CN116963907A

CN116963907A - Laminate and method for producing same

Info

Publication number: CN116963907A
Application number: CN202280018541.XA
Authority: CN
Inventors: 长谷部花子; 小山治规; 嶋本幸展
Original assignee: Kaneka Corp
Current assignee: Kaneka Corp
Priority date: 2021-03-05
Filing date: 2022-02-01
Publication date: 2023-10-27

Abstract

The invention aims to provide a laminate comprising an acrylic resin film with excellent moldability. A method for producing a laminate having a specific crack growth rate, comprising: and (B) forming a low refractive index layer containing an acrylate resin having a particle size of less than 40% of hollow silica particles having a particle size of 100nm on the hard coat layer obtained in the step (A).

Description

Laminate and method for producing same

Technical Field

The present invention relates to a laminate including an acrylic resin film as a base material and a method for producing the laminate.

Background

An acrylic resin film obtained by molding an acrylic resin composition containing an elastomer is used and developed for various applications by using excellent properties such as transparency, hardness, weather resistance and post-moldability. Examples of the use of the acrylic resin film include use of a laminate film formed on the three-dimensional surface of a molded article by a method such as heat lamination, adhesion, in-mold injection molding, insert molding, or three-dimensional lamination molding, use of a decorative, protective, or display film used instead of coating or printing of an interior or exterior part of an automobile, use of decorative, protective, or display film for exterior parts of products such as mobile electronic devices, personal computers, and home appliances, and use as a building material. In addition, the transparency, low inherent retardation characteristics, and the like of an acrylic resin film are also being used as optical film members for constituting various display devices such as liquid crystal panels and organic EL panels.

In recent years, in automobiles, products having a design in which an information display portion such as an instrument panel and a navigation system is integrated with an automobile interior part have been developed. In order to decorate and protect the surface of a molded article for such applications, it is preferable to have, in addition to the transparency and the post-moldability required for a conventional film for interior decoration, a low retardation property, a surface hardness, a scratch resistance, an antifouling property, an antireflection property, an antiglare property, and other functions considered preferable in a display section of a display provided with a touch panel section. From this point, the acrylic resin film is considered suitable for such applications, but the surface hardness, scratch resistance, antifouling property, antireflection property, antiglare property, and the like are not sufficient.

As a method for imparting further functionalities such as surface hardness, scratch resistance, antireflection, antiglare properties, etc. to a decorative and protective film comprising such an acrylic resin film, a method of forming a functional layer on a film substrate by a method such as coating has been carried out. For example, patent document 1 describes a hard coat film for molding and the like, characterized in that a hard coat layer is provided, which is obtained by applying a coating composition containing an ionizing radiation-curable resin having a pencil hardness of B or more and exhibiting a moldability elongation of 100% or more, a fluorine-based leveling agent or fluorosilicone-based leveling agent, and inorganic oxide fine particles on a film substrate and curing the coating composition.

Patent document 2 describes a transparent resin substrate or the like comprising a light-transmitting resin substrate sheet, a base layer formed on the substrate sheet, a hard coat layer formed on the base layer, a medium refractive index layer formed on the hard coat layer, and a low refractive index layer formed on the medium refractive index layer.

Patent document 3 describes an antireflection film for insert molding in which 4 layers of a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer are sequentially provided on a thermoplastic transparent base film.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication 2016-040105

Patent document 2: international publication No. 2018/117018

Patent document 3: japanese patent laid-open publication 2016-071307

Patent document 4: japanese patent application laid-open No. 2015-152691

Patent document 5: japanese patent application laid-open No. 2012-189978

Disclosure of Invention

However, the techniques described in patent documents 1 to 3 cannot be said to have sufficient performance from the viewpoint of the formability of the laminate and the functionality of the laminate such as pencil hardness and scratch resistance of the laminate surface, and there is room for further improvement.

Accordingly, an object of one embodiment of the present invention is to provide a laminate containing an acrylic resin film having excellent moldability while having functionality such as surface hardness and antireflection, and a method for producing the laminate.

As a result of intensive studies to solve the above problems, the present inventors have found for the first time that a laminate excellent in moldability can be obtained by using a hard coat layer having specific physical properties in a laminate composed of an acrylic resin film, a hard coat layer, a low refractive index layer, and the like, and have completed an embodiment of the present invention.

Accordingly, one embodiment of the present invention is a method for manufacturing a laminate, including: a step (A1) of irradiating a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer, and a step (B1) of applying an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step (A1), and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin to form a low refractive index layer; the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, the hard coat layer contains a urethane acrylate resin, and the laminate has a crack growth of 80% or more at 120 ℃.

Further, one embodiment of the present invention is a method for producing a laminate, comprising (A1) a step of irradiating a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer, wherein the tensile elongation at break of the acrylic resin film at 120 ℃ is 170% or more, the hard coat layer contains the urethane acrylate resin, and the crack growth rate of the laminate at 120 ℃ is 80% or more.

Further, one embodiment of the present invention is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the tensile elongation at break of the acrylic resin film is 170% or more at 120 ℃, the hard coat layer comprises a urethane acrylate resin, the pencil hardness of the laminate is H or more, and the crack growth rate at 120 ℃ is 80% or more.

According to one embodiment of the present invention, there can be provided a laminate comprising an acrylic resin film having excellent moldability while having functionality such as surface hardness and antireflection, and a method for producing the laminate.

Drawings

Fig. 1 is a drawing showing TEM images after a tensile test of a laminate in which an acrylic resin film, a hard coat layer, and a low refractive index layer are laminated according to an embodiment of the present invention.

Detailed Description

One embodiment of the present invention will be described in detail below. Unless otherwise specified in the present specification, "a to B" representing a numerical range means "a or more and B or less". All documents described in the present specification are incorporated by reference in the present specification. In this specification, a constituent unit derived from an "X monomer" is referred to as an "X unit".

[ 1. Embodiment 1 ]

[ 1-1. Summary of embodiment 1 of the invention ]

The method for producing a laminated body according to embodiment 1 of the present invention (hereinafter referred to as "method for producing a1 st laminated body") is characterized by comprising: a step (A1) of irradiating a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer, and a step (B1) of applying an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step (A1), and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin to form a low refractive index layer; the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, the hard coat layer contains a urethane acrylate resin, and the laminate has a crack growth of 80% or more at 120 ℃.

