the low refractive index layer. And a fluorine-based compound and / or a siliceous compound having compatibility with fine particles, a photocurable resin composition having a fluorine atom in the molecule, and fine particles.

4). Use The hard coat film of the present invention is used as a hard coat laminate, preferably as an antireflection laminate. In addition, the hard coat film of the present invention is used for a transmissive display device. In particular, it is used for display displays of televisions, computers, word processors and the like. In particular, it is used on the surface of displays such as CRTs, liquid crystal panels, and plasma displays.

Hereinafter, the manufacturing method of the hard coat film of this invention is demonstrated.
First, the transparent resin base material mentioned in the description of the hard coat layer is prepared.
Next, the curable resin composition of the present invention is prepared.
Next, the obtained curable resin composition is applied on a transparent substrate and dried.
The coating method is not particularly limited as long as it can uniformly coat the resin composition for forming a hard coat layer on the surface of the base film, and is not limited to spin coating, dipping, spraying, and slide coating. Various methods such as a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
The coating amount on the light-transmitting resin base material varies depending on the performance required of the obtained hard coat film, but the coating amount after drying is 1 g / m ^{2 to} 30 g / m ^2. in the range of, particularly preferably in the range of ^{5g / m 2 ~25g / m 2} .

  Examples of the drying method include reduced-pressure drying or heat drying, and a method combining these drying methods. For example, when a ketone solvent is used as the solvent, it is usually dried at a temperature in the range of room temperature to 80 ° C., preferably 40 ° C. to 60 ° C., for 20 seconds to 3 minutes, preferably 30 seconds to 1 minute. A process is performed.

Next, according to the reactive functional group contained in the resin composition, the coating film is cured by applying light and / or heating to the coating film on which the resin composition for forming a hard coat layer has been applied and dried. Thereby, the hard-coat layer which consists of hardened | cured material of the resin composition for hard-coat layer formation is formed, and the hard-coat film of this invention is obtained.
For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used. The irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. In the present invention, all of the essential components (A), (B), and inorganic fine particles (C) contained in the hard coat layer resin composition have a reactive functional group, Since all components are cross-linked, it can be effectively cured even at low energy. For example, the irradiation amount of the energy ray source can be set to 100 to 200 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. As a result, curing can be performed for a short time, and production efficiency can be increased. In the case of electron beam curing, an electron beam having energy of 100 keV to 300 keV is used.
When heating, it processes at the temperature of 40 to 120 degreeC normally. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.

The evaluation method performed in the Example mentioned later is as follows.
(1) Pencil hardness Pencil hardness of the hard coat layer surface of the obtained hard coat film was evaluated according to JISK5600-5-4 (1999). Using a 4H pencil, five lines were drawn with a load of 500 g, and the subsequent hard coat layer was visually checked for scratches and evaluated according to the following criteria.
<Evaluation criteria>
Evaluation A: The number of scratches was 0 to 1.
Evaluation ○: There were 2 to 3 scratches.
Evaluation x: There were 4 to 5 scratches.

(2) Curling test A sheet obtained by cutting a hard coat film to a size of 10 × 10 cm is placed on a flat place with the hard coat layer facing upward, and the floating state of both ends is observed, and the four corners are lifted from the plane. It was evaluated by measuring the average value of the height.
<Evaluation criteria>
Evaluation A: Less than 30 mm.
Evaluation (circle): It was 30-50 mm.
Evaluation x: It exceeded 50 mm.

(3) Crack generation curvature The hard coat film cut to a size of 10 × 2 cm was wound around a cylinder with a curvature with the hard coat surface facing upward, and the curvature diameter at which cracking started to occur was measured.
<Evaluation criteria>
Evaluation A: Less than 10 mm.
Evaluation (circle): It was 10-20 mm.
Evaluation x: exceeded 20 mm.

