JP2018192704A - Transfer film and in-mold molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film capable of forming a hard coat layer having high surface hardness and excellent adhesion between layers by in-mold injection molding. SOLUTION: A base material, a hard coat layer laminated on a release layer formed on at least one surface of the base material, and an anchor coat layer laminated on at least one surface of the hard coat layer. Further, a transfer film having an adhesive layer, wherein the hard coat layer is formed from a curable composition containing a polyorganosylsesquioxane having a structural unit represented by the following formula (1). A transfer film in which the anchor coat layer contains an epoxy resin: [Chemical formula 1] [In formula (1), R1 represents a group containing a polymerizable functional group. ]. [Selection diagram] None

Description

  The present invention relates to a transfer film (in particular, an in-mold injection molding transfer film). More specifically, a transfer in which a hard coat layer, an anchor coat layer, and an adhesive layer are laminated in this order on a substrate and a release layer formed on at least one surface of the substrate. It is related with the film. The present invention also relates to an in-mold molded product to which a transfer layer of the transfer film is transferred.

  An in-mold injection molding method is used as a manufacturing method for decorating a surface of a plastic product such as wood grain or hard coating. The in-mold injection molding method forms a release layer on one side of a base film, and laminates a transfer layer (a layer in which a hard coat layer, an anchor coat layer, a colored layer, an adhesive layer, etc. are laminated) on the release layer. Insert the transfer film into the mold, place the base film side in close contact with the inner surface of the mold, close the mold, and inject the molten thermoplastic resin into the mold from the transfer layer side. Then, when the mold is opened and the molded product is taken out, the release layer and the hard coat layer are peeled off to transfer the transfer layer to the outermost surface to obtain a molded product. As a material for forming a hard coat layer in such an in-mold injection molding transfer film, UV acrylic monomer is mainly used (for example, see Patent Document 1). There is also an example in which nanoparticles are added to the hard coat layer in order to further improve the pencil hardness of the hard coat layer surface.

JP 2014-232122 A

  However, the pencil hardness of the transfer film having the hard coat layer using the above-described UV acrylic monomer is about 2H, and it cannot be said that the film still has sufficient surface hardness. Generally, in order to increase the hardness, it is conceivable to use a polyfunctional UV acryl monomer or to increase the thickness of the hard coat layer. As a result, there is a problem that cracks occur in the hard coat layer. Further, when nanoparticles are added to the hard coat layer, if the compatibility between the nanoparticles and the UV acrylic monomer is poor, there is a problem that the nanoparticles aggregate and the hard coat layer is whitened.

In addition, the basic structure of a transfer film used for in-mold injection molding is to first laminate a hard coat layer on a release layer formed on a base film to impart surface hardness to the molded product and to mold it. In order to transfer to the product with good adhesiveness, an adhesive layer is provided on the outermost surface (the surface in contact with the molded product). However, depending on the resin material constituting the hard coat layer, the adhesive layer, and the colored layer provided if necessary, sufficient adhesion cannot be obtained between these layers, and particularly high durability such as a dashboard of a car. There is a problem that the hard coat layer is floated or peeled off in applications where properties are required.
In order to cope with such low adhesion and its reduction, an anchor coat layer may be provided between layers such as a hard coat layer, an adhesive layer, and a colored layer. However, what type of resin to select as the material for the anchor coat layer to achieve high adhesion varies greatly depending on the type and combination of materials in each layer in the transfer layer, and is difficult to predict. The current situation requires consideration.

Therefore, an object of the present invention is to provide a hard coat having high surface hardness and excellent adhesion between each layer (particularly, between the hard coat layer and the adhesive layer or the colored layer) by an in-mold injection molding method. It is to provide a transfer film (in particular, an in-mold injection molding transfer film) capable of forming a layer.
Another object of the present invention is to provide an in-mold molded article having a high surface hardness and excellent adhesion, to which the transfer layer of the transfer film is transferred.

  In the transfer film, it is preferable that the surface of the uncured or semi-cured hard coat layer is coated with a hard coat solution or the like on the release layer of the base film and dried. This is because if the surface has tackiness, the blocking resistance is lowered, and it may be difficult to wind it on a roll.

  Furthermore, the use of transfer films having a hard coat layer has been expanding in recent years. In addition to having a high surface hardness as described above, the hard coat layer of a transfer film has a particularly high surface hardness. It is also required to have excellent heat resistance. The hard coat layer in the transfer film using the UV acrylic monomer described above cannot be said to be sufficient from the viewpoint of such heat resistance.

  In-mold injection molding transfer films are also generally required to have high flexibility and workability. This is because if the flexibility and workability are poor, the transfer film is difficult to follow the mold at the time of in-mold injection molding, which causes floating and peeling.

The inventors have used a transfer film having an uncured or semi-cured hard coat layer containing a polyorganosilsesquioxane having a silsesquioxane structural unit (unit structure) containing a polymerizable functional group. It has been found that a molded article covered with a hard coat layer having a high surface hardness can be produced by performing mold injection molding. In addition, as a result of examining various anchor coat layers suitable for the hard coat layer containing the polyorganosilsesquioxane, the present inventors have provided an anchor coat layer containing a specific material on the hard coat layer. It has been found that high adhesion to an adhesive layer, a colored layer, etc. can be realized, and that the surface hardness is unexpectedly improved.
The present invention has been completed based on these findings.

［式（１）中、Ｒ¹は、重合性官能基を含有する基を示す。］ That is, the present invention comprises a substrate,
A hard coat layer laminated on a release layer formed on at least one surface of the substrate;
An anchor coat layer laminated on at least one surface of the hard coat layer;
Furthermore, a transfer film having an adhesive layer,
The hard coat layer is formed from a curable composition containing a polyorganosilsesquioxane having a structural unit represented by the following formula (1),
Provided is a transfer film, wherein the anchor coat layer contains an epoxy resin.

[In the formula (1), R ¹ represents a group containing a polymerizable functional group. ]

［式（Ｉ）中、Ｒ^aは、重合性官能基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。］
で表される構成単位と、下記式（ＩＩ）

［式（ＩＩ）中、Ｒ^bは、重合性官能基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す。］
で表される構成単位を有し、前記式（Ｉ）で表される構成単位と前記式（ＩＩ）で表される構成単位のモル比［式（Ｉ）で表される構成単位／式（ＩＩ）で表される構成単位］は２０以上５００以下であってもよい。 In the transfer film, the polyorganosilsesquioxane is further represented by the following formula (I):

[In the formula (I), R ^a is a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
A structural unit represented by the following formula (II):

[In the formula (II), R ^b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The structural unit represented by the formula (I) and the molar ratio of the structural unit represented by the formula (II) [the structural unit represented by the formula (I) / formula (formula (I) The structural unit represented by II)] may be 20 or more and 500 or less.

  In the transfer film, the polyorganosilsesquioxane may have a number average molecular weight of 2500 to 50000.

［式（４）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（ＩＩ）におけるものと同じ。］
で表される構成単位を有し、シロキサン構成単位の全量（１００モル％）に対する前記式（１）で表される構成単位及び前記式（４）で表される構成単位の割合は５５〜１００モル％であってもよい。 In the transfer film, the polyorganosilsesquioxane further includes the following formula (4):

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
The ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) to the total amount (100 mol%) of the siloxane structural unit is 55-100. It may be mol%.

  In the transfer film, the polyorganosilsesquioxane may have a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

［式（２）中、Ｒ²は、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、又は、置換若しくは無置換のアルケニル基を示す。］
で表される構成単位を有していてもよい。 In the transfer film, the polyorganosilsesquioxane further includes the following formula (2):

[In the formula (2), R ² represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. An alkenyl group of ]
You may have the structural unit represented by these.

In the transfer film, R ² may be a substituted or unsubstituted aryl group.

  In the transfer film, the polymerizable functional group may be an epoxy group.

［式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｂ）

［式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｃ）

［式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、又は、下記式（１ｄ）

［式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基であってもよい。 In the transfer film, the R ¹ is represented by the following formula (1a)

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by formula (1c):

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
Or a group represented by the following formula (1d)

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The group represented by these may be sufficient.

In the transfer film, the curable composition may further contain a curing catalyst.
In the transfer film, the curing catalyst may be a photocationic polymerization initiator.
In the transfer film, the curing catalyst may be a thermal cationic polymerization initiator.
In the transfer film, the curing catalyst may be a radical photopolymerization initiator.
In the transfer film, the curing catalyst may be a thermal radical polymerization initiator.

In the transfer film, the curable composition may further contain a vinyl ether compound.
In the transfer film, the curable composition may further contain a vinyl ether compound having a hydroxyl group in the molecule.

  In the transfer film, the adhesive layer may include at least one selected from the group consisting of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin.

  The transfer film may further include at least one colored layer.

  In the transfer film, the hard coat layer may have a thickness of 3 to 150 μm.

  The transfer film may be a transfer film used for in-mold injection molding.

  Furthermore, the present invention provides an in-mold molded product in which a layer (transfer layer) excluding a substrate on which a release layer is formed from a transfer film is transferred.

  Since the transfer film of the present invention has a hard coat layer containing a polyorganosilsesquioxane containing a silsesquioxane structural unit having a polymerizable functional group as an essential component, in-mold injection is performed using the transfer film. By performing the molding, a molded product covered with a hard coat layer having a high surface hardness can be produced. In addition, since the transfer film of the present invention is provided with an anchor coat layer containing an epoxy resin on the hard coat layer, high adhesion to an adhesive layer or a colored layer is realized. The surface hardness of the coat layer is further improved. For this reason, the transfer film of the present invention can be suitably used as a transfer film for in-mold injection molding.

2 is a ¹ H-NMR chart of an epoxy group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 1. FIG. 2 is a ²⁹ Si-NMR chart of an epoxy group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 1. FIG. 2 is a ¹ H-NMR chart of an epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 2. FIG. 3 is a ²⁹ Si-NMR chart of an epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 2. FIG. 2 is a ¹ H-NMR chart of an epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 4. FIG. 6 is a ²⁹ Si-NMR chart of an epoxy group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 4. FIG. 6 is a ¹ H-NMR chart of an acrylic group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 5. FIG. 6 is a ²⁹ Si-NMR chart of an acrylic group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 5. FIG. 6 is a ¹ H-NMR chart of an acrylic group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 6. 6 is a ²⁹ Si-NMR chart of acrylic group-containing high molecular weight polyorganosilsesquioxane obtained in Production Example 6. FIG.

［式（１）中、Ｒ¹は、重合性官能基を含有する基を示す。］ [Transfer film]
The transfer film of the present invention was laminated on a substrate, a hard coat layer laminated on a release layer formed on at least one surface of the substrate, and on at least one surface of the hard coat layer. A transfer film having an anchor coat layer and an adhesive layer, wherein the hard coat layer has a structural unit represented by the following formula (1) (hereinafter referred to as “polyorganosilsesquioxane”). Formed from a curable composition (sometimes referred to as "organosilsesquioxane") (hereinafter sometimes referred to as "the curable composition of the present invention" or "the hard coat agent of the present invention"), The anchor coat layer includes an epoxy resin.

[In the formula (1), R ¹ represents a group containing a polymerizable functional group. ]

[Base material]
The base material in the transfer film of the present invention is a base material of the transfer film and refers to a portion constituting other than the transfer layer including the hard coat layer of the present invention. Here, the transfer layer is a layer excluding the substrate on which the release layer is formed in the transfer film of the present invention, and refers to a portion transferred to the surface of the molded product. As said base material, well-known, such as a plastic base material, a metal base material, a ceramic base material, a semiconductor base material, a glass base material, a paper base material, a wood base material (wood base material), and the base material whose surface is a coating surface Thru | or a usual base material can be used and it does not specifically limit. Among these, a plastic substrate (a substrate made of a plastic material) is preferable.