The laminate obtained by the above-described method for producing a 1 st laminate has a surface hardness, and is also said to be excellent in surface hardness. In the present specification, the surface hardness of the laminate was evaluated by "pencil hardness" of the laminate. The method for measuring "pencil hardness" of the laminate is described in detail below. The laminate obtained by the method for producing the 1 st laminate has an antireflection property, and is also said to be excellent in antireflection property. In the present specification, the antireflection property of the laminate is evaluated by the "light reflectance" of the laminate. The method for measuring the "light reflectance" of the laminate is described in detail below. Further, the laminate obtained by the method for producing a 1 st laminate is excellent in moldability. In the present specification, the formability of the laminate was evaluated by "crack growth rate at 120 ℃. The method for measuring the "crack growth rate at 120℃" of the laminate is described in detail below.

The laminate obtained by the above-described method for producing a 1 st laminate is also excellent in scratch resistance. In addition, when particles are contained in the hard coat layer, the laminate obtained by the above-described method for producing the 1 st laminate has antiglare properties, which is also said to be excellent.

In another embodiment of embodiment 1 of the present invention, the method for producing a laminate comprises (A1) a step of irradiating a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin and form a hard coat layer, wherein the tensile elongation at break of the acrylic resin film at 120 ℃ is 170% or more, the hard coat layer contains the urethane acrylate resin, and the crack growth rate of the laminate at 120 ℃ is 80% or more. The production method is also a production method of the 1 st layered body.

The laminate of embodiment 1 of the present invention (hereinafter referred to as "laminate 1") is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the tensile elongation at break of the acrylic resin film at 120 ℃ is 170% or more, the hard coat layer comprises a urethane acrylate resin, the pencil hardness of the laminate is H or more, and the crack growth rate at 120 ℃ is 80% or more.

In this specification, both the laminate obtained by the method for producing a laminate of embodiment 1 and the laminate of embodiment 1 are sometimes referred to as "1 st laminate".

In recent years, in the field of in-vehicle displays, the size and the curvature have been increasing. As such a film for an in-vehicle display, an antireflection film having a higher molding rate than the conventional film is required.

However, in the techniques described in patent documents 1 and 2, the surface hardness is low, and for example, when the technique is used for surface protection of a display device having a touch panel function, defects such as scratches may occur in a display portion. In addition, in the techniques described in patent documents 2 and 3, for example, when a decorative and protective film is laminated on the three-dimensional surface of a large-sized molded body such as an automotive interior part formed by integrating an information display portion as described above, it is known that defects such as partial whitening, cracking, peeling from the surface of the molded body, and cracking and peeling of a functional layer may occur in the stretched portion of the film as the film is stretched and shaped along the shape of the molded body. That is, the prior art has the following problems: (1) a problem of moldability of a laminate, (2) a problem of antireflection of a laminate having a low refractive index layer, and (3) a problem of whitening of a laminate. Therefore, a film for decoration and protection which satisfies the requirements when used for the above-mentioned applications has not yet been found, and there is room for further improvement.

Accordingly, the present inventors have studied mainly on improvement of the moldability of a laminate, and as a result, they have found for the first time that, by making a hard coat layer, a refractive index adjusting layer, and the like in a laminate specific physical properties, peeling, cracking, and the like of a functional layer do not occur when stacking three-dimensional surfaces of a large-sized molded body, and a laminate excellent in moldability can be obtained. The inventors of the present invention have found that the laminate obtained by the above method can solve the problems of antireflection and whitening of the stretched portion in addition to moldability.

The inventors of the present invention have found that, in the course of the above-described studies, the occurrence of micro-cracks on the surface of the low refractive index layer located on the outermost surface of the laminate, which are not recognized as cracks of a size that can be recognized when looking at, is one cause of whitening in the stretched portion. Surprisingly, although the cause of whitening is microcracks in the low refractive index layer, by designing the hard coat layer located below the low refractive index layer, not only the formability of the laminate but also the whitening of the stretched portion due to microcracks in the low refractive index layer can be improved. As described above, a laminate having various functions and excellent moldability, which is composed of an acrylic resin film and a hard coat layer or an acrylic resin film, a hard coat layer and a low refractive index layer, has not been reported so far, and a method for producing the 1 st laminate is an extremely excellent technique.

As a mechanism for suppressing the whitening, the present inventors speculated as follows: by adjusting the composition of the hard coat layer, the curing conditions of the active energy rays, and the like, the hard coat layer before forming the low refractive index layer has uncured residual functional groups, and the crosslink density is lower than that in the fully cured state, whereby the adhesion between the hard coat layer and the low refractive index layer is improved, and as a result, whitening due to the shape of microcracks of the low refractive index layer is suppressed. It should be noted that the present invention is not limited in any way. Hereinafter, a method for producing the 1 st laminate will be described in detail.

In embodiment 1, the term "laminate" refers to a product (laminate) including a hard coat layer, and a product (laminate) not including a hard coat layer is referred to as a "laminate film". More specifically, in embodiment 1, for example, the "laminate" means (1) a laminate composed of an acrylic resin film and a hard coat layer, or (2) a laminate composed of an acrylic resin film, a hard coat layer and a low refractive index layer, and the "laminate film" means (3) a laminate composed of an acrylic resin film and a low refractive index layer.

The curable resin composition constituting the hard coat layer in the 1 st laminate is required to have high crack growth rate while improving the surface hardness of the hard coat layer, and is not likely to be broken or significantly whitened by stretching when the laminate is formed into a molded article. However, in general, a cured product of the curable resin composition exhibits surface hardness and scratch resistance by suppressing deformation of the surface of the cured product against external stress by highly crosslinking and/or containing a filler having high hardness. Therefore, it is difficult to achieve both the surface hardness and scratch resistance and the deformability and stretchability.

As a method for imparting high stretchability in the secondary molding to such a curable resin for a hard coat layer while maintaining the hardness, for example, the following method is mentioned.

(1) The glass transition temperature of the curable resin is designed to be between room temperature and the secondary molding temperature, and is designed to be hard at room temperature and to be capable of softening and deforming at the secondary molding temperature. Thus, the composition exhibits high surface hardness at room temperature and high stretchability in secondary molding.