(Synthesis Example 1: Synthesis of Compound (A) -1)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe, 10.0 parts by weight of 1,4-butanediol (raw material 1), p-methoxyphenol 0.05 Part by weight, 0.05 part by weight of dibutyltin dilaurate and 50.0 parts by weight of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. with stirring under a nitrogen stream. On the other hand, 49.3 parts by weight of isophorone diisocyanate (raw material 2) was charged in a dropping container and uniformly dropped into the reaction container over 1 hour. At that time, the reaction vessel temperature was kept at 50 ± 3 ° C. After keeping the temperature for 1 hour with stirring, 0.05 parts by weight of p-methoxyphenol and 0.05 parts by weight of dibutyltin dilaurate were further added, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream. Thereafter, 32.0 parts by weight of 4-hydroxybutyl acrylate (raw material 3) charged in the dropping vessel was uniformly dropped into the reaction vessel over 1 hour with stirring.
After completion of the dropping, the dropping container was washed with 50.0 parts by weight of methyl ethyl ketone, and the washed solution was put into the reaction container as it was. The mixture was further kept warm for 2 hours with stirring, and then heated to 75 ° C. Thereafter, stirring and heating were continued at 75 ± 3 ° C. until the peak derived from the isocyanate in the infrared absorption spectrum disappeared. The peak derived from the isocyanate disappeared in about 4 to 6 hours. After confirming the disappearance of this peak, the temperature was lowered to 60 ° C., 3.5 parts by weight of methanol was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 60.4 parts by weight of methyl ethyl ketone was added to obtain a transparent resin solution. Finally, the solvent was removed using an evaporator to obtain 72.5 parts by weight of Compound (A) -1.

(Synthesis Examples 2 to 4: Synthesis of Compound (A) -2 to 4)
The target compound was obtained using the following raw materials in the same manner as for compound (A) -1.

(Synthesis Example 5: Synthesis of Compound (A) -5)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 10.0 parts by weight of 1,6-hexane diisocyanate trimer, 0.05 weight of dibutyltin dilaurate And 50.0 parts by weight of methyl ethyl ketone were charged, and the temperature was raised to 65 ° C. with stirring under an air stream. 21.2 parts by weight of pentaerythritol triacrylate was charged into the dropping container and uniformly dropped into the reaction container over 3 hours. At that time, the reaction vessel temperature was kept at 65 ± 3 ° C.
After completion of the dropping, the dropping container was washed with 50.0 parts by weight of methyl ethyl ketone, and the washed solution was put into the reaction container as it was. The mixture was further kept warm for 2 hours with stirring, and then heated to 75 ° C. Thereafter, stirring and heating were continued at 75 ± 3 ° C. until the peak derived from the isocyanate in the infrared absorption spectrum disappeared. The peak derived from the isocyanate disappeared in about 4 to 6 hours. After confirming the disappearance of this peak, the temperature was lowered to 60 ° C., 5.0 parts by weight of methanol was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 50.0 parts by weight of methyl ethyl ketone was added to obtain a transparent resin solution. Finally, the solvent was removed using an evaporator to obtain 29.3 parts by weight of Compound (A) -5.

(Synthesis Example 6: Synthesis of Compound (A) -6)
Except for using 10.0 parts by weight of 1,6-hexane diisocyanate dimer instead of 10.0 parts by weight of 1,6-hexane diisocyanate trimer, and 17.7 parts by weight of pentaerythritol triacrylate. In the same manner as in Synthesis Example 5, 26.7 parts by weight of Compound (A) -6 was obtained.

(Production Example 1: Preparation of inorganic fine particles (C) -1)
(1) Removal of surface adsorbed ions Water-dispersed colloidal silica having a particle diameter of 90 nm (Snowtex ZL, trade name, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 40% by weight, pH 9 to 10) is exchanged with a cation exchange resin (Diaion) After performing ion exchange for 3 hours using 400 g of SK1B (Mitsubishi Chemical Corporation) and then performing ion exchange for 3 hours using 200 g of anion exchange resin (Diaion SA20A, Mitsubishi Chemical Corporation) To obtain an aqueous dispersion of silica fine particles having a solid content concentration of 20% by weight.
At this time, the Na ₂ O content of the aqueous dispersion of silica fine particles was 7 ppm for each silica fine particle.