  Although the plastic material which comprises the said plastic base material is not specifically limited, For example, Polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Polyimide; Polycarbonate; Polyamide; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide; Polyether Sulfone; Polyetheretherketone; Norbornene monomer homopolymer (addition polymer, ring-opening polymer, etc.), Norbornene monomer and olefin monomer copolymer (addition polymer, such as norbornene and ethylene copolymer) And cyclic olefin copolymers such as ring-opening polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA), polystyrene , Polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin, etc.); vinylidene polymer (for example, polyvinylidene chloride, etc.); cellulose resin such as triacetyl cellulose (TAC); epoxy resin; phenol resin; Various plastic materials such as melamine resin; urea resin; maleimide resin; The plastic substrate may be composed of only one kind of plastic material or may be composed of two or more kinds of plastic materials.

  Among them, as the plastic substrate, it is preferable to use a substrate excellent in heat resistance, moldability, and mechanical strength, more preferably a polyester film (particularly PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film. , PMMA film.

  If necessary, the plastic substrate is made of an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant aid, a filler, a plasticizer, and an impact modifier. , Other additives such as reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents and the like may be included. In addition, an additive can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The plastic substrate may have a single-layer configuration or a multilayer (lamination) configuration, and the configuration (structure) is not particularly limited. For example, the above-mentioned plastic substrate is a “plastic film / other layer” in which a layer other than the transfer layer of the present invention (sometimes referred to as “other layer”) is formed on at least one surface of the plastic film. It may be a plastic substrate having a laminated structure such as “other layer / plastic film / other layer”. Examples of the other layers include hard coat layers other than the hard coat layer constituting the transfer film of the present invention. In addition, as a material which comprises the said other layer, the above-mentioned plastic material etc. are mentioned, for example.

  Roughening, easy adhesion, antistatic treatment, sandblasting (sandmat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, watermat treatment, flame are applied to part or all of the surface of the plastic substrate. Known or conventional surface treatments such as treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, etc. may be applied. The plastic substrate may be an unstretched film or a stretched film (uniaxially stretched film, biaxially stretched film, etc.).

  The plastic base material is, for example, a method of forming the above plastic material into a film shape to form a plastic base material (plastic film), and if necessary, an appropriate layer (for example, the above-mentioned other layers) with respect to the plastic film. For example, a layer or the like, or an appropriate surface treatment. In addition, a commercial item can also be used as said plastic base material.

  The thickness of the base material is not particularly limited, and can be appropriately selected from, for example, a range of 0.01 to 10000 μm. 5-100 micrometers is more preferable and 20-100 micrometers is further more preferable.

[Release layer]
The release layer in the transfer film of the present invention is a layer that constitutes at least one surface layer of the substrate in the transfer film of the present invention, and is provided for easily peeling the transfer layer from the substrate. Is a layer. By providing the release layer, the transfer layer can be reliably and easily transferred from the transfer film to the transfer target (molded product), and the substrate sheet can be reliably peeled off.

  In the transfer film of the present invention, the peel strength between the release layer and the hard coat layer is not particularly limited, but is preferably 30 to 500 mN / 24 mm, more preferably 40 to 300 mN / 24 mm, and still more preferably 50. ~ 200 mN / 24 mm. When the peel strength is within this range, the hard coat layer does not peel off during normal handling, and the hard coat tends to be easily peeled off simultaneously with transfer to a molded product. The peel strength between the hard coat layer and the release layer of the present invention can be measured according to JIS Z0237.

In addition, the release layer in the transfer film of the present invention may be formed only on one surface (one side) of the substrate, or may be formed on both surfaces (both sides).
In addition, the release layer in the transfer film of the present invention may be formed on only a part or on the entire surface of each surface of the substrate.

  As the component for forming the release layer, publicly known release agents can be used without particular limitation. For example, unsaturated ester resins, epoxy resins, epoxy-melamine resins, aminoalkyd resins, At least one selected from acrylic resins, melamine resins, silicon resins, fluorine resins, cellulose resins, urea resin resins, polyolefin resins, paraffin resins, and cycloolefin resins can be used. From the viewpoint of peelability from the hard coat layer of the present invention in contact with the release layer in the transfer layer, the release layer is preferably a melamine resin or a cycloolefin resin, particularly 2-norbornene / ethylene copolymer. A cycloolefin copolymer resin (COC resin) such as a coalescence is preferable.

  As the method for forming the release layer on the substrate surface, a publicly known release treatment method can be used without any particular limitation. For example, the above resin is dispersed or dissolved in a solvent (eg, alcohols such as methanol and butanol, aromatic hydrocarbons such as toluene and xylene, tetrahydrofuran, etc.), and bar coat, Mayer bar coat, gravure coat, roll coat, etc. The release layer can be formed by coating, drying, and heating at 80 to 200 ° C. by a known coating method. The thickness of the release layer is not particularly limited, and can usually be selected from a range of 0.01 to 5 μm, preferably 0.1 to 3.0 μm.

[Hard coat layer]
The hard coat layer in the transfer film of the present invention is a layer laminated on at least one surface of the release layer, and is formed from the curable composition (hard coat agent) of the present invention. Uncured or semi-cured layer. Here, uncured means a state in which the polymerizable functional group of the polyorganosilsesquioxane of the present invention contained in the curable composition (hard coat agent) of the present invention is not polymerized. Semi-curing means a state in which a part of the polymerizable functional group undergoes a polymerization reaction and an unreacted polymerizable functional group remains. The semi-cured hard coat layer can be formed by partially curing the uncured hard coat layer by irradiation with active energy rays or heating described later. In the present specification, an uncured or semi-cured hard coat layer formed by the curable composition (hard coat agent) of the present invention was simply transferred to a “hard coat layer” and molded product. The hard coat layer may be referred to as a “cured hard coat layer”.

  The uncured or semi-cured hard coat layer of the present invention preferably has a low tack property that prevents the resin from adhering to the surface when the finger is brought into contact with the surface, and excellent blocking resistance. Can be handled.

In addition, the hard coat layer of the present invention in the transfer film of the present invention may be formed only on one release layer (one side) of the substrate, or formed on both release layers (both sides). It may be.
Further, the hard coat layer of the present invention in the transfer film of the present invention may be formed on only a part of the surface of each of the release layers, or may be formed on the entire surface.

The method for laminating the hard coat layer of the present invention on the release layer of the transfer film of the present invention is not particularly limited, but the curable composition (hard coat agent) of the present invention is formed on the release layer by a known method. ) Is applied and dried to form an uncured hard coat layer, or further, a semi-hardened hard coat layer is formed by irradiating or heating an activation energy ray to the uncured hard coat layer. As a coating method of the curable composition (hard coat agent) of the present invention, a known coating method can be used without limitation, and examples thereof include bar coater coating, Mayer bar coating, air knife coating, and gravure coating. Examples thereof include offset printing, offset printing, flexographic printing, and screen printing.
Although the heating temperature at the time of forming a hard-coat layer is not specifically limited, Preferably it can select from 50-200 degreeC suitably. The heating time is not particularly limited, but can be appropriately selected from 1 to 60 minutes.
The conditions for irradiating the activation energy rays to the hard coat layer are not particularly limited, and for example, any of infrared rays, visible rays, ultraviolet rays, X rays, electron beams, α rays, β rays, γ rays, etc. may be used. it can. Among these, ultraviolet rays are preferable in terms of excellent handleability. The active energy ray irradiation conditions and the like can be appropriately adjusted according to the type and energy of the active energy ray to be irradiated, the thickness and size of the hard coat layer, etc., and are not particularly limited. For example, it is preferably about 1 to 1000 mJ / cm ² . For irradiation with active energy rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After the irradiation with the active energy ray, a heat treatment (annealing or aging) may be further performed to further advance the curing reaction.

  The thickness of the hard coat layer in the transfer film of the present invention (when having the hard coat layer of the present invention on both surfaces of the substrate) is not particularly limited, but preferably 1 to 200 μm, More preferably, it is 3-150 micrometers. In particular, even when the hard coat layer of the present invention is thin (for example, when the thickness is 5 μm or less), the hard coat layer maintains a high hardness on the surface (for example, the pencil hardness is 5H or more). Is possible. In addition, even when the thickness is thick (for example, when the thickness is 50 μm or more), it is difficult to cause defects such as cracks due to curing shrinkage, etc. 9H or higher).

  The haze of the hard coat layer in the transfer film of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less in the case of a thickness of 50 μm. The lower limit of haze is not particularly limited, but is 0.1%, for example. By setting the haze to 1.0% or less, for example, when the transfer film of the present invention is used as a decorative film, it is preferable because a pattern, a pattern, and the like can be clearly transferred. The haze of the hard coat layer of the present invention can be measured according to JIS K7136.

  The total light transmittance of the hard coat layer in the transfer film of the present invention is not particularly limited, but is preferably 85% or more, more preferably 90% or more in the case of a thickness of 50 μm. The upper limit of the total light transmittance is not particularly limited, but is 99%, for example. By setting the total light transmittance to 85% or more, for example, when the transfer film of the present invention is used as a decorative film, it is preferable because a pattern, a pattern, and the like can be clearly transferred. The total light transmittance of the hard coat layer of the present invention can be measured according to JIS K7361-1.

[Curable composition (hard coat agent)]
The curable composition of the present invention is a curable composition (curable resin composition) containing the polyorganosilsesquioxane of the present invention as an essential component, and the hard coat layer in the transfer film of the present invention. It is used as a hard coat agent for forming. As will be described later, the curable composition (hard coat agent) of the present invention further includes other catalysts such as a curing catalyst (particularly a photocationic polymerization initiator and a radical polymerizable initiator), a surface conditioner or a surface modifier. Ingredients may be included.

The polyorganosilsesquioxane of the present invention, which is an essential component of the curable composition (hard coat agent) of the present invention, has a structural unit represented by the above formula (1).
In addition, the polyorganosilsesquioxane of the present invention includes a structural unit represented by the following formula (I) (sometimes referred to as “T3 body”) and a structural unit represented by the following formula (II) (“ It may be referred to as “T2 body”).
Furthermore, the polyorganosilsesquioxane of the present invention preferably has a structural unit represented by the following formula (4).

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO _3/2 ]. In the above formula, R represents a hydrogen atom or a monovalent organic group, and the same applies to the following. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (a)). Is done.

R ¹ in the formula (1) represents a group containing a polymerizable functional group (monovalent group). That is, the polyorganosilsesquioxane of the present invention is a cationic curable compound (cationic polymerizable compound) or a radical curable compound (radical polymerizable compound) having at least a polymerizable functional group in the molecule.

The “cationic polymerizable functional group” in the group containing the polymerizable functional group is not particularly limited as long as it has cationic polymerizability, and examples thereof include an epoxy group, an oxetane group, a vinyl ether group, and a vinylphenyl group. Can be mentioned.
The “radical polymerizable functional group” in the group containing the polymerizable functional group is not particularly limited as long as it has radical polymerizability. For example, (meth) acryloxy group, (meth) acrylamide group, vinyl Group, vinylthio group and the like.
The polymerizable functional group is preferably an epoxy group, a (meth) acryloxy group or the like, and particularly preferably an epoxy group, from the viewpoint of the surface hardness (eg, 4H or more) of the cured product (cured hard coat layer).

Examples of the group containing an epoxy group include known or conventional groups having an oxirane ring, and are not particularly limited. However, the curability of the curable composition (hard coat agent) and the cured product (cured hard coat layer) are not limited. From the viewpoint of surface hardness and heat resistance, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the following formula (1d) The group represented by the following formula (1a), the group represented by the following formula (1c), more preferably the group represented by the following formula (1a).