(2) The curable resin having a plurality of different structures is designed to be used in combination, so that the cured crosslinked structure of the curable resin is not uniform, and the curable resin has a portion having a high crosslinked density and a portion having a low crosslinked density, and is not uniform in microstructure. Thus, the cured product exhibits high surface hardness by the portion having high crosslink density, and the portion having low crosslink density deforms and exhibits high stretchability at the time of secondary molding.

(3) The curable resin is blended with a low-crosslinking or non-crosslinking resin component and/or a low-elastic modulus resin component. Accordingly, after the curable resin is cured, a structure in which fine domains (domains) having a low crosslinking degree or no crosslinking and/or a low elastic modulus are dispersed in the curable resin phase having a high crosslinking density is formed, whereby deformability and stretchability are imparted while maintaining the surface hardness of the curable resin to some extent. Examples of such a resin component having a low crosslinking degree or an uncrosslinked or low elastic modulus include (a) thermoplastic resins such as methacrylic resins, styrene acrylonitrile resins, aliphatic or aromatic polycarbonate resins, polyester resins, phenoxy resins, and cellulose acylate resins, (b) crosslinked or uncrosslinked soft resins such as acrylic rubber, silicone rubber, hydrogenated styrene butadiene rubber, acrylonitrile butadiene rubber, and olefin rubber, which may have a reactive functional group as needed, and (c) core-shell rubber particles in which thermoplastic resins are graft polymerized on the surfaces of crosslinked rubber particles.

These methods may be used alone, for example, in (1) to (3) or in combination with each other as appropriate for the hard coat layer in the 1 st laminate.

[ 1-2. Method for producing 1 st layered body ]

The method for producing the 1 st laminate includes the following steps (A1) and (B1).

Step (A1): a step of forming a hard coat layer by irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with an active energy ray and curing the resin layer containing the urethane acrylate resin

Step (B1): and (b) a step of applying an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step (A1), and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin, thereby forming a low refractive index layer.

In the method for producing the 1 st laminate, the elongation at break of the acrylic resin film at 120 ℃ is 170% or more, the hard coat layer contains urethane acrylate resin, and the crack growth rate of the laminate at 120 ℃ is 80% or more.

In the step (A1), the resin layer containing urethane acrylate resin applied to at least one side of the acrylic resin film is irradiated with an active energy ray, and the resin layer containing urethane acrylate resin is cured to form a hard coat layer. In step (B1), a resin layer containing an acrylic resin is applied in a solution state to the cured hard coat layer containing a urethane acrylic resin formed in step (A1), and the resin layer is dried, and the resin layer is irradiated with an active energy ray to cure the resin layer, thereby forming a low refractive index layer.

In order to provide a laminate obtained by the method for producing a1 st laminate with high surface hardness, high crack growth rate at 120 ℃ and less whitening of the stretched portion, it is preferable that the hard coat layer and the low refractive index layer adhere well. In general, the low refractive index layer often contains a hard filler such as hollow silica, and the crack growth rate is generally lower than that of the hard coating layer. Therefore, microcracks, which cause whitening, may be generated at a lower elongation than the crack growth rate of the hard coat layer alone. In this case, if the adhesion between the hard coat layer and the low refractive index layer is good, the opening width of the micro-crack generated by stretching the low refractive index layer becomes extremely small, for example, 1 μm or less, and whitening due to stretching is less likely to occur.

In order to improve the adhesion between the hard coat layer and the low refractive index layer, for example, the following (a) and (b) are preferable: (a) When the resin layer to be the low refractive index layer is applied in the solution state in the step (B1), the applied resin layer (low refractive index layer) is impregnated to a certain extent into the surface of the hard coat layer within a range where the interface between the final 2 layers is not made unclear and the antireflection property is not impaired; (b) The acrylate group remaining after curing of the hard coat layer is reacted and cured together with the resin layer (low refractive index layer) when the resin layer (low refractive index layer) after coating is cured by irradiation of active energy rays, and a chemical bond is formed at the interface between the finally obtained hard coat layer and the low refractive index layer.

Therefore, for example, in the step (A1), it is preferable that the resin layer containing urethane acrylate resin forming the hard coat layer is not completely cured, the crosslinking density is slightly low, and unreacted acrylate groups remain partially. Further, in the step (B1), in order to impregnate the resin layer containing the acrylic resin to the hard coat layer surface to a certain extent in the step of coating the resin layer containing the acrylic resin forming the low refractive index layer in a solution state and optionally drying, it is preferable to (a) appropriately adjust the coating conditions and the drying conditions of the solvent and/or (B) use a certain amount of a solvent having a high boiling point which dries slowly as the solvent used in the solution, or the like.

In the method for producing the 1 st laminate, the tensile elongation at break of the acrylic resin film in the laminate at 120 ℃ is 170% or more, preferably 180% or more, and more preferably 190% or more. If the tensile elongation at break at 120℃of the acrylic resin film is 170% or more, there is an advantage that the molded shape-following property is excellent. In the method for producing the 1 st laminate, the upper limit of the tensile elongation at break is not particularly limited, but is, for example, 350% or less, preferably 300% or less, from the viewpoint of improving the tensile strength and the elastic modulus. In the present specification, "tensile elongation at break at 120" means an elongation at break of a film by a tensile test in a constant temperature bath at 120 ℃. The tensile elongation at break at 120℃of the acrylic resin film can be measured by the method described in the examples.

In the method for producing the 1 st laminate, the crack growth rate of the laminate at 120 ℃ is, for example, 80% or more, preferably 100% or more, more preferably 110% or more, and particularly preferably 120% or more. If the crack growth rate of the laminate at 120 ℃ is 80% or more, there is an advantage that shape following property at the time of molding is excellent and whitening of a portion stretched with molding is suppressed. In the method for producing the 1 st laminate, the upper limit of the crack growth rate is not particularly limited, but is, for example, 200% or less, preferably 180% or less, from the viewpoint of improving the surface hardness and the abrasion resistance. In the present specification, the term "crack growth rate of the laminate at 120" means the growth rate of cracks in the coating layer by performing a tensile test of the laminate in a constant temperature bath at 120 ℃. In the present specification, the crack growth rate of the laminate at 120℃can be measured by the method described in examples.

Further, the 1 st laminate is composed of an acrylic resin film and a hard coat layer, and when the laminate does not contain a low refractive index layer, the crack growth rate at 120 ℃ is preferably 80% or more, more preferably 100% or more, still more preferably 120% or more, and most preferably 130% or more. In the present specification, unless otherwise specified, "crack growth rate of a laminate at 120 ℃ means" crack growth rate of a laminate composed of an acrylic resin film, a hard coat layer, and a low refractive index layer at 120 ℃.