(2) Surface treatment (introduction of monofunctional monomer)
150 g of isopropanol, 4.0 g of 3,6,9-trioxadecanoic acid, and 4.0 g of methacrylic acid are added to 10 g of the silica fine particle aqueous dispersion subjected to the treatment (1), and the mixture is stirred for 30 minutes. Mixed.
The obtained mixed liquid was stirred while heating at 60 ° C. for 5 hours to obtain a silica fine particle dispersion in which a methacryloyl group was introduced on the surface of the silica fine particles. Distilled water and izopropanol were distilled off from the obtained silica fine particle dispersion using a rotary evaporator, and while adding methyl ethyl ketone so as not to dry, the final remaining water and isopropanol were adjusted to 0.1% by weight, A silica-dispersed methyl ethyl ketone solution having a solid content of 50% by weight was obtained.
The inorganic fine particles (C) -1 thus obtained had an average particle diameter of d50 = 92 nm as a result of measurement with a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd. Further, the amount of the organic component covering the surface of the silica fine particles was 4.05 × 10 −3 g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 2: Preparation of inorganic fine particles (C) -2)
(1) Surface Adsorbed Ion Removal As in Production Example 1, an aqueous dispersion of silica fine particles from which surface adsorbed ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1 except that methacrylic acid in Production Example 1 was changed to dipentaerythritol pentaacrylate (SR399, trade name, manufactured by Sartomer Co., Ltd.).
The inorganic fine particles (C) -2 thus obtained had an average particle diameter of d50 = 93 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the silica surface was 3.84 × 10 −3 g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 3: Preparation of inorganic fine particles (C) -3)
To a solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 part of dibutyltin dilaurate in dry air, 20.6 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour with stirring, then at 60 ° C. Stir for 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain Compound (1).

Under nitrogen flow, methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name, methanol solvent colloidal silica dispersion (number average particle size 0.012 μm, silica concentration 30%)) 88.5 parts (solid content 26.6 parts) ), 8.5 parts of the compound (1) synthesized above and 0.01 part of p-methoxyphenol were stirred at 60 ° C. for 4 hours. Subsequently, 3 parts of methyltrimethoxysilane as compound (2) is added to this mixed solution, and after stirring for 1 hour at 60 ° C., 9 parts of methyl orthoformate is added, and further heated and stirred at the same temperature for 1 hour. Thus, crosslinkable inorganic fine particles were obtained. The inorganic fine particles (C) -3 thus obtained had an average particle diameter of d50 = 63 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface was 7.08 × 10 −3 g / m ² as a result of measurement by thermogravimetric analysis.

[ Reference Example 1]
(1) Preparation of curable resin composition The following components were mixed and adjusted to a solid content of 50% by weight with a solvent to prepare a curable resin composition.
<Composition of curable resin composition>
-KRM7804 (trade name, manufactured by Daicel-Cytec; corresponding to the above compound (A), 9 functional, molecular weight 3,000): 20 parts by weight (in terms of solid content)
UV1700B (trade name, manufactured by Nippon Synthetic Chemical; corresponding to the above compound (B), 10 functional, molecular weight 2,000): 50 parts by weight (in terms of solid content)
-Inorganic fine particles (C) -1 in Production Example 1: 30 parts by weight (in terms of solid content)
・ Methyl ethyl ketone: 100 parts by weight ・ Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals, radical polymerization initiator): 0.4 parts by weight

(2) Production of Hard Coat Film Using a 80 μm cellulose triacetate film as the light-transmitting resin base material, the curable resin composition prepared in (1) was placed on the base material with a WET weight of 40 g / m ² (dry weight). 20 g / m ² ) was applied. The hard coat film of Reference Example 1 was prepared by drying at 50 ° C. for 30 seconds and irradiating with ultraviolet rays of 200 mJ / cm ² . Table 1 also shows the evaluation results.

[ Reference Example 2]
In the curable resin composition of Reference Example 1, instead of 20 parts by weight of KRM7804, 20 parts by weight of KRM8321 (trade name, manufactured by Daicel Cytec; 9-functional, molecular weight 3,000) was used as the compound (A). Except for the above, a curable resin composition was prepared in the same manner as in Reference Example 1.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[ Reference Example 3]
In the curable resin composition of Reference Example 1, instead of 20 parts by weight of KRM7804, 20 parts by weight of HMP-2M (trade name, manufactured by Negami Kogyo; 9 functional, molecular weight 8400) was used as the compound (A). In the same manner as in Reference Example 1, a curable resin composition was prepared.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[ Reference Example 4]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -1, except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[ Reference Example 5]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -2 except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Example 1 ]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -3, except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Example 2 ]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -4, except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Example 3 ]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -5 Except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Example 4 ]
Preparation In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, compound (A) -6, except for using 20 parts by weight, in the same manner as in Reference Example 1, a curable resin composition did.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[ Reference Examples 6 to 10 ]
Furthermore, in the said curable resin composition, each component of a compound (A), a compound (B), and an inorganic fine particle (C) is made into the thing of the reference examples 6-10 of Table 1, and is the same as that of the reference example 2. A curable resin composition was prepared.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 shows the evaluation results.