In the above formula (1a), R ^1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among these, as R ^1a , from the viewpoint of the surface hardness and curability of the cured product (cured hard coat layer), a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 or 4 carbon atoms. Are more preferable, ethylene group, trimethylene group and propylene group are more preferable, and ethylene group and trimethylene group are more preferable.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, as R ^1b , from the viewpoint of surface hardness and curability of the cured product (cured hard coat layer), a linear alkylene group having 1 to 4 carbon atoms, a branched alkylene group having 3 or 4 carbon atoms, and the like. Are more preferable, ethylene group, trimethylene group and propylene group are more preferable, and ethylene group and trimethylene group are more preferable.

In said formula (1c), R ^<1c> shows a linear or branched alkylene group, and the group similar to R ^<1a> is illustrated. Among them, R ^1c is a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms from the viewpoint of surface hardness or curability of a cured product (cured hard coat layer). Are more preferable, ethylene group, trimethylene group and propylene group are more preferable, and ethylene group and trimethylene group are more preferable.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, as R ^1d , a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms from the viewpoint of the surface hardness or curability of the cured product (cured hard coat layer). Are more preferable, ethylene group, trimethylene group and propylene group are more preferable, and ethylene group and trimethylene group are more preferable.

R ¹ in formula (1) is particularly a group represented by the above formula (1a), wherein R ^1a is an ethylene group [in particular, 2- (3 ′, 4′-epoxycyclohexyl) Ethyl group] is preferable.

  Examples of the group containing an oxetane group include known or commonly used groups having an oxetane ring, and are not particularly limited. 1-5 alkyl groups), or a group obtained by substituting one or more, preferably one hydrogen atom, with an oxetane group. From the viewpoint of the curability of the curable composition (hard coat agent) and the heat resistance of the cured product (cured hard coat layer), a 3-oxetanyl group, an oxetane-3-ylmethyl group, a 3-ethyloxetane-3-ylmethyl group, 2- (oxetane-3-yl) ethyl group, 2- (3-ethyloxetane-3-yl) ethyl group, 3- (oxetane-3-ylmethoxy) propyl group, 3- (3-ethyloxetane-3-ylmethoxy) ) A propyl group or the like is preferable.

  Examples of the group containing the vinyl ether group include known or commonly used groups having a vinyl ether group, and are not particularly limited. For example, the vinyl ether group itself, an alkyl group (preferably having a carbon number of 1 to 10, more preferably a carbon number). And a group obtained by substituting one or more hydrogen atoms (usually one or more, preferably one hydrogen atom) with a vinyl ether group. From the viewpoint of curability of the curable composition (hard coat agent) and heat resistance of the cured product (cured hard coat layer), vinyloxymethyl group, 2- (vinyloxy) ethyl group, 3- (vinyloxy) propyl group, and the like. preferable.

  Examples of the group containing the vinylphenyl group include known or conventional groups having a vinylphenyl group, and are not particularly limited. For example, the vinylphenyl group itself, an alkyl group (preferably having 1 to 10 carbon atoms, more preferably Is a group formed by substituting a vinylphenyl group for a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group having 1 to 5 carbon atoms. From the viewpoints of curability of the curable composition (hard coat agent) and heat resistance of the cured product (cured hard coat layer), 4-vinylphenyl group, 3-vinylphenyl group, 2-vinylphenyl group and the like are preferable.

  Examples of the group containing the (meth) acryloxy group include known or conventional groups having a (meth) acryloxy group, and are not particularly limited. For example, the (meth) acryloxy group itself, an alkyl group (preferably Is a group formed by substituting a (meth) acryloxy group for a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. It is done. From the viewpoint of curability of the curable composition (cured hard coat layer) and heat resistance of the cured product (cured hard coat layer), 2-((meth) acryloxy) ethyl group, 3-((meth) acryloxy) A propyl group or the like is preferable.

  Examples of the group containing the (meth) acrylamide group include known or conventional groups having a (meth) acrylamide group, and are not particularly limited. For example, the (meth) acrylamide group itself, an alkyl group (preferably having a carbon number) And a group formed by substituting a (meth) acrylamide group for a hydrogen atom (usually one or more, preferably one hydrogen atom) of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms. From the viewpoint of curability of the curable composition (cured hard coat layer) and heat resistance of the cured product (cured hard coat layer), 2-((meth) acrylamide) ethyl group, 3-((meth) acrylamide) propyl group Etc. are preferred.

  Examples of the group containing a vinyl group include known or conventional groups having a vinyl group, and are not particularly limited. For example, the vinyl group itself, an alkyl group (preferably having 1 to 10 carbon atoms, more preferably having carbon atoms). 1-5 alkyl groups) and a group obtained by substituting one or more, preferably one hydrogen atom, with a vinyl group. From the viewpoints of curability of the curable composition (hard coat agent) and heat resistance of the cured product (cured hard coat layer), a vinyl group, a vinylmethyl group, a 2-vinylethyl group, a 3-vinylpropyl group, and the like are preferable.

  Examples of the group containing a vinylthio group include known or commonly used groups having a vinylthio group, and are not particularly limited. And a group obtained by substituting one or more hydrogen atoms (usually one or more, preferably one hydrogen atom) with a vinylthio group. From the viewpoint of the curability of the curable composition (hard coat agent) and the heat resistance of the cured product (cured hard coat layer), vinylthiomethyl group, 2- (vinylthio) ethyl group, 3- (vinylthio) propyl group, etc. preferable.

As R < ¹ > in Formula (1), the group containing an epoxy group and the group containing a (meth) acryloxy group are preferable, Especially, it is group represented by the said Formula (1a), Comprising: R ^<1a> Groups that are ethylene groups [among others, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group], 3- (acryloxy) propyl group, and 3- (methacryloxy) propyl group are preferable.

  The polyorganosilsesquioxane of the present invention may have only one type of structural unit represented by the above formula (1), or two or more types of structural units represented by the above formula (1). You may have.

The polyorganosilsesquioxane of the present invention is represented by the following formula (2) in addition to the structural unit represented by the above formula (1) as the silsesquioxane structural unit [RSiO _3/2 ]. You may have a unit.

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (b)). It is formed by.

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group An alkenyl group of As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Groups. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group, are mentioned, for example.

  As the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group, the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group are each a hydrogen atom or main chain. Part or all of the case is an ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacryl group, mercapto group, amino group, and hydroxy group (hydroxyl group). And a group substituted with at least one selected.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, more preferably a phenyl group. is there.

  In the polyorganosilsesquioxane of the present invention, the proportion of each of the above silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) It is possible to adjust appropriately according to the composition of the raw material (hydrolyzable trifunctional silane) for forming the slag.

The polyorganosilsesquioxane of the present invention is not limited to the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), and is further represented by the above structural formula (1). And a structural unit (so-called M unit) represented by silsesquioxane structural units [RSiO _3/2 ], [R ₃ SiO _1/2 ] other than the structural unit represented by formula (2), [R ₂ SiO _2/2 ] and at least one siloxane structural unit selected from the group consisting of a structural unit represented by [SiO _4/2 ] (so-called Q unit). You may do it. In addition, as a silsesquioxane structural unit other than the structural unit represented by the said Formula (1) and the structural unit represented by Formula (2), the structural unit etc. which are represented by following formula (3) etc. are mentioned, for example. Can be mentioned.

  When the polyorganosilsesquioxane of the present invention has the structural unit (T3 form) represented by the above formula (I) and the structural unit (T2 form) represented by the above formula (II), the proportion thereof [T3 body / T2 body] is not particularly limited, but can be appropriately selected from a range of, for example, 5 or more (for example, 5 or more and 500 or less). The lower limit of the above ratio [T3 / T2] is preferably 20, more preferably 21, more preferably 23, still more preferably 25 (for example, preferably 5, more preferably 6, more preferably 7). is there. By setting the ratio [T3 body / T2 body] to 5 or more, the surface hardness of the hard coat layer is improved and the adhesion to the anchor coat layer tends to be improved. In addition, for example, by setting the ratio [T3 body / T2 body] to 20 or more, in addition to improving surface hardness and adhesion, the surface when an uncured or semi-cured hard coat layer is made tack-free. The anti-blocking property is improved, the film can be easily wound on a roll, and can be preferably used as a component of a hard coat layer of a transfer film for in-mold injection molding. On the other hand, the upper limit of the above ratio [T3 body / T2 body] is preferably 500, more preferably 100, more preferably 50, still more preferably 40 (for example, preferably less than 20, more preferably 18, more preferably). 16, more preferably 14). By setting the ratio [T3 body / T2 body] to 500 or less (for example, preferably less than 20, more preferably 18 or less), compatibility with other components in the curable composition (hard coat agent) is improved. In addition, since the viscosity is also suppressed, the handling becomes easy, and it becomes easy to apply as a hard coat layer.

When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I ′). Moreover, when the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II ′). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)). . On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II ′) are each replaced with another silicon atom (a silicon atom not shown in the formula (II ′)). Are connected. That is, the T3 body and the T2 body are structural units (T units) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, polymerizable A group containing a functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or hydrogen Indicates an atom. Specific examples of R ^a and R ^b are the same as R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R ^a in the formula (I) and R ^b in the formula (II) were bonded to silicon atoms in the hydrolyzable trifunctional silane compound used as the raw material of the polyorganosilsesquioxane of the present invention, respectively. It is derived from a group (a group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² and a hydrogen atom in the formulas (a) to (c) described later).

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. . In general, the alkyl group in R ^c in the formula (II) is generally an alkoxy group (for example, X ^{1 to} X ³ described later) in the hydrolyzable silane compound used as a raw material of the polyorganosilsesquioxane of the present invention. Derived from an alkyl group forming an alkoxy group or the like.

The said ratio [T3 body / T2 body] in the polyorganosilsesquioxane of this invention can be calculated | required by ²⁹ Si-NMR spectrum measurement, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the above formula (I) is different from the silicon atom in the structural unit (T2 form) represented by the above formula (II). In order to show a signal (peak) in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, the polyorganosilsesquioxane of the present invention has a structural unit represented by the above formula (1) and R ¹ is a 2- (3 ′, 4′-epoxycyclohexyl) ethyl group. In this case, the signal of the silicon atom in the structure (T3 form) represented by the above formula (I) appears at −64 to −70 ppm, and the silicon atom in the structure (T2 form) represented by the above formula (II) The signal appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of −64 to −70 ppm and the signal (T2 body) of −54 to −60 ppm. it can. When R ¹ is a group containing a polymerizable functional group other than 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, [T3 body / T2 body] can be obtained in the same manner.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane of the present invention can be measured, for example, with the following apparatus and conditions.
Measuring apparatus: Trade name “JNM-ECA500NMR” (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Accumulated times: 1800 times Measurement temperature: 25 ° C

When the ratio [T3 / T2] of the polyorganosilsesquioxane of the present invention is in the above range (for example, 5 or more and 500 or less), It means that a certain amount of T2 is present. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the formula (4) to (6), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  The polyorganosilsesquioxane of the present invention may have any cage-type, incomplete cage-type, ladder-type, or random-type silsesquioxane structure. You may have in combination.

  When the polyorganosilsesquioxane of the present invention has a structural unit represented by the above formula (4), the total amount of siloxane structural units [total siloxane structural unit; total amount of M units, D units, T units, and Q units The ratio (total amount) of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) to (100 mol%) is not particularly limited, but is preferably 55 to 100 mol%. More preferably, it is 65-100 mol%, More preferably, it is 80-99 mol%. When the ratio is 55 mol% or more, the curability of the curable composition (hard coat agent) is improved, and the surface hardness and adhesiveness of the cured product (cured hard coat layer) are remarkably increased. In addition, the ratio of each siloxane structural unit in the polyorganosilsesquioxane of this invention is computable by the composition of a raw material, NMR spectrum measurement, etc., for example.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). Although the ratio (total amount) of the structural unit represented and the structural unit represented by the above formula (5) is not particularly limited, it is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 0 mol%. It is 40 mol%, particularly preferably 1 to 15 mol%. Since the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased by setting the ratio to 70 mol% or less, the curable composition The curability of (hard coat agent) is improved, and the surface hardness and adhesiveness of the cured product (cured hard coat layer) tend to be higher. On the other hand, the gas barrier property of the cured product (cured hard coat layer) tends to be improved by setting the ratio to 1 mol% or more.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by the structural unit represented by the formula (2), the structural unit represented by the formula (4), and the structural unit represented by the formula (5) is particularly limited. However, it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By making the said ratio 60 mol% or more, there exists a tendency for the surface hardness and adhesiveness of hardened | cured material (hardened hard-coat layer) to become higher.