(acrylic resin film)

The acrylic resin film is preferably composed of an acrylic resin composition containing acrylic resin and graft copolymer particles containing a rubber component.

The acrylic resin film preferably contains, as the graft copolymer particles containing a rubber component, graft copolymer particles (A) having an average particle diameter of 20nm to 200nm, and may contain, in addition to the graft copolymer particles (A), graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A). Specifically, in the acrylic resin film of embodiment 1, it is preferable that the graft copolymer particles (a) are dispersed in an acrylic resin or a matrix containing an acrylic resin and other components, or that the graft copolymer particles (a) and the graft copolymer particles (B) are dispersed in an acrylic resin or a matrix containing an acrylic resin and other components.

Acrylic resin >, acrylic resin

As the acrylic resin used for the acrylic resin film, a conventionally known acrylic resin can be used. For example, from the viewpoint of hardness and moldability, when the total amount of the acrylic resin is set to 100 mass%, the acrylic resin preferably contains 20 to 100 mass% of a thermoplastic acrylic polymer composed of 50 to 100 mass% of a methyl methacrylate unit and 0 to 50 mass% of other constituent units. The total amount of the methyl methacrylate unit and other constituent units in the thermoplastic acrylic polymer is 100% by mass.

Examples of the other constituent units include constituent units derived from acrylic acid, acrylic acid derivatives, methacrylic acid derivatives, aromatic vinyl derivatives, vinyl cyanide derivatives, and the like. The other constituent units contained in the acrylic resin may be 1 or a combination of 2 or more.

Examples of the acrylic acid derivative include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate.

Examples of the methacrylic acid derivative include methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, and isobornyl methacrylate.

Examples of the aromatic vinyl derivative include styrene, vinyl toluene, and α -methylstyrene.

Examples of the vinyl cyanide derivative include acrylonitrile and methacrylonitrile.

In order to improve heat resistance, rigidity, surface hardness, and the like of the acrylic resin, a constituent unit having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, and the like. Examples of such specific structures include a glutarimide structure shown in Japanese patent application laid-open No. 62-89705, japanese patent application laid-open No. 02-178310, WO2005/54311, etc., a lactone ring structure shown in Japanese patent application laid-open No. 2004-168882, japanese patent application laid-open No. 2006-171464, etc., a glutarimide structure obtained by heat-condensing and cyclizing a (meth) acrylic acid unit shown in Japanese patent application laid-open No. 2004-307834, etc., a maleic anhydride structure shown in Japanese patent application laid-open No. 5-119217, an N-substituted maleimide structure shown in WO2009/84541, an unsubstituted maleimide structure, etc. For example, by introducing these structures into an acrylic resin, the molecular chain becomes rigid. As a result, effects such as an improvement in heat resistance, an improvement in surface hardness, a reduction in heat shrinkage, and an improvement in chemical resistance can be expected.

The method for producing the acrylic resin is not particularly limited, and for example, a known polymerization method such as a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method can be used. In addition, known radical polymerization methods, living radical polymerization methods, anionic polymerization methods, and cationic polymerization methods can be used.

The acrylic resin film is preferably formed by molding an acrylic resin composition containing a thermoplastic acrylic polymer and polymer particles containing a crosslinked elastomer.

The crosslinked elastomer is a rubber component. Therefore, the polymer particles can be said to be polymer particles containing a rubber component. The polymer particles preferably have a core-shell structure (multilayer structure) including a crosslinked elastomer as a rubber component and a graft polymer layer located on the surface layer side of the crosslinked elastomer. Polymer particles having a core-shell structure including a crosslinked elastomer and a graft polymer layer are sometimes referred to as graft copolymer particles.

The crosslinked elastomer preferably contains 50 mass% or more of the acrylate unit in 100 mass% of the crosslinked elastomer. The crosslinked elastomer is preferably a crosslinked elastomer (A1) and/or a crosslinked elastomer (B1) described later.

The polymer particles are preferably graft copolymer particles comprising a crosslinked elastomer and a graft polymer layer located on the surface layer side of the crosslinked elastomer. The graft copolymer particles are preferably graft copolymer particles (A) and/or graft copolymer particles (B) described later.

Graft copolymer containing rubber component

As described above, the acrylic resin film preferably contains the graft copolymer particles (a) as the graft copolymer particles containing the rubber component, and may further contain the graft copolymer particles (B) in addition to the graft copolymer particles (a) as needed.

The graft copolymer particles (a) preferably have a core-shell structure (multilayer structure) comprising a crosslinked elastomer (A1) as a rubber component and a graft polymer layer (A2) located on the surface layer side of the crosslinked elastomer (A1).

The crosslinked elastomer (A1) may be a known crosslinked elastomer. The crosslinked elastomer (A1) is preferably an acrylate-based crosslinked elastomer (a crosslinked elastomer composed of a polymer containing an acrylate as a main component).

The particles of the acrylic crosslinked elastomer (A1) may have a concentric spherical multilayer structure including a hard or semi-hard crosslinked resin layer in the crosslinked elastomer layer. Examples of such a hard or semi-hard crosslinked resin layer include hard crosslinked methacrylic resin particles as shown in Japanese patent publication No. 55-27576, semi-hard crosslinked particles composed of methyl methacrylate-acrylate-styrene as shown in Japanese patent application laid-open No. 4-270751, and crosslinked rubber particles having a high degree of crosslinking. By providing such a hard or semi-hard crosslinked resin layer, improvement in transparency, color tone, and the like may be expected.

The graft copolymer particles (a) preferably have a core-shell structure formed by graft polymerizing a monomer mixture forming the graft polymer layer (A2) in the presence of the particles of the acrylic crosslinked elastomer (A1) described above.

The average particle diameter of the graft copolymer particles (A) is preferably 20nm to 200nm, more preferably 50nm to 150nm, particularly preferably 50nm to 120nm.

When the average particle diameter of the graft copolymer particles (a) is too small, the impact resistance and bending fracture resistance of the acrylic resin film tend to be lowered. When the average particle diameter of the graft copolymer particles (a) is too large, the transparency of the acrylic resin film tends to be poor, and whitening due to bending tends to occur easily.