[Comparative Example 1]
A curable resin composition was prepared in the same manner as in Reference Example 1 except that KRM7804 (the above compound (A)) in the curable resin composition of Reference Example 1 was not used and UV1700-B was 70 parts by weight. .
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Comparative Example 2]
In the curable resin composition of Reference Example 1, instead of 20 parts by weight of KRM7804, the compound represented by the formula (1) and A is a chain structure having 6 carbon atoms, UN-904 (trade name, A curable resin composition was prepared in the same manner as in Reference Example 1 except that Negami Industries, Ltd .; 10 functional, molecular weight 5,000) was 20 parts by weight.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Comparative Example 3]
In the curable resin composition of Reference Example 1, in place of 20 parts by weight of KRM7804, UV-7605B (trade name, manufactured by Nihon Gosei; hexafunctional, which is a compound represented by the formula (1) and A is a cyclic structure, A curable resin composition was prepared in the same manner as in Reference Example 1 except that the molecular weight 1200) was 20 parts by weight.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

[Comparative Example 4]
In the curable resin composition of Reference Example 1, in place of 30 parts by weight of inorganic fine particles (C) -1 of Production Example 1 in terms of solid content, untreated silica fine particles (Snowtex YL, trade name, Nissan A curable resin composition was prepared in the same manner as in Reference Example 1 except that 30 parts by weight in terms of solid content was used.
Moreover, the hard coat film was produced similarly to the reference example 1. Table 1 also shows the evaluation results.

It is a figure which shows the basic layer structure of the hard coat film which concerns on this invention. It is a figure which shows the other basic layer structure of the hard coat film which concerns on this invention.

Explanation of symbols

1 light transmissive resin base material 2 hard coat layer 3 low refractive index layer

Claims (8)

(A) below (1) to either of compound (4),
(1) was synthesized from pentaerythritol triacrylate and 1,4-butane diol and isophorone diisocyanate Natick DOO, weight average molecular weight of 3,000 or more compounds having two or more reactive functional groups at the ends (2) was synthesized from pentaerythritol triacrylate 1,4-butanediol and a xylylene diisocyanate Natick DOO, weight average molecular weight having two or more reactive functional groups at the ends 3,000 or more compounds (3) pentaerythritol acrylate and were synthesized from a dimer of 1,6-hexane diisocyanate, a compound having two or more reactive functional groups at the ends (4) and the trimer of pentaerythritol triacrylate and 1,6-hexane diisocyanate synthesized, compounds having two or more reactive functional groups at the ends (B) above ingredients Urethane (meth) acrylates with the exception of compounds of A), or selected from epoxy (meth) acrylate compound weight average molecular weight of less than 10,000 with more than one reactive functional group, and,
(C) Inorganic fine particles having a (meth) acryloyl group introduced on the surface thereof, the organic component being coated on at least a part of the surface,
A curable resin composition comprising:   The content of the compound (A) is 5 to 100 parts by weight with respect to 100 parts by weight of the compound (B), and the content of the inorganic fine particles (C) is the compound (A) and the compound ( The curable resin composition of Claim 1 which is 10-60 weight part with respect to 100 weight part of total amounts of B).   The curable resin composition according to claim 1 or 2, wherein the inorganic fine particles (C) have an average particle size of 20 to 500 nm. The organic component that coats the inorganic fine particles (C) is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating. The curable resin composition described in 1.   A hard coat film having a hard coat layer on at least one surface of a substrate, wherein the hard coat layer forming material comprises the curable resin composition according to any one of claims 1 to 4, and the compound ( A hard coat film, wherein A), the compound (B), and the inorganic fine particles (C) are reacted with each other.   The hard coat film according to claim 5, wherein the substrate is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.   An optical element having the hard coat film according to claim 5 or 6 on a surface of the optical element.   An image display device comprising the hard coat film according to claim 5.

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