  The number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is not particularly limited, but can be appropriately selected from a range of 1000 to 50000, for example. The lower limit of the number average molecular weight is preferably 2500, more preferably 2800, still more preferably 3000 (for example, preferably 1000, more preferably 1100). By setting the number average molecular weight to 1000 or more, the heat resistance, scratch resistance, and adhesion of the cured product (cured hard coat layer) tend to be further improved. For example, by setting the number average molecular weight to 2500 or more, in addition to improving the heat resistance, scratch resistance and adhesion of the cured product (cured hard coat layer), an uncured or semi-cured hard coat layer is obtained. The surface at the time is easily tack-free, the blocking resistance is improved, the film is easily wound up on a roll, and can be preferably used as a component of a hard coat layer of a transfer film for in-mold injection molding. On the other hand, the upper limit of the number average molecular weight is preferably 50,000, more preferably 10,000, and still more preferably 8000 (for example, preferably 3000, more preferably 2800, and further preferably 2600). By setting the number average molecular weight to 50000 or less (for example, 3000 or less), compatibility with other components in the curable composition (hard coat agent) is improved, and the heat resistance of the cured product (cured hard coat layer) is improved. There is a tendency to improve.

  The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is not particularly limited, but may be appropriately selected from the range of 1.0 to 4.0. it can. The lower limit of the molecular weight dispersity is preferably 1.0, more preferably 1.1, and still more preferably 1.2. By setting the molecular weight dispersity to 1.1 or more, it tends to be liquid and the handling property tends to be improved. On the other hand, the upper limit value of the molecular weight dispersity is preferably 4.0, more preferably 3.0, still more preferably 2.5 (for example, preferably 3.0, more preferably 2.0, still more preferably 1. 9). By setting the molecular weight dispersity to 4.0 or less (for example, 3.0 or less), the surface hardness and adhesiveness of the cured product (cured hard coat layer) tend to be higher.

In addition, the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane of this invention can be measured with the following apparatus and conditions.
Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) in the air atmosphere of the polyorganosilsesquioxane of the present invention is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), more preferably 340 ° C. or higher. More preferably, it is 350 ° C. or higher. When the 5% weight reduction temperature is 330 ° C. or higher, the heat resistance of the cured product (cured hard coat layer) tends to be further improved. In particular, in the polyorganosilsesquioxane of the present invention, the ratio [T3 / T2] is 5 or more and 500 or less, the number average molecular weight is 1000 to 50000, and the molecular weight dispersity is 1.0 to 4.0. Therefore, the 5% weight loss temperature is controlled to 330 ° C. or higher. The 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min.

  The polyorganosilsesquioxane of the present invention can be produced by a known or conventional polysiloxane production method, and is not particularly limited. For example, one or two or more hydrolyzable silane compounds are hydrolyzed and It can be produced by a method of condensation. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above formula (1) is essential. It is necessary to use it as a hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present invention. If necessary, the polyorganosilsesquioxane of the present invention can be produced by hydrolysis and condensation of a compound represented by the following formula (b) and a compound represented by the following formula (c). .

The compound represented by the above formula (a) is a compound that forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane of the present invention. R ¹ in the formula (a) represents a group containing a polymerizable functional group, similarly to R ¹ in the formula (1). That is, R ¹ in the formula (a) is a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or the above formula (1d). The group represented by the above formula (1a), the group represented by the above formula (1c), more preferably the group represented by the above formula (1a), particularly preferably Is a group represented by the above formula (1a), wherein R ^1a is an ethylene group [in particular, a 2- (3 ′, 4′-epoxycyclohexyl) ethyl group].

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ^1, for example, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group having 1 to 4 carbon atoms such as isobutyl group and the like. As the halogen atom in X ^1, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ¹ may be the same or different.

The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) in the polyorganosilsesquioxane of the present invention. R ² in formula (b), like the R ² in the formula (2), a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted An alkyl group, or a substituted or unsubstituted alkenyl group. That is, R ² in formula (b) is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, More preferred is a phenyl group.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ² may be the same or different.

The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane of the present invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

  As said hydrolysable silane compound, you may use together hydrolysable silane compounds other than the compound represented by said formula (a)-(c). For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds that form M units, and hydrolyzable bifunctional silanes that form D units Examples thereof include hydrolyzable tetrafunctional silane compounds that form compounds and Q units.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, although the usage-amount of the compound represented by the said formula (a) is not specifically limited, 55-100 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 65 to 100 mol%, more preferably 80 to 99 mol%.

  The amount of the compound represented by the formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%.

  Furthermore, the ratio (total ratio) of the compound represented by the formula (a) and the compound represented by the formula (b) with respect to the total amount (100 mol%) of the hydrolyzable silane compound to be used is not particularly limited. 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

  Moreover, when using together 2 or more types as said hydrolysable silane compound, the hydrolysis and condensation reaction of these hydrolysable silane compounds can also be performed simultaneously, and can also be performed sequentially. When performing the said reaction sequentially, the order which performs reaction is not specifically limited.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound may be performed in one step or may be performed in two or more steps. For example, the above-mentioned ratio [T3 body / T2 body] is less than 20 and / or the polyorganosilsesquioxane of the present invention having a number average molecular weight of less than 2500 (hereinafter referred to as “low molecular weight polyorganosilsesquioxane”). In order to efficiently produce (A), it is preferable to carry out the hydrolysis and condensation reaction in one step. Further, the polyorganosilsesquioxane of the present invention (hereinafter referred to as “high molecular weight polyorganosilsesquioxane”) having a ratio [T3 / T2] of 20 or more and / or a number average molecular weight of 2500 or more. In order to efficiently produce a compound, the hydrolysis and condensation reaction is performed in two or more stages (preferably two stages), that is, the low molecular weight polyorganosilsesquioxane is used as a raw material. It is preferable that the hydrolysis and condensation reaction be further performed once or more. The hydrolysis and condensation reaction of the hydrolyzable silane compound is performed in one step to obtain a low molecular weight polyorganosilsesquioxane, and the low molecular weight polyorganosilsesquioxane is further subjected to hydrolysis and condensation reactions. Although the aspect which obtains high molecular weight polyorgano silsesquioxane by this is demonstrated, the manufacturing method of the polyorgano silsesquioxane of this invention is not limited to this.

  When the hydrolysis and condensation reaction of the present invention is performed in two stages, preferably, the ratio [T3 body / T2 body] is 5 or more and less than 20 in the first stage hydrolysis and condensation reaction, and the number average molecular weight A low molecular weight polyorganosilsesquioxane having a molecular weight of 1000 or more and less than 2500 is obtained. In the second stage, the low molecular weight polyorganosilsesquioxane is further subjected to hydrolysis and condensation reaction, whereby the ratio [T3 Body / T2 body] is 20 or more and 500 or less, and a high molecular weight polyorganosilsesquioxane having a number average molecular weight of 2500 or more and 50000 or less can be obtained.

  The first stage hydrolysis and condensation reaction can be carried out in the presence of a solvent or in the absence. Among these, it is preferable to perform in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc. Among them, ketone and ether are preferable. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The amount of the solvent used in the first stage hydrolysis and condensation reaction is not particularly limited, and the desired reaction time is within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound. It can adjust suitably according to etc.

  The first stage hydrolysis and condensation reaction is preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferable in order to suppress decomposition of a polymerizable functional group such as an epoxy group. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the alkali catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Alkali metal hydrogen carbonates such as cesium hydrogen carbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (for example, acetate); organic acids of alkaline earth metals such as magnesium acetate Salt (eg acetate); lithium methoxide, sodium methoxy Alkali metal alkoxides such as sodium ethoxide, sodium isopropoxide, potassium ethoxide and potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4 0.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and the like amines (tertiary amine, etc.); pyridine, 2,2′-bipyridyl, 1,10 -Nitrogen-containing aromatic heterocyclic compounds such as phenanthroline. In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent or the like.

  The amount of the catalyst used in the first-stage hydrolysis and condensation reaction is not particularly limited, and is appropriately within a range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. Can be adjusted.

  The amount of water used in the first stage hydrolysis and condensation reaction is not particularly limited, and is appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. be able to.

  The method for adding water in the hydrolysis and condensation reaction in the first stage is not particularly limited, and the total amount of water to be used (total amount used) may be added all at once or sequentially. Good. When adding sequentially, you may add continuously and may add intermittently.

  As reaction conditions for the hydrolysis and condensation reaction in the first stage, the reaction conditions are selected so that the ratio [T3 / T2] in the low molecular weight polyorganosilsesquioxane is 5 or more and less than 20. This is very important. The reaction temperature of the first stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40 to 100 ° C, more preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be more efficiently controlled to 5 or more and less than 20. The reaction time for the first stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.1 to 10 hours, and more preferably 1.5 to 8 hours. Further, the hydrolysis and condensation reaction in the first stage can be performed under normal pressure, or can be performed under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the first stage hydrolysis and condensation reaction is not particularly limited, for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as under air. Although it may be present, an inert gas atmosphere is preferred.

  Low molecular weight polyorganosilsesquioxane is obtained by the hydrolysis and condensation reaction in the first stage. After completion of the hydrolysis and condensation reaction in the first stage, it is preferable to neutralize the catalyst in order to suppress decomposition of the polymerizable functional group such as ring opening of the epoxy group. In addition, low molecular weight polyorganosilsesquioxane can be separated from, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. It may be separated and purified by means or the like.

The low molecular weight polyorganosilsesquioxane obtained by the first stage hydrolysis and condensation reaction is subjected to the second stage hydrolysis and condensation reaction to produce a high molecular weight polyorganosilsesquioxane. be able to.
The second stage hydrolysis and condensation reaction can be carried out in the presence of a solvent or in the absence. When the second-stage hydrolysis and condensation reaction is performed in the presence of a solvent, the solvents mentioned in the first-stage hydrolysis and condensation reaction can be used. As the solvent for the second stage hydrolysis and condensation reaction, the low molecular weight polyorganosilsesquioxane containing the reaction solvent for the first stage hydrolysis and condensation reaction, the extraction solvent, or the like is distilled off as it is or partly. You may use what you did. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  When the solvent is used in the second stage hydrolysis and condensation reaction, the amount used is not particularly limited, and is within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the low molecular weight polyorganosilsesquioxane. Thus, it can be appropriately adjusted according to the desired reaction time and the like.

  The second stage hydrolysis and condensation reaction is preferably allowed to proceed in the presence of a catalyst and water. As the catalyst, the catalyst mentioned in the first stage hydrolysis and condensation reaction can be used, and in order to suppress the decomposition of the polymerizable functional group such as an epoxy group, an alkali catalyst is preferable. Preferred are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate. In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent or the like.

  The amount of the catalyst used in the second stage hydrolysis and condensation reaction is not particularly limited, and is preferably 0.01 to 10000 ppm, more preferably 0 with respect to the low molecular weight polyorganosilsesquioxane (1000000 ppm). Within the range of 1 to 1000 ppm, it can be adjusted as appropriate.

  The amount of water used in the second stage hydrolysis and condensation reaction is not particularly limited, and is preferably 10 to 100000 ppm, more preferably 100 to 20000 ppm relative to low molecular weight polyorganosilsesquioxane (1000000 ppm). Within the range, it can be adjusted as appropriate. If the amount of water used is greater than 100,000 ppm, the ratio of the high molecular weight polyorganosilsesquioxane [T3 body / T2 body] and the number average molecular weight tend to be difficult to control within a predetermined range.