As the acrylate-based crosslinked elastomer (A1), crosslinked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing (a) an acrylate, (b) a polyfunctional monomer capable of copolymerizing with the acrylate and having 2 or more non-conjugated double bonds per 1 molecule, and (c) other vinyl-based monomers capable of copolymerizing with the acrylate as desired are preferably used.

The acrylic acid ester, other vinyl monomer and polyfunctional monomer may be all mixed and polymerized in 1 step. In addition, for the purpose of adjusting the toughness, whitening resistance, and the like of the acrylic resin film, the composition of the acrylic acid ester, the other vinyl monomer, and the polyfunctional monomer may be appropriately changed, or the acrylic acid ester, the other vinyl monomer, and the polyfunctional monomer may be polymerized in a plurality of steps of 2 or more steps in the same composition.

The acrylic acid ester is preferably an aliphatic ester of acrylic acid, more preferably an alkyl acrylate, and particularly preferably an alkyl acrylate having 1 to 22 carbon atoms in the alkyl group, from the viewpoints of excellent polymerizability, low cost, and provision of a polymer having a low Tg.

Specific examples of the preferable alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, and octadecyl acrylate. The number of these may be 1 alone or 2 or more.

The amount of the acrylic acid ester in 100% by mass of the monomer mixture (a-1) is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more. When the amount of the acrylic acid ester is 50% by mass or more, the impact resistance and elongation at tensile break of the acrylic resin film are good, and cracking is less likely to occur during secondary molding.

Examples of the other vinyl monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; aromatic vinyl derivatives such as styrene, vinyl toluene and α -methylstyrene; acrylic acid; acrylic acid derivatives such as beta-hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate; methacrylic acid; methacrylic acid derivatives such as beta-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate and glycidyl methacrylate; maleic anhydride; maleic acid derivatives such as N-alkyl maleimide and N-phenyl maleimide. The number of these may be 1 alone or 2 or more. Among these, from the viewpoints of weather resistance and transparency, 1 or more monomers selected from the group consisting of methacrylic acid esters and aromatic vinyl derivatives are particularly preferable.

The amount of the other vinyl monomer is preferably 0 to 49.9% by mass, more preferably 0 to 30% by mass, and most preferably 0 to 20% by mass based on 100% by mass of the monomer mixture (a-1). If the amount of the other vinyl monomer exceeds 49.9 mass%, the impact resistance of the acrylic resin film may be easily lowered, the elongation at the time of stretch breaking may be lowered, and cracks may be easily generated at the time of secondary molding.

As the polyfunctional monomer, monomers generally used as a crosslinking agent and/or a grafting crossover can be preferably used. Examples of the polyfunctional monomer include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate. These polyfunctional monomers may be used alone or in combination of at least 2 kinds.

As these polyfunctional monomers, a polyfunctional monomer having a function as a graft cross-linking agent is more preferable because it increases the graft bond number of the graft polymer layer (A2) to the crosslinked elastomer (A1) described later, and as a result, it gives good dispersibility of the graft copolymer (a) in the acrylic resin, improves crack resistance against tensile and bending deformation, and reduces stress whitening. As the polyfunctional monomer having the function of such a grafting-cross agent, monomers having an allyl group such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate and the like are preferable, and allyl methacrylate, allyl acrylate and the like are particularly preferable.

The amount of the polyfunctional monomer in 100% by mass of the monomer mixture (a-1) is preferably 0.1% by mass to 10% by mass, more preferably 1.0% by mass to 4% by mass. If the blending amount of the polyfunctional monomer is within the above range, it is preferable from the viewpoints of the bending fracture resistance and bending whitening resistance of the acrylic resin film, and the flowability of the resin at the time of molding.

In the acrylic crosslinked elastomer (A1), the amount of the polyfunctional monomer may be changed in the interior and the vicinity of the surface of the crosslinked elastomer (A1) for the purpose of improving the graft coating efficiency of the graft polymer layer (A2) described later. Specifically, as shown in japanese patent publication No. 1460364 and japanese patent publication No. 1786959, by increasing the content of the polyfunctional monomer having a function as a grafting cross-linking agent in the vicinity of the surface of the crosslinked elastomer (A1) to be larger than that in the inside, it is possible to improve the coating of the graft polymer layer of the graft copolymer particles (a), to improve the dispersibility in the acrylic resin, or to suppress the decrease in crack resistance due to the peeling of the interface between the graft copolymer particles (a) and the acrylic resin. Further, since a sufficient coating can be obtained by using a relatively small amount of the graft polymer layer (A2), the amount of the graft copolymer particles (a) to be blended for introducing a predetermined amount of the crosslinked elastomer (A1) into the acrylic resin composition can be reduced, and therefore the melt viscosity of the acrylic resin composition can be reduced, and improvement in melt processability, film processing accuracy, surface hardness, and the like of the acrylic resin film can be expected.

Further, a chain transfer agent may be added to the monomer mixture (a-1) for the purpose of controlling the molecular weight and crosslinking density of the acrylic ester-based crosslinked elastomer (A1), and for the purpose of controlling the thermal stability by reducing the double bond end of the polymer accompanying the disproportionation termination reaction at the time of polymerization. The chain transfer agent may be selected from chain transfer agents commonly used in radical polymerization. The chain transfer agent is preferably a monofunctional or polyfunctional thiol compound having 2 to 20 carbon atoms such as n-octylthiol, n-dodecylthiol and t-dodecylthiol, a mercapto acid, thiophenol, carbon tetrachloride or a mixture thereof. The amount of the chain transfer agent to be added is preferably 0 to 1.0 parts by mass, more preferably 0 to 0.2 parts by mass, based on 100 parts by mass of the total amount of the monomer mixture (a-1).

The particles of the crosslinked elastomer (A1) may be a single layer composed of the above-mentioned acrylate-based crosslinked elastomer (A1), may have a multilayer structure including 2 or more layers composed of the above-mentioned acrylate-based crosslinked elastomer (A1), or may have an acrylate-based crosslinked elastomer (A1) in at least 1 layer of the multilayer particles including a hard or semi-hard crosslinked resin layer.

Examples of the monomer constituting the hard or semi-hard crosslinked resin layer include methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate, alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, aromatic vinyl derivatives such as styrene and α -methylstyrene, vinyl cyanide derivatives such as acrylonitrile, maleic acid derivatives such as maleic anhydride and maleimide, and polyfunctional monomers having 2 or more non-conjugated double bonds per 1 molecule.

Of these, 1 or more selected from methyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile, and the like are particularly preferable. As the polyfunctional monomer, the same polyfunctional monomer as that used for polymerization of the acrylate-based crosslinked elastomer (A1) layer can be used. Further, in the polymerization of the hard or semi-hard crosslinked resin layer, a chain transfer agent may be used in combination for the purpose of controlling the crosslinking density, controlling the thermal stability by the reduction of the double bond terminal of the polymer, and the like, in addition to these monomers. The chain transfer agent may be the same as that used in the polymerization of the acrylate-based crosslinked elastomer (A1) layer. The amount of the chain transfer agent to be added is preferably 0 to 2 parts by mass or less, more preferably 0 to 0.5 parts by mass or less, based on 100 parts by mass of the total amount of the hard or semi-hard crosslinked resin layer.

When the graft copolymer particle (a) has A2-layer structure of the crosslinked elastomer particle (A1) and the graft polymer layer (A2) as core particles, the graft copolymer particle (a) can be typically obtained by graft copolymerizing a monomer mixture (a-2) containing 50 to 100 mass% of a methacrylate and 0 to 50 mass% of another vinyl monomer copolymerizable with the methacrylate (wherein the total of the methacrylate and the other vinyl monomer is 100 mass%) in the presence of the crosslinked elastomer particle (A1) to form the graft polymer layer (A2).

The amount of the methacrylate in 100 mass% of the monomer mixture (a-2) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, from the viewpoints of (a) securing compatibility with the acrylic resin as a base, and (b) suppressing a decrease in toughness of a coating film due to impregnation of a solvent or the like at the time of coating on the acrylic resin film, and whitening and cracking due to stretching at the time of molding.

The graft polymer layer (A2) is preferably obtained by graft copolymerizing 10 to 95 parts by mass of a monomer mixture (a-2) containing 70 to 99% by mass of an alkyl methacrylate, 0.5 to 30% by mass of an alkyl acrylate having 2 or more carbon atoms in the alkyl group, and 0 to 19% by mass of another vinyl monomer (wherein the total of the alkyl methacrylate, the alkyl acrylate, and the other vinyl monomer is 100% by mass) in the presence of 5 to 90 parts by mass of the crosslinked elastomer particles (A1) in at least 1 step. Wherein the total amount of the crosslinked elastomer particles (A1) and the monomer mixture (a-2) satisfies 100 parts by mass.

Examples of the methacrylic acid ester in the graft polymer layer (A2) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and alkyl methacrylates such as benzyl methacrylate. Among them, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group are preferable.

In the graft polymer layer (A2), as the other vinyl monomer, an alkyl acrylate having an alkyl group with 2 or more carbon atoms may be used. The alkyl acrylate having 2 or more carbon atoms in the alkyl group is preferably 1 or more selected from ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate and the like, more preferably 1 or more selected from ethyl acrylate, n-butyl acrylate, isobutyl acrylate and t-butyl acrylate, and particularly preferably n-butyl acrylate.

Examples of the other vinyl monomer that can be used in the monomer mixture (a-2) include aromatic vinyl derivatives such as styrene and nuclear substituents thereof, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid and derivatives thereof, acrylic acid and derivatives thereof, N-substituted maleimides, maleic anhydride, methacrylamides, acrylamides, and the like.

The monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as the other vinyl monomer. Briefly, the graft polymer layer (A2) preferably contains constituent units derived from a reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, an acrylic resin film having good weather resistance and chemical resistance can be easily obtained.

As the reactive ultraviolet absorber, a known reactive ultraviolet absorber can be used, and is not particularly limited. From the viewpoints of moldability and weather resistance of the acrylic resin film, the reactive ultraviolet absorber is preferably a compound represented by the following general formula (1).

(in the general formula (1), X is a hydrogen atom or a halogen atom, R ₁ Is hydrogen atom, methyl or tertiary alkyl with 4-6 carbon atoms, R ₂ Is a linear or branched alkylene group having 2 to 10 carbon atoms, R ₃ Hydrogen atom or methyl group).

The reactive ultraviolet absorber represented by the general formula (1) is specifically exemplified by 2- (2 ' -hydroxy-5 ' - (meth) acryloyloxyethylphenyl) -2H-benzotriazoles, more specifically exemplified by 2- (2 ' -hydroxy-5 ' -acryloyloxyethylphenyl) -2H-benzotriazoles, 2- (2 ' -hydroxy-5 ' -methacryloyloxyethylphenyl) -5-chloro-2H-benzotriazoles, 2- (2 ' -hydroxy-5 ' -methacryloyloxypropylphenyl) -2H-benzotriazoles, 2- (2 ' -hydroxy-5 ' -methacryloyloxyethyl-3 ' -tert-butylphenyl) -2H-benzotriazoles, and the like, and from the viewpoint of cost and operability, 2- (2 ' -hydroxy-5 ' -methacryloyloxyethylphenyl) -2H-benzotriazoles are preferably used.

The content of the constituent unit derived from the reactive ultraviolet absorber in 100% by mass of the graft polymer layer (A2) is preferably 0.01% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass.

In the production of the graft copolymer particles (a), in particular, in the graft copolymerization of the crosslinked elastomer particles (A1) and the monomer mixture (a-2) in the presence of the crosslinked elastomer particles (A1) of, for example, an acrylic ester, a polymer component (free polymer) which is not graft-bonded to the crosslinked elastomer particles (A1) of an acrylic ester may be generated. Such a free polymer (a film) can be used as a part or all of an acrylic resin constituting a matrix phase of the acrylic resin composition and the acrylic resin film.

The chain transfer agent may be added to the monomer mixture (a-2) for the purpose of controlling the molecular weight of the polymer, the grafting ratio to the above-mentioned crosslinked elastomer (A1) and the amount of the free polymer not bonded to the crosslinked elastomer (A1), and the heat stability by the reduction of the double bond terminal of the polymer accompanied by the disproportionation termination reaction at the time of polymerization. The chain transfer agent may be the same as the chain transfer agent that can be used for polymerization of the crosslinked elastomer (A1). The amount of the chain transfer agent to be used is 0 to 2 parts by mass, preferably 0 to 0.5 parts by mass, based on 100 parts by mass of the total amount of the monomer mixture (a-2).