  The method for adding water in the hydrolysis and condensation reaction in the second stage is not particularly limited, and the total amount of water to be used (total amount used) may be added all at once or sequentially. Good. When adding sequentially, you may add continuously and may add intermittently.

As the reaction conditions for the second stage hydrolysis and condensation reaction, the ratio [T3 / T2] in the high molecular weight polyorganosilsesquioxane is 20 or more and 500 or less, and the number average molecular weight is 2500 to 50000. It is important to select such reaction conditions. The reaction temperature of the hydrolysis and condensation reaction in the second stage varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200 ° C, more preferably 30 to 100 ° C. By controlling the reaction temperature within the above range, the ratio [T3 body / T2 body] and the number average molecular weight tend to be more efficiently controlled within the desired range. The reaction time for the hydrolysis and condensation reaction in the second stage is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours.
In addition, by performing timely sampling while carrying out hydrolysis and condensation reaction within the above reaction temperature range and performing the reaction while monitoring the above ratio [T3 / T2] and the number average molecular weight, a desired ratio [T3 body / T2 body], a high molecular weight polyorganosilsesquioxane having a number average molecular weight can also be obtained.

  The second stage hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the hydrolysis and condensation reaction in the second stage is not particularly limited, and for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as under air. Although it may be present, an inert gas atmosphere is preferred.

  High molecular weight polyorganosilsesquioxane is obtained by the hydrolysis and condensation reaction in the second stage. After completion of the hydrolysis and condensation reaction in the second stage, it is preferable to neutralize the catalyst in order to suppress decomposition of the polymerizable functional group such as ring opening of the epoxy group. In addition, high molecular weight polyorganosilsesquioxane can be separated from, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. It may be separated and purified by means or the like.

  Since the polyorganosilsesquioxane of the present invention has the above-described configuration, an uncured or semi-cured hard coat coated with a curable composition (hard coat agent) containing the polyorganosilsesquioxane as an essential component. By curing the layer, a cured product (cured hard coat layer) having high surface hardness and heat resistance and excellent flexibility and workability can be formed. Moreover, the hardened | cured material (cured hard-coat layer) excellent in adhesiveness can be formed. In addition, when a high molecular weight polyorganosilsesquioxane is used as the polyorganosilsesquioxane of the present invention, the uncured or semi-cured hard coat layer tends to be tack-free, and the blocking resistance is improved. For example, it can be suitably used as a component of a hard coat layer of an in-mold injection transfer film.

  In the curable composition (hard coat agent) of the present invention, the polyorganosilsesquioxane of the present invention can be used singly or in combination of two or more.

  The content (blending amount) of the polyorganosilsesquioxane of the present invention in the curable composition (hard coat agent) of the present invention is not particularly limited, but is the total amount of the curable composition (hard coat agent) excluding the solvent. 70 wt% or more and less than 100 wt% is preferable with respect to (100 wt%), more preferably 80 to 99.8 wt%, still more preferably 90 to 99.5 wt%. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness and adhesiveness of the cured product (cured hard coat layer) tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane of the present invention to less than 100% by weight, a curing catalyst can be contained, thereby more efficiently curing the curable composition (hard coat agent). Tend to be able to progress.

  The ratio of the polyorganosilsesquioxane of the present invention to the total amount (100% by weight) of the cationic curable compound or radical curable compound contained in the curable composition (hard coat agent) of the present invention is not particularly limited, 70-100 weight% is preferable, More preferably, it is 75-98 weight%, More preferably, it is 80-95 weight%. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness and adhesiveness of the cured product (cured hard coat layer) tend to be further improved.

  The curable composition (hard coat agent) of the present invention preferably further contains a curing catalyst. Among these, it is particularly preferable to include a cationic polymerization initiator or a radical polymerization initiator as a curing catalyst in that the curing time until tack-free is further shortened.

  The cationic polymerization initiator is a compound that can initiate or accelerate the cationic polymerization reaction of a cationically curable compound such as the polyorganosilsesquioxane of the present invention. Although it does not specifically limit as said cationic polymerization initiator, For example, a photocationic polymerization initiator (photoacid generator), a thermal cationic polymerization initiator (thermal acid generator), etc. are mentioned.

  As the photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions). Selenium salt (selenium ion and anion salt), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion salt, etc. . These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the sulfonium salt include [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, triphenylsulfonium salt, tri-p-tolylsulfonium salt, Tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, Tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium Diarylsulfonium salts such as diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium And monoarylsulfonium salts such as 4-methoxyphenylmethylbenzylsulfonium salt; and trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, and dimethylbenzylsulfonium salt.

  Examples of the diphenyl [4- (phenylthio) phenyl] sulfonium salt include diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate. .

  Examples of the iodonium salt include, for example, trade name “UV9380C” (Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkyl glycidyl ether solution), trade name “ RHODORSIL PHOTOINITIATOR 2074 "(manufactured by Rhodia Japan Ltd., tetrakis (pentafluorophenyl) borate = [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name" WPI-124 "(Wako Pure Chemical Industries, Ltd.) Co., Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt, and the like.

  Examples of the selenium salt include triaryl selenium such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts: Diaryl phenacyl selenium salts, diphenyl benzyl selenium salts, diaryl selenium salts such as diphenyl methyl selenium salts; monoaryl selenium salts such as phenyl methyl benzyl selenium salts; .

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholini Morpholinium salts such as N salt, piperidinium salts such as N, N-dimethylpiperidinium salt and N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N '-Imidazolium salt such as dimethylimidazolium salt; Quinolium salt such as N-methylquinolium salt; Isoquinolium salt such as N-methylisoquinolium salt; Thiazonium salt such as benzylbenzothiazonium salt; And the like.

  Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ^+. And salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

Examples of the anion constituting the above-described salt include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate Anion, p-toluenesulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate Ion, hexafluorobismuth acid ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

  Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Examples of the arylsulfonium salts include hexafluoroantimonate salts. In the curable composition (hard coat agent) of the present invention, for example, trade names “SP-66”, “SP-77” (manufactured by ADEKA Corporation); trade names “Sun-Aid SI-60L”, “ Commercial products such as “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, and “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate). Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

  The radical polymerization initiator is a compound capable of initiating or promoting a radical polymerization reaction of a radical curable compound such as the polyorganosilsesquioxane of the present invention. The radical polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator and a thermal radical polymerization initiator.

  Examples of the photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, Orthobenzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name) “Kayacure DETX”, etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Gaigi Co., Ltd., trade name “Irgacure 907”, etc.), 1-hydroxycyclo F 2-amino-2-benzoyl-1- such as silphenylketone (Ciba-Geigy Co., Ltd., trade name “Irgacure 184”, etc.), 2-dimethylamino-2- (4-morpholino) benzoyl-1-phenylpropane, etc. Aminobenzene derivatives such as phenylalkane compounds, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2, 2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (made by Hodogaya Chemical Co., Ltd., trade name “B-CIM”, etc.), etc. 1,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-tri Halomethyl triazines compounds such as gin, 2-trichloromethyl-5- (2-benzofuran-2-yl - ethenyl) -1,3,4 oxadiazole, and the like halomethyl oxadiazole compounds, and the like. Moreover, a photosensitizer can be added as needed.

  Examples of the thermal radical polymerization initiator include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, peroxyketal, and ketone peroxide (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butylperoxybenzoate, t-butylperoxide, cumene hydro Peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di (2-t- Butyl peroxyisopropyl) benzene, , 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc.) Mention may be made of peroxides.

  In the curable composition (hard coat agent) of the present invention, one type of curing catalyst can be used alone, or two or more types can be used in combination.

  The content (blending amount) of the curing catalyst in the curable composition (hard coat agent) of the present invention is not particularly limited, but is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention. 3.0 weight part is preferable, More preferably, it is 0.05-3.0 weight part, More preferably, it is 0.1-1.0 weight part (for example, 0.3-1.0 weight part). By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently advanced, and the surface hardness and adhesiveness of the cured product (cured hard coat layer) tend to be further improved. There is. On the other hand, by setting the content of the curing catalyst to 3.0 parts by weight or less, the preservability of the curable composition (hard coat agent) is further improved, and coloring of the cured product (cured hard coat layer) is suppressed. There is a tendency to.

  The curable composition (hard coat agent) of the present invention further includes a cationic curable compound other than the polyorganosilsesquioxane of the present invention (sometimes referred to as “other cationic curable compounds”) and / or the present invention. Radical curable compounds other than the polyorganosilsesquioxane of the invention (may be referred to as “other radical curable compounds”) may be included. As other cationic curable compounds, known or conventional cationic curable compounds can be used, and are not particularly limited. For example, epoxy compounds other than the polyorganosilsesquioxane of the present invention, oxetane compounds, vinyl ether compounds. Etc. In the curable composition (hard coat agent) of the present invention, other cationic curable compounds may be used alone or in combination of two or more.

  As said epoxy compound, the well-known thru | or usual compound which has 1 or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an alicyclic epoxy compound (alicyclic epoxy resin) ), Aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.

  Examples of the alicyclic epoxy compound include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. For example, (1) A compound having an epoxy group (referred to as “alicyclic epoxy group”) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) the epoxy group is directly bonded to the alicyclic ring by a single bond. (3) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like.

As said (1) compound which has an alicyclic epoxy group in a molecule | numerator, the compound represented by following formula (i) is mentioned.

  In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, the following formulas (i-1) to (i-10). ) And the like. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred. N1-n6 in following formula (i-9) and (i-10) show the integer of 1-30, respectively. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (ii).

In formula (ii), R ″ is a group obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number. P Examples of the valent alcohol [R ″ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl] Compound obtained by hydrogenating bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound) Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And hydrogenated epoxy compounds of the following aromatic epoxy compounds.

  Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

  Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a monovalent or polyvalent carboxylic acid [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly Epoxidized product of alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and other dihydric alcohols; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

  Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3- Oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bi Chlohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- {[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xylylenebisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane And phenol novolac oxetane.

  The vinyl ether compound may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. For example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedi Methanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xy Glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, penta Ethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol Coal divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, ha Droquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1, Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

  In the curable composition (hard coat agent) of the present invention, it is preferable to use a vinyl ether compound in combination with the polyorganosilsesquioxane of the present invention as another cationic curable compound. Thereby, the surface hardness of the cured product (cured hard coat layer) tends to be higher. In particular, when the curable composition (hard coat agent) of the present invention is cured by irradiation with active energy rays (particularly ultraviolet rays), the surface hardness is very high even when the irradiation amount of active energy rays is reduced. There is an advantage that a high cured product (cured hard coat layer) can be obtained with excellent productivity (for example, it is not necessary to perform a heat treatment for aging). For this reason, it is possible to further increase the production line speed of in-mold injection molding using the transfer film of the present invention, and the productivity is further improved.

  In addition, as the other cationic curable compound, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used, the surface hardness is higher, and further, heat-resistant yellowing (yellowing due to heating hardly occurs). There is an advantage that a cured product (cured hard coat layer) excellent in characteristics) can be obtained. For this reason, an in-mold molded product or a hard coat film to which a cured product (cured hard coat layer) of higher quality and durability is transferred can be obtained. The number of hydroxyl groups in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. Specifically, examples of the vinyl ether compound having one or more hydroxyl groups in the molecule include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl. Vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl Vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexa Diol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol Monovinyl ether, tetra B propylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta vinyl ether.

  As the other radical curable compound, a known or conventional radical curable compound can be used, and is not particularly limited, and examples thereof include (meth) acrylic compounds other than the polyorganosilsesquioxane of the present invention. . In addition, in the curable composition (hard coat agent) of this invention, another radical curable compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  As the (meth) acrylic compound, a known or conventional compound having one or more (meth) acrylic groups in the molecule can be used, and is not particularly limited. For example, trimethylolpropane tri (meth) acrylate, Trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Sri penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, tris ((meth) acryloyloxyethyl) polyfunctional acrylic acid esters such as isocyanurate.