The grafting ratio of the monomer mixture (a-2) to the crosslinked elastomer particles (A1) is preferably 5% to 250%, more preferably 10% to 200%, and even more preferably 20% to 150% or less. If the grafting ratio is less than 5%, the acrylic resin film tends to have reduced bending whitening resistance, reduced transparency, reduced elongation at tensile fracture, and easy occurrence of cracks at the time of secondary molding. If the grafting ratio exceeds 250%, the melt viscosity of the acrylic resin composition tends to be high during film molding, and the moldability of the acrylic resin film tends to be lowered.

The average particle diameter d (nm) of the crosslinked elastomer particles (A1) in the acrylic resin film and the amount w (mass%) of the polyfunctional monomer used in the acrylate-based crosslinked elastomer preferably satisfy the relationship: 0.015 d.ltoreq.w.ltoreq.0.06 d, more preferably 0.02 d.ltoreq.w.ltoreq.0.05 d. If the amount of the polyfunctional monomer is within the range of the above-mentioned relational expression, there are advantages as follows: the acrylic resin film is less likely to decrease in elongation during secondary molding, is less likely to crack during molding and cutting, is excellent in transparency, and is less likely to undergo stress whitening during bending or tensile deformation at normal temperature, at a high temperature higher than the softening temperature of the acrylic resin film, or at a low temperature between the normal temperature and the Tg of the crosslinked elastomer particles (A1).

As described above, the graft copolymer particles (B) used as needed also include the crosslinked elastomer (B1) as a rubber component, similarly to the graft copolymer particles (a). The graft copolymer particles (B) typically have a graft polymer layer (B2) located on the surface layer side of the crosslinked elastomer (B1) as in the case of the graft copolymer particles (a). In short, the graft copolymer particles (B) are preferably provided with a crosslinked elastomer (B1) and a graft polymer layer (B2).

The graft copolymer particles (B) may be substantially the same as the graft copolymer particles (A) except that the average particle diameter thereof is larger than that of the graft copolymer particles (A). The particles of the acrylic crosslinked elastomer (B1) preferably have a concentric spherical multilayer structure having a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. Examples of such a hard or semi-hard crosslinked resin layer include hard crosslinked methacrylic resin particles as shown in Japanese patent publication No. 55-27576, crosslinked particles having a semi-hard layer composed of a methyl methacrylate-acrylate-styrene copolymer as shown in Japanese patent application laid-open No. 4-270751 and WO 2014/41803. By introducing such a hard or semi-hard crosslinked resin layer, the transparency, bending whitening resistance, bending fracture resistance, and the like of the graft copolymer particles (B) having a larger particle diameter than the graft copolymer particles (a) can be improved.

The average particle diameter of the graft copolymer particles (B) is preferably 150nm to 400nm, more preferably 200nm to 350nm.

The average particle diameter of the graft copolymer particles (B) is larger than that of the graft copolymer particles (A). The graft copolymer particles (B) having a large average particle diameter are more effective in causing plastic deformation (cracking) in the acrylic resin phase around the graft copolymer particles with respect to the action of external force on the acrylic resin material. Therefore, the graft copolymer particles (B) are excellent in the effect of imparting impact resistance and crack resistance to the acrylic resin material. On the other hand, the graft copolymer particles (B) are inferior to the graft copolymer particles (A) in bending whitening resistance and/or solvent whitening resistance, etc. Therefore, for example, by adding a small amount of the graft copolymer particles (B) to the acrylic resin composition containing the acrylic resin and the graft copolymer particles (a), the following effects can be expected: the resin composition is characterized by comprising (a) a reduced total content of soft components relative to an acrylic resin film, without deteriorating the surface hardness of the acrylic resin film, (b) less likely to deteriorate the whitening properties when external stress is applied to the acrylic resin film, when a coating liquid containing an organic solvent is applied and/or during molding processing, and (c) effectively improving the crack resistance, post-moldability, and the like of the functional film.

In 1 or more embodiments of the present invention, the average particle diameters of the graft copolymer particles (a) and the graft copolymer particles (B) can be measured by a laser diffraction type particle size distribution measuring apparatus such as Microtrac particle size distribution measuring apparatus MT3000 manufactured by daily necessaries, and by a light scattering method in a latex state.

The method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and known emulsion polymerization methods, miniemulsion polymerization methods, suspension polymerization methods, and solution polymerization methods can be used. In particular, the emulsion polymerization method is preferable in view of a large adjustment range of the resin structure.

As the initiator used in emulsion polymerization of the graft copolymer particles (a) and/or the graft copolymer particles (B), known initiators such as organic peroxides, inorganic peroxides, azo compounds and the like can be used. Specifically, organic peroxides such as t-butyl hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, alkyl peroxycarbonate esters and alkyl peroxyesters; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as azobisisobutyronitrile. The number of these may be 1 alone or 2 or more.

These initiators may be used as (a) a radical polymerization initiator of thermal decomposition type, or (b) a redox type polymerization initiator system by combining these initiators with a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxypyruvate, ferrous sulfate, etc. Ferrous sulfate may be used in combination with a complex such as ethylenediamine tetraacetic acid-2-sodium.

Among these, from the viewpoint of controlling polymerization stability and particle diameter, it is more preferable to use an inorganic peroxide such as potassium persulfate, sodium persulfate, ammonium persulfate, or a redox initiator system comprising an organic peroxide such as t-butyl hydroperoxide, cumene hydroperoxide, or the like, and an inorganic reducing agent such as a 2-valent iron salt, or the like, and/or an organic reducing agent such as sodium formaldehyde sulfoxylate, reducing sugar, ascorbic acid, or the like.

The inorganic peroxide or the organic peroxide may be added by a known method such as a method of directly adding the inorganic peroxide or the organic peroxide to the polymerization system, a method of adding the inorganic peroxide or the organic peroxide to the monomer by mixing the inorganic peroxide or the organic peroxide with the monomer, or a method of adding the inorganic peroxide or the organic peroxide to the aqueous solution of the emulsifier by dispersing the inorganic peroxide or the organic peroxide in the aqueous solution of the emulsifier. From the viewpoint of transparency of the acrylic resin film, a method of adding the acrylic resin film by mixing with a monomer and a method of adding the acrylic resin film by dispersing the acrylic resin film in an aqueous solution of an emulsifier are preferable.