  The content (blending amount) of other cationic curable compounds and / or other radical curable compounds in the curable composition (hard coat agent) of the present invention is not particularly limited, but the polyorganosilsesquioki of the present invention is not limited. Sun, 50% by weight or less (for example, 0 to 50% by weight) based on the total amount of the other cationic curable compound and the other radical curable compound (100% by weight; the total amount of the cationic curable compound and the radical curable compound) ), More preferably 30% by weight or less (for example, 0 to 30% by weight), and still more preferably 10% by weight or less. By setting the content of other cationic curable compounds and / or other radical curable compounds to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the cured product (cured hard coat layer) is further improved. Tend to. On the other hand, by setting the content of other cationic curable compounds and / or other radical curable compounds to 10% by weight or more, the curable composition (hard coat agent) or the cured product (cured hard coat layer) is used. In some cases, desired performance (for example, quick curability and viscosity adjustment for a curable composition (hard coat agent)) can be imparted.

  The content (blending amount) of the vinyl ether compound (particularly, the vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition (hard coat agent) of the present invention is not particularly limited, but the polyorgano of the present invention 0.01 to 10% by weight is preferable based on the total amount of silsesquioxane, other cationic curable compounds and other radical curable compounds (100% by weight; total amount of cationic curable compounds and radical curable compounds). More preferably, it is 0.05-9 weight%, More preferably, it is 1-8 weight%. By controlling the content of the vinyl ether compound within the above range, the surface hardness of the cured product (cured hard coat layer) becomes higher, and even when the irradiation amount of active energy rays (for example, ultraviolet rays) is lowered, the surface There is a tendency to obtain a cured product (cured hard coat layer) having a very high hardness. In particular, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, the surface hardness of the cured product (cured hard coat layer) becomes particularly high, and its heat-resistant yellowing There is a tendency to improve even more.

  The curable composition (hard coat agent) of the present invention further includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, Inorganic fillers such as zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilane, organoalkoxysilane, and organosilazane; Organic resin fine powder such as silicone resin, epoxy resin, fluororesin; filler such as conductive metal powder such as silver and copper, curing aid, solvent (organic solvent, etc.), stabilizer (antioxidant, UV absorption) Agent, light stabilizer, heat stabilizer, heavy metal deactivator, etc.), flame retardant (phosphorus flame retardant, halogen flame retardant, inorganic) Flame retardants), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hues Improver, clearing agent, rheology adjuster (flowability improver, etc.), processability improver, colorant (dye, pigment, etc.), antistatic agent, dispersant, surface conditioner (antifoaming agent, leveling agent, Anti-waxing agents, etc.), surface modifiers (slip agents, etc.), matting agents, antifoaming agents, antifoaming agents, antifoaming agents, antibacterial agents, antiseptics, viscosity modifiers, thickeners, photosensitizers Conventional additives such as foaming agents may be included. These additives can be used individually by 1 type or in combination of 2 or more types.

  Although the curable composition (hard coat agent) of this invention is not specifically limited, It can prepare by stirring and mixing each said component, heating at room temperature or as needed. In addition, the curable composition (hard coat agent) of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, stored separately. It can also be used as a multi-liquid (for example, two-liquid) composition in which two or more components are mixed at a predetermined ratio before use.

  The curable composition (hard coat agent) of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the curable composition (hard coat agent) of the present invention is a solution diluted in a solvent of 20% [particularly, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight]. As a viscosity in 25 degreeC, 300-20000 mPa * s is preferable, More preferably, it is 500-10000 mPa * s, More preferably, it is 1000-8000 mPa * s. By setting the viscosity to 300 mPa · s or more, the heat resistance of the cured product (cured hard coat layer) tends to be further improved. On the other hand, when the viscosity is 20000 mPa · s or less, preparation and handling of the curable composition (hard coat agent) are facilitated, and bubbles are less likely to remain in the cured product (cured hard coat layer). There is. In addition, the viscosity of the curable composition (hard coat agent) of the present invention was determined using a viscometer (trade name “MCR301”, manufactured by Anton Paar) with a swing angle of 5% and a frequency of 0.1 to 100 (1 / s) Temperature: measured at 25 ° C.

[Anchor coat layer]
The anchor coat layer in the transfer film of the present invention is provided to improve the adhesion between the hard coat layer and the adhesive layer or the colored layer, and is an epoxy resin (hereinafter referred to as “anchor of the present invention”). It may be referred to as a “coating resin”). Since the anchor coat layer in the transfer film of the present invention contains the anchor coat resin of the present invention, since the transparency is high, the pattern of the colored layer, the pattern and the like can be clearly transferred, and the cured hardware of the present invention The adhesion between the coat layer and the adhesive layer, colored layer, etc. is significantly improved. Furthermore, surprisingly, by combining the hard coat layer of the present invention and the anchor coat layer containing the anchor coat resin of the present invention, the surface hardness of the cured hard coat layer transferred to the molded product is further improved. It was also found.

  The epoxy resin as the anchor coat resin of the present invention is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, Examples thereof include glycidyl ester type epoxy resins, polymer type epoxy resins, biphenyl type epoxy resins and the like.

  The resin for anchor coating of the present invention further includes, as other optional components, wax, silica, plasticizer, leveling agent, surfactant, dispersant, antifoaming agent, ultraviolet absorber, ultraviolet stabilizer, antioxidant, etc. These conventional additives may be included as long as the effects of the present invention are not impaired. These additives can be used individually by 1 type or in combination of 2 or more types.

The resin for anchor coats of the present invention is a resin that is commonly used for anchor coat layers other than epoxy resins (sometimes referred to as “other anchor coat resins”) as long as the effects of the present invention are not impaired. May be included. Other anchor coating resins are preferably those that can form a transparent or translucent layer in order to clearly transfer the pattern and pattern of the colored layer, such as phenol resins, alkyd resins, melamine resins ( For example, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, methylbutyl mixed etherified melamine resin), urea resin, unsaturated polyester resin, urethane resin [for example, 2 isocyanate groups Polyisocyanate compound having more than one (O═C═N—R—N═C═O), polyol compound having two or more hydroxyl groups (HO—R′—OH), polyamine (H ₂ N—R ″) -NH _2), or an active hydrogen (-NH _2, such as water, -NH, anti and the like compounds having a -CONH-, etc.) Urethane resin that can be obtained by reaction], thermosetting resin such as thermosetting polyimide, silicone resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin (for example, acrylic polyol resin), chlorinated rubber, One type or a mixture of two or more types of thermoplastic resins such as polyamide resin, nitrified cotton resin, and cyclic polyolefin-based resin can be used.

The anchor coat layer is obtained by applying a coating solution obtained by dissolving the above resin in a solvent to the hard coat layer of the present invention by a known coating method such as bar coating, Mayer bar coating, gravure coating, roll coating, and drying. If necessary, it can be formed by heating.
The temperature at the time of heating when forming the anchor coat layer is not particularly limited, but can be suitably selected from 50 to 200 ° C. The heating time is not particularly limited, but can be suitably selected from 10 seconds to 60 minutes.
The thickness of the anchor coat layer is usually about 0.1 to 20 μm, and preferably in the range of 0.5 to 5 μm.

  As the anchor coat resin of the present invention, a commercially available anchor coat agent may be used. Examples of commercially available anchor coating agents include K468HP anchor (an epoxy resin anchor coating agent manufactured by Toyo Ink Co., Ltd.).

[Adhesive layer]
The adhesive layer in the transfer film of the present invention is provided to transfer a transfer layer (including a hard coat layer, an anchor coat layer, and a colored layer laminated as required) to a molded product with good adhesiveness. is there. Examples of the adhesive layer include those composed of a heat-sensitive adhesive, a pressure-sensitive adhesive, and the like, but in the present invention, heat sealing that exhibits adhesion to a molded product by heating and pressing as necessary. A layer is preferred. Examples of the resin used for the adhesive layer include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. One kind of resin such as resin or a mixture of two or more kinds is used, and acrylic resins and vinyl chloride-vinyl acetate copolymer resins are preferable, and acrylic resins are particularly preferable. In particular, by using an acrylic resin in the adhesive layer in combination with a hard coat layer containing the polyorganosilsesquioxane of the present invention and an anchor coat layer containing an epoxy resin, a cured hard coat transferred to a molded product The surface hardness of the layer is significantly improved.

  Although it does not specifically limit as acrylic resin used for the adhesive bond layer of this invention, For example, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) Examples thereof include acrylic resins such as acrylate copolymers and methyl (meth) acrylate-styrene copolymers, and modified acrylic resins such as fluorine, and these can be used as one kind or a mixture of two or more kinds. In addition, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl ( Acrylic polyol obtained by copolymerizing (meth) acrylate ester having a hydroxyl group in the molecule such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Can also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. In addition, as a subcomponent resin, if necessary, other resins, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polypropylene, and other chlorinated polyolefin resins. May be mixed.

For the adhesive layer, one or two or more solutions or emulsions of the above resins that can be applied are applied by a known coating method such as bar coating, Mayer bar coating, gravure coating, roll coating, and dried. And if necessary, it can be formed by heating.
The temperature at the time of heating when forming the adhesive layer is not particularly limited but can be suitably selected from 50 to 200 ° C. The heating time is not particularly limited, but can be suitably selected from 10 seconds to 60 minutes.
The thickness of the adhesive layer is preferably about 0.1 to 10 [mu] m, more preferably 0.5 to 5 [mu] m, from the viewpoint that the transfer film can be efficiently transferred to a molded product.

  For the adhesive layer, organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, cyanoacrylate compounds, salicylate compounds, zinc, titanium, cerium, tin, iron, etc. An additive of fine particles having an inorganic ultraviolet absorbing ability such as an oxide of the above may be blended. Further, as an additive, a coloring pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent brightening agent, and the like can be used as necessary.

  A commercially available product may be used as the adhesive of the present invention. Examples of the commercially available adhesive include K588HP adhesive gloss A varnish (vinyl chloride-vinyl acetate copolymer resin adhesive manufactured by Toyo Ink Co., Ltd.) and PSHP780 (acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.). .

[Colored layer]
The colored layer in the transfer film of the present invention is provided when a decorative film for transferring a picture layer and / or a concealing layer to a molded product is provided. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is generally a solid layer and is provided for concealing coloring such as injection resin. Is a layer. In the concealing layer, a decorative layer may be formed alone in addition to the case of being provided inside the pattern layer in order to enhance the pattern of the pattern layer.

The pattern layer according to the present invention is a layer provided to express a pattern, a character, and a pattern-like pattern. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and the like can be mentioned.
The colored layer is usually a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, ink jet printing on the hard coat layer or anchor coat layer. By forming by, it can form between a hard-coat layer and an adhesive bond layer, or between an anchor-coat layer and an adhesive bond layer. The thickness of the colored layer is preferably 3 to 40 μm and more preferably 10 to 30 μm from the viewpoint of design.

  Preferable examples of the printing ink binder resin used for forming the colored layer include polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins. However, it is preferable that the main component is an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. Among these, when an acrylic resin, vinyl chloride-vinyl acetate copolymer resin or another acrylic resin is mixed, the printability and moldability are improved, and the adjacent hard coat layer and anchor of the present invention are used. This is preferable because adhesion to the coat layer and the adhesive layer tends to be improved. Here, the acrylic resin includes polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer. Examples thereof include acrylic resins such as polymers and modified acrylic resins by fluorine, and these can be used as one kind or a mixture of two or more kinds. In addition, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl ( Acrylic polyol obtained by copolymerizing (meth) acrylate ester having a hydroxyl group in the molecule such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Can also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin / vinyl chloride-vinyl acetate copolymer resin = 1/9 to 9/1 (mass ratio). In addition, as a subcomponent resin, if necessary, other resins, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polypropylene, and other chlorinated polyolefin resins. May be mixed.

  Examples of the colorant used in the colored layer according to the present invention include aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass and other metals, alloys, and scale-like foil powders of metal compounds. Pearl made of foil powder such as metallic pigment, mica-like iron oxide, titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, bismuth oxychloride, titanium dioxide coated talc, fish scale foil, colored titanium dioxide coated mica, basic lead carbonate Glossy (pearl) pigments, fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, zinc white, petal, vermilion , Inorganic pigments such as ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone yellow Can Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, be mixed Indanthrene Blue RS, (including dyes) organic pigments such as aniline black one or more.

Although such a colored layer is a layer provided in order to provide the designability to the transfer film of the present invention, a metal thin film layer or the like may be further formed for the purpose of improving the designability. The metal thin film layer can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. This metal thin film layer may be provided on the entire surface or may be partially provided in a pattern.
In addition to the above components, the printing ink used for forming the colored layer should be appropriately added with an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like. Can do. The printing ink is provided in a form in which the above components are usually dissolved or dispersed in a solvent. Any solvent can be used as long as it dissolves or disperses the binder resin, and an organic solvent and / or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve acetate, and alcohols.

  The transfer film of the present invention includes a low reflection layer, an antistatic layer, and an ultraviolet absorption layer as required in addition to the above-mentioned substrate, release layer, hard coat layer, anchor coat layer, adhesive layer, and colored layer. A layer, a near infrared ray blocking layer, an electromagnetic wave absorbing layer, and the like may be laminated in any order.

  The thickness of the transfer film of the present invention is not particularly limited, and can be appropriately selected from the range of 1 to 10000 μm. -150 micrometers is more preferable, and 25-150 micrometers is still more preferable.

  Since the hard coat layer of the transfer film of the present invention is tack-free and excellent in blocking resistance and can be wound and handled in a roll shape, it can be suitably used as a transfer film for in-mold injection molding. it can. For example, the transfer film of the present invention was continuously transported by a transport roll or the like into a mold composed of a fixed mold and a movable mold, and the base film side was in contact with the fixed mold surface, and appropriate position adjustment was made. Later, the movable mold moves and clamps. Then, the thermoplastic resin previously melted by heat is injected and filled from the transfer layer side of the transfer film into the mold at high temperature and high pressure, and after quenching, the mold is opened, and the hard coat layer of the present invention is the outermost surface. The molded product (in-mold molded product) transferred to the can be taken out.

When the hard coat layer of the present invention is uncured or semi-cured, the hard coat layer may be cured by irradiation with active energy rays and / or heating. The curing method can be appropriately selected from well-known methods and is not particularly limited, and examples thereof include a method of irradiation with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Among these, ultraviolet rays are preferable in terms of excellent handleability.
Conditions for curing the hard coat layer of the present invention by irradiation with active energy rays (such as irradiation conditions of active energy rays) depend on the type and energy of the active energy rays to be irradiated, the thickness and size of the hard coat layer, and the like. Although it can adjust suitably and it is not specifically limited, When irradiating an ultraviolet-ray, it is preferable to set it as about 1-1000 mJ / cm < ² >, for example. For irradiation with active energy rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After the irradiation with the active energy ray, a heating treatment (annealing and aging) can be further performed to further advance the curing reaction.

  On the other hand, conditions for curing the hard coat layer of the present invention by heating are not particularly limited, but are preferably 30 to 200 ° C, and more preferably 50 to 190 ° C, for example. The curing time can be appropriately set.

  Since the cured hard coat layer of the present invention is formed on the outermost surface of the molded product after the transfer layer of the transfer film of the present invention has been transferred to the molded product, the pencil hardness on the surface of the molded product can be made extremely high. Preferably 5H or more, more preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

  Molded products manufactured by the in-mold injection molding method using the transfer film of the present invention (in-mold molded products) have a very high surface hardness, the pattern and pattern are clearly transferred, and the transfer layer is closely attached. High durability and excellent durability. Therefore, it can be preferably used for any molded product that requires such characteristics. The transfer film of the present invention is, for example, various exteriors that require high surface hardness and scratch resistance, design, adhesion, and durability, such as interior and exterior products of automobile dashboards, housings of home appliances, etc. It can be suitably used for molded products.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corp.), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corp.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C. Moreover, the measurement of the ratio [T3 body / T2 body] of T2 body and T3 body in a product was performed by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Production Example 1 Production of Epoxy Group-Containing Low Molecular Weight Polyorganosilsesquioxane A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- Charged 27,4 mmol (68.30 g) of (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone, and raised the temperature to 50 ° C. . After adding 7.74 g (2.8 mmol as potassium carbonate) of 5% aqueous potassium carbonate solution over 5 minutes to the mixture thus obtained, 2800.0 mmol (50.40 g) of water was added over 20 minutes. Added. There was no significant temperature rise during the addition. Thereafter, the polycondensation reaction was carried out under a nitrogen stream for 5 hours while maintaining the temperature at 50 ° C.
Thereafter, simultaneously with cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% saline were added. This solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again, followed by washing with water. After separation, the aqueous layer is extracted, washed with water until the lower layer solution becomes neutral, the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 50 ° C. to obtain 25 ml of methyl isobutyl ketone. 75.18 g of a colorless transparent liquid product (epoxy group-containing low molecular weight polyorganosilsesquioxane) containing 0.04% by weight was obtained.
Analysis of the product revealed a number average molecular weight of 2235 and a molecular weight dispersity of 1.54. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 11.9.
The ¹ H-NMR chart of the resulting epoxy group-containing low molecular weight polyorganosilsesquioxane is shown in FIG. 1, and the ²⁹ Si-NMR chart is shown in FIG.

Production Example 2: Production of high molecular weight polyorganosilsesquioxane containing epoxy group (1)
The epoxy group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 1 was placed in a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube under a nitrogen stream. The mixture (75 g) was charged, and 100 ppm (5.6 mg) of potassium hydroxide and 2000 ppm (112 mg) of water were added to the net content (56.2 g) of the epoxy group-containing low molecular weight polyorganosilsesquioxane. When the molecular weight was measured by sampling at 80 ° C. for 18 hours, the number average molecular weight Mn had increased to 6000, then cooled to room temperature, 300 mL of methyl isobutyl ketone was added, and 300 mL of water was added. After removing the alkali component by repeating washing with water and concentrating, methyl isobutyl ketone 2 Colorless transparent liquid product containing wt% (epoxy group-containing high molecular weight polyorganosilsesquioxane 1) to give 74.5 g.
Analysis of the product revealed a number average molecular weight of 6176 and a molecular weight dispersity of 2.31. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 50.2.
The ¹ H-NMR chart of the resulting epoxy group-containing high molecular weight polyorganosilsesquioxane ¹ is shown in FIG. 3, and the ²⁹ Si-NMR chart is shown in FIG.

Production Example 3: Production of epoxy group-containing high molecular weight polyorganosilsesquioxane (2)
An epoxy group-containing low molecular weight polyorganosyl obtained in the same manner as in Production Example 1 under a nitrogen stream in a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube A mixture (75 g) containing sesquioxane was charged, and 100 ppm (5.6 mg) of potassium carbonate and 2000 ppm (112 mg) of water with respect to the net content (56.2 g) of the epoxy group-containing low molecular weight polyorganosilsesquioxane. ), And when the molecular weight was measured by sampling when heated at 80 ° C. for 18 hours, the number average molecular weight Mn increased to 4800, then cooled to room temperature, 300 mL of methyl isobutyl ketone was added, and water was added. Add 300mL, repeat washing with water to remove the alkali component and concentrate, methyl isobutyl Ton colorless transparent liquid product containing 25 wt% (epoxy group-containing high molecular weight polyorganosilsesquioxane 2) to give 74.5 g.

Production Example 4: Production of epoxy group-containing high molecular weight polyorganosilsesquioxane (3)
An epoxy group-containing low molecular weight polyorganosyl obtained in the same manner as in Production Example 1 under a nitrogen stream in a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube A mixture (75 g) containing sesquioxane was charged, and 100 ppm (5.6 mg) of potassium carbonate and 2000 ppm (112 mg) of water with respect to the net content (56.2 g) of the epoxy group-containing low molecular weight polyorganosilsesquioxane. ) When added and heated at 80 ° C. for 3 hours and sampled and measured for molecular weight, the number average molecular weight Mn increased to 3500, then cooled to room temperature, 300 mL of methyl isobutyl ketone was added, and water was added. Add 300mL and repeat washing with water to remove alkali components and concentrate. 74.5 g of a colorless, transparent and liquid product (epoxy group-containing high molecular weight polyorganosilsesquioxane 3) containing 25% by weight of ethylene was obtained.
When the product was analyzed, the number average molecular weight was 3500 and the molecular weight dispersity was 2.14. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 21.
The ¹ H-NMR chart of the resulting epoxy group-containing high molecular weight polyorganosilsesquioxane 3 is shown in FIG. 5, and the ²⁹ Si-NMR chart is shown in FIG.

Production Example 5: Production of acrylic group-containing low molecular weight polyorganosilsesquioxane A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was subjected to 3- 370 mmol (80 g) of (acryloxy) propyltrimethoxysilane and 320 g of acetone were charged, and the temperature was raised to 50 ° C. After adding 10.144 g of a 5% aqueous potassium carbonate solution (3.67 mmol as potassium carbonate) in 5 minutes, 3670.0 mmol of water (66.08 g) was added over 20 minutes to the mixture thus obtained. Added. There was no significant temperature rise during the addition. Thereafter, the polycondensation reaction was performed for 2 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Thereafter, simultaneously with cooling the reaction solution, 160 g of methyl isobutyl ketone and 99.056 g of 5% saline were added. This solution was transferred to a 1 L separatory funnel, and 160 g of methyl isobutyl ketone was added again, followed by washing with water. After separation, the aqueous layer is extracted, washed with water until the lower layer solution is neutral, and after the upper layer solution is separated, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 50 ° C., and methyl isobutyl ketone 22 71 g of a colorless transparent liquid product (acrylic group-containing low molecular weight polyorganosilsesquioxane) containing 0.5% by weight was obtained.
When the product was analyzed, the number average molecular weight was 2051, and the molecular weight dispersity was 1.29. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 13.4.
A ¹ H-NMR chart of the resulting acrylic group-containing low molecular weight polyorganosilsesquioxane is shown in FIG. 7, and a ²⁹ Si-NMR chart is shown in FIG.

Production Example 6: Production of acrylic group-containing high molecular weight polyorganosilsesquioxane (1)
Into a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introducing tube, the acrylic group-containing low molecular weight polyorganosilsesquioxane obtained in Production Example 5 was placed under a nitrogen stream. The mixture (71 g) was charged, and 10 ppm (0.55 mg) of potassium hydroxide and 2000 ppm (110 mg) of water were added to the net content (55.0 g) of silsesquioxane to the acrylic group-containing low molecular weight polyorgano. When the molecular weight was measured by sampling at the time of heating at 40 ° C. for 30 hours, the number average molecular weight Mn was increased to 5663, then cooled to room temperature, 300 mL of methyl isobutyl ketone was added, and 300 mL of water was added. Repeat the water washing to remove the alkali components and concentrate to remove methyl isobutyl ketone. 5 wt% colorless transparent liquid product containing (acrylic group-containing high molecular weight polyorganosilsesquioxane) to give 71 g.
When the product was analyzed, the number average molecular weight was 5893 and the molecular weight dispersity was 2.58. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 47.3.
The ¹ H-NMR chart of the resulting acrylic group-containing high molecular weight polyorganosilsesquioxane ¹ is shown in FIG. 9, and the ²⁹ Si-NMR chart is shown in FIG.

Example 1: Production of transfer film A and molded body 1 (Preparation of release agent coating liquid A)
Methyl paratoluenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing accelerator with respect to 100 parts by weight of a methylated melamine resin (“Super Becamine L-105-60” manufactured by DIC Corporation, solid content 60% by weight). ) 20 parts by weight of a solution prepared by dissolving 7 parts by weight in a mixed solvent of 2.5 parts by weight of methanol and 0.5 parts by weight of triethylamine, and 345 parts by weight of xylene, 160 parts by weight of methanol, and 115 parts by weight of butanol were added. Mixing was performed to prepare a release agent coating solution A.

(Preparation of release film A)
A biaxially stretched polyethylene terephthalate film ("Embret S50" manufactured by Unitika Ltd., thickness 50 μm) was used as the base material layer, and the release agent coating solution A was coated on one side of this film by the Mayer bar coating method. The film was dried at 150 ° C. for 30 seconds to form a release layer having an average thickness of 0.3 μm, and a release film A was obtained.

(Preparation of hard coat coating solution A)
100 parts by weight of the epoxy group-containing high molecular weight polyorganosilsesquioxane 3 (number average molecular weight Mn3500) obtained in Production Example 4 and 1.13 parts by weight of CPI-210S (photocation polymerization initiator manufactured by San Apro Co., Ltd.) It added to methyl isobutyl ketone so that solid content concentration might be 70 weight%, and the hard-coat coating liquid A was prepared.

(Preparation of transfer film A)
A hard coat coating liquid A is coated on the release layer surface of the release film A by the Mayer bar coating method, dried at a temperature of 80 ° C. for 2 minutes, and further dried at a temperature of 150 ° C. for 8 minutes to give a thickness of 40 μm. An uncured hard coat layer was formed. When the surface of the obtained hard coat layer was touched with a finger, it was confirmed that no resin adhered to the finger and no surface tackiness was exhibited (tack-free). On this hard coat layer, K468HP anchor (an epoxy resin anchor coat agent manufactured by Toyo Ink Co., Ltd.) is coated by the Mayer bar coating method and dried at a temperature of 80 ° C. for 30 seconds to form an anchor coat layer having a thickness of 1 μm. Further, on this anchor coat layer, K588HP adhesive gloss A varnish (vinyl chloride-vinyl acetate copolymer resin adhesive manufactured by Toyo Ink) was coated by the Mayer bar coating method and dried at a temperature of 80 ° C. for 30 seconds. An adhesive layer having a thickness of 4 μm was formed to obtain a transfer film A.

(Preparation of molded body 1)
The transfer film A is installed in the mold of SE130DU-CI (all electric two-material injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.), and the transparent PC (Iupilon ML-300 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) is molded. A molded body 1 having an uncured hard coat layer was obtained by injection molding at a temperature of 75 ° C. and a resin temperature of 270 ° C. The hard coat surface of the obtained hard coat layer uncured molded body 1 is irradiated with ultraviolet rays from a high-pressure mercury lamp (made by Eye Graphics Co., Ltd.) for about 10 seconds (accumulated light amount: about 400 mJ / cm ² ) to cure the ultraviolet rays After that, annealing was further performed at 40 ° C. for 1 week to obtain a molded body 1 in which the hard coat layer was cured.

Example 2: Production of transfer film B and molded body 2 A transfer film B was obtained in the same manner as in Example 1 except that PSHP780 (acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.) was used. Using the transfer film B, a molded body 2 having a hard coat layer cured by the same method as in Example 1 was obtained.

Example 3: Production of transfer film C and molded body 3 Instead of release agent coating solution A, 2-norbornene-ethylene copolymer ("TOPAS (registered trademark) 6017S-04" manufactured by Topas Advanced Polymers GmbH), 100 parts by weight of glass transition temperature (178 ° C.) and 1 part by weight of PVDC were added to a mixed solvent of toluene and tetrahydrofuran (toluene / tetrahydrofuran = 70/30 (weight ratio)) so that the solid content concentration was 5% by weight, A transfer film C was obtained in the same manner as in Example 1 except that the solution dissolved by heating (release agent coating solution C) was used, and the transfer film C was used in the same manner as in Example 1. The molding 3 in which the hard coat layer was cured by the method was obtained.

Example 4 Production of Transfer Film D and Molded Body 4 Release agent coating solution C was used in place of release agent coating solution A, and PSHP780 (acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.) was used as the adhesive. A transfer film D was obtained by the same method as in Example 1 except that the hard coat layer was cured by the same method as in Example 1 using the transfer film D.

Comparative Example 1: Production of Transfer Film E and Molded Body 5 As an anchor coat agent, TM-VMAC (acrylic polyol resin-based anchor coat agent manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 28%) and a UVRC curing agent (Daiichi Seika) Kogyo Co., Ltd. isocyanate-based curing agent (solid content: 75%) mixed at a weight ratio of 100/10 (anchor coating agent E) and coated by the Mayer bar coating method at a temperature of 60 ° C. for 1 minute. Further, a transfer film E was obtained in the same manner as in Example 1 except that the anchor coat layer having a thickness of 1 μm was formed by drying at 40 ° C. for 48 hours, and using this transfer film E, the same as in Example 1 was obtained. The molding 5 in which the hard coat layer was cured by the method was obtained.

Comparative Example 2: Production of transfer film F and molded body 6 In place of release agent coating solution A, release agent coating solution C was used, and anchor coating agent E was used as an anchor coating agent. After that, a transfer film F was obtained in the same manner as in Example 1 except that the anchor coat layer having a thickness of 1 μm was formed by drying at 60 ° C. for 1 minute and further at 40 ° C. for 48 hours. Was used to obtain a molded body 6 in which the hard coat layer was cured in the same manner as in Example 1.

Comparative Example 3: Production of Transfer Film G and Molded Body 7 Mold release agent coating solution C was used in place of release agent coating solution A, and PSHP780 (acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.) was used as the adhesive. Except for forming an anchor coat layer having a thickness of 1 μm by coating the anchor coat agent E as an anchor coat agent using a Mayer bar coating method and then drying at 60 ° C. for 1 minute and further at 40 ° C. for 48 hours. A transfer film G was obtained by the same method as in Example 1, and a molded body 7 in which the hard coat layer was cured by the same method as in Example 1 was obtained using the transfer film G.

Comparative Example 4: Production of Transfer Film H and Molded Body 8 A transfer film H was obtained in the same manner as in Example 1 except that the anchor coat layer was not provided. A molded body 8 in which the hard coat layer was cured was obtained in the same manner.

Comparative Example 5: Production of Transfer Film I and Molded Body 9 A transfer film I was obtained in the same manner as in Example 2 except that no anchor coat layer was provided. A molded body 9 in which the hard coat layer was cured was obtained in the same manner.

Comparative Example 6: Production of transfer film J and molded body 10 ( production of transfer film J)
The hard coat layer was formed by coating Seika Beam HT-S (urethane acrylate hard coat agent manufactured by Dainichi Seika Kogyo Co., Ltd.) by the Mayer bar coating method and drying it at a temperature of 100 ° C. for 1 minute. The same as the transfer film A, except that a semi-hardened hard coat layer having a thickness of 5 μm was formed by UV curing treatment (integrated light amount: about 30 mJ / cm ² ) for about 2 seconds with ultraviolet rays from Eye Graphics Co., Ltd. The transfer film J was obtained by this method.
(Production of molded body 10)
The transfer film J was used instead of the transfer film A, and the treatment after injection molding was irradiated with ultraviolet rays from a high-pressure mercury lamp (made by Eye Graphics Co., Ltd.) for about 30 seconds (integrated light amount: about 930 mJ / cm ² ). A molded body 10 in which the hard coat layer was cured was obtained in the same manner as the molded body 1 except that the semi-cured hard coat layer was cured.

(Evaluation of hardness)
The pencil hardness of the obtained molded bodies 1 to 10 was evaluated according to the pencil hardness evaluation method defined in JIS-K-5600. The results of this evaluation method are shown in Table 1.

(Adhesion)
The adhesion of the obtained molded bodies 1 to 10 was evaluated according to the adhesion evaluation method (cross cut method) defined in JIS-K-5400.

Comparative Example 7: Production of transfer film K As an anchor coating agent, LSNT primer (a urethane resin anchor coating agent manufactured by Toyo Ink Co., Ltd.) was used for coating by the Mayer bar coating method, followed by drying at 80 ° C. for 30 seconds. A transfer film K was obtained in the same manner as in Example 1 except that an anchor coat layer having a thickness of 1 μm was formed. However, the anchor coat agent could not be applied uniformly and the appearance was poor.

Comparative Example 8: Production of transfer film L As an anchor coating agent, LPE medium (aromatic resin-based anchor coating agent manufactured by Toyo Ink Co., Ltd.) was used for coating by the Mayer bar coating method, followed by drying at 80 ° C. for 30 seconds. The transfer film L was obtained in the same manner as in Example 1 except that a 1 μm thick anchor coat layer was formed. However, the anchor coat agent could not be applied uniformly and the appearance was poor.

Claims (21)

A substrate;
A hard coat layer laminated on a release layer formed on at least one surface of the substrate;
An anchor coat layer laminated on at least one surface of the hard coat layer;
Furthermore, a transfer film having an adhesive layer,
The hard coat layer is formed from a curable composition containing a polyorganosilsesquioxane having a structural unit represented by the following formula (1),
The transfer film, wherein the anchor coat layer contains an epoxy resin:

[In the formula (1), R ¹ represents a group containing a polymerizable functional group. ]. The polyorganosilsesquioxane further comprises the following formula (I)

[In the formula (I), R ^a is a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
A structural unit represented by the following formula (II):

[In the formula (II), R ^b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The structural unit represented by the formula (I) and the molar ratio of the structural unit represented by the formula (II) [the structural unit represented by the formula (I) / formula (formula (I) The transfer film according to claim 1, wherein the structural unit represented by II) is 20 or more and 500 or less.   The transfer film according to claim 1 or 2, wherein the polyorganosilsesquioxane has a number average molecular weight of 2500 to 50000. The polyorganosilsesquioxane further comprises the following formula (4)

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
The ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) to the total amount (100 mol%) of the siloxane structural unit is 55 to 100. The transfer film according to claim 1, wherein the transfer film is mol%.   The transfer film according to claim 1, wherein the polyorganosilsesquioxane has a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 4.0. The polyorganosilsesquioxane further comprises the following formula (2)

[In the formula (2), R ² represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. An alkenyl group of ]
The transfer film according to claim 1, comprising a structural unit represented by: The transfer film according to claim 6, wherein R ² is a substituted or unsubstituted aryl group.   The transfer film according to claim 1, wherein the polymerizable functional group is an epoxy group. R ¹ represents the formula (1a)

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by formula (1c):

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
Or a group represented by the following formula (1d)

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The transfer film according to claim 1, wherein the transfer film is a group represented by:   The transfer film according to claim 1, wherein the curable composition further contains a curing catalyst.   The transfer film according to claim 10, wherein the curing catalyst is a cationic photopolymerization initiator.   The transfer film according to claim 10, wherein the curing catalyst is a thermal cationic polymerization initiator.   The transfer film according to claim 10, wherein the curing catalyst is a radical photopolymerization initiator.   The transfer film according to claim 10, wherein the curing catalyst is a thermal radical polymerization initiator.   The transfer film according to claim 1, wherein the curable composition further contains a vinyl ether compound.   The transfer film according to claim 1, wherein the curable composition further contains a vinyl ether compound having a hydroxyl group in the molecule.   The transfer film according to any one of claims 1 to 16, wherein the adhesive layer contains at least one selected from the group consisting of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin.   The transfer film according to claim 1, further comprising at least one colored layer.   The transfer film according to claim 1, wherein the hard coat layer has a thickness of 3 to 150 μm.   The transfer film according to any one of claims 1 to 19, which is a transfer film used for in-mold injection molding.   An in-mold molded product obtained by transferring a layer (transfer layer) excluding the substrate on which the release layer is formed from the transfer film according to claim 20.

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