The surfactant (also referred to as an emulsifier) used in emulsion polymerization of the graft copolymer particles (a) and/or the graft copolymer particles (B) is not particularly limited. Well-known surfactants can be widely used in emulsion polymerization. Preferable examples of the surfactant include anionic surfactants such as sodium salts, potassium salts, and ammonium salts of (a) alkylsulfonic acids, alkylbenzenesulfonic acids, dioctylsulfosuccinic acids, alkylsulfuric acids, sodium fatty acids, polyoxyethylene alkyl ether acetic acids, alkylphosphoric acids, alkylether phosphoric acids, alkylphenyl ether phosphoric acids, and surfactants (surfactants), and nonionic surfactants such as reaction products of (b) alkylphenols, aliphatic alcohols, and propylene oxide and/or ethylene oxide. These surfactants may be used alone or in combination of 2 or more.

The graft copolymer particles (A) or the graft copolymer particles (B) may be separated and recovered from the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) obtained by emulsion polymerization by a known method. For example, the graft copolymer particles (a) or (B) may be separated and recovered by adding a water-soluble electrolyte such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate, sodium chloride, hydrochloric acid, acetic acid, sulfuric acid, or the like to the latex to coagulate the graft copolymer particles, or by freezing the latex to coagulate the graft copolymer particles, and then filtering out the solid content, washing and drying the solid content. The graft copolymer particles (A) and the graft copolymer particles (B) may be isolated and recovered by a treatment such as spray drying or freeze drying of the latex.

For the purpose of reducing the appearance defect and/or the internal foreign matter of the acrylic resin film, it is preferable to filter the latex of the graft copolymer particle (a) or the latex of the graft copolymer particle (B) with a filter and/or a screen in advance before the separation and recovery of the graft copolymer particle (a) or the graft copolymer particle (B), thereby removing the substances causing the foreign matter defect such as the environmental foreign matter and the polymer dirt.

As the filter and the mesh, a known filter and mesh used for filtering a liquid medium can be used. The form of the filter and the mesh, the pore diameter of the filter and the mesh, the filtration accuracy, the filtration capacity, and the like can be appropriately selected according to the intended use, the type, size, and amount of the foreign matter to be removed. The pore diameter and the filtration accuracy of the filter and the screen are preferably 2 times or more larger than the average particle diameter of the graft copolymer particles (A) or the graft copolymer particles (B), respectively.

The content of the graft copolymer particles (a) in 100 mass% of the acrylic resin film is not particularly limited, but is preferably 1 mass% to 70 mass%, more preferably 5 mass% to 65 mass%, and still more preferably 10 mass% to 60 mass%.

The content of the graft copolymer particles (B) in 100 mass% of the acrylic resin film is not particularly limited, but is preferably 20 mass% or less, more preferably 10 mass% or less, and most preferably 5 mass% or less.

< other Components >)

The acrylic resin film (acrylic resin composition constituting the acrylic resin film) may contain a thermoplastic resin having at least partial compatibility with the acrylic resin as required within a range not impairing the object of the present invention. Examples of such thermoplastic resins include styrene resins, polycarbonate resins, amorphous saturated polyester resins, polyamide resins, phenoxy resins, polyarylate resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, cellulose derivatives (such as cellulose acylate), vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polylactic acid resins, and PHBH (poly (3-hydroxybutyrate-co-3-hydroxycaproate) resins, and examples of such thermoplastic resins include styrene-acrylonitrile resins, styrene- (meth) acrylic resins, styrene-maleic anhydride resins, styrene-N-substituted or unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, and styrene-acrylonitrile-acrylate resins, and thermoplastic resins selected from 1 or more of styrene resins, polycarbonate resins, and cellulose acylate resins are preferable from the viewpoint of excellent compatibility with acrylic resins, and improvement of bending fracture resistance, solvent resistance, low hygroscopicity, glass-free property of the laminate, and the like of the acrylic resin film.

The acrylic resin film (acrylic resin composition constituting the acrylic resin film) may contain a conventionally known additive used for the acrylic resin film as needed within a range that does not impair the object of one embodiment of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusers, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents composed of organic particles and/or inorganic particles, infrared reflectors composed of metals and/or metal oxides, plasticizers, antistatic agents, and the like. The additive is not limited to these. These additives may be used in any amount depending on the kind of additives, insofar as the purpose of one embodiment of the present invention is not impaired, or in order to enhance the effect of one embodiment of the present invention.

Physical Properties of acrylic resin film

The glass transition temperature (Tg) of the acrylic resin film is preferably 140 ℃ or less, more preferably 135 ℃ or less, and still more preferably 130 ℃ or less. If the glass transition temperature of the acrylic resin film is 140 ℃ or lower, there is an advantage that molding can be performed without increasing the molding temperature, and occurrence of cracks during molding can be suppressed. The lower limit of the glass transition temperature of the acrylic resin film is not particularly limited, but is preferably 100 ℃ or higher from the viewpoint of preventing print offset and improving reliability during drying of printing. The glass transition temperature of the acrylic resin film was measured by the method described in examples.

The film thickness of the acrylic resin film is not particularly limited, and is, for example, 75 to 500. Mu.m, more preferably 75 to 300. Mu.m, still more preferably 100 to 250. Mu.m. If the film thickness of the acrylic resin film is 75 to 500. Mu.m, the film is elastic and has an advantage of excellent handleability. The film thickness of the acrylic resin film was measured by the method described in the examples.

The pencil hardness of the acrylic resin film measured in accordance with JIS K5600-5-4 is preferably 2B or more, more preferably B or more, particularly preferably HB or more.

Method for producing acrylic resin film

The acrylic resin film can be produced by a known processing method. Specific examples of the known processing method include a melt processing method, a calender molding method, a press molding method, and a solvent casting method. Examples of the melt processing method include a blow-up method and a T-die extrusion method. In the solvent casting method, the acrylic resin composition is dissolved and dispersed in a solvent, and then the resulting dispersion (dope) is cast in a film form onto a tape-like substrate. Then, the solvent was volatilized from the cast film-like dope, thereby obtaining an acrylic resin film.

Among these methods, a melt processing method using no solvent is preferable, and a T-die extrusion method is particularly preferable. According to the melt processing method, the limitation of the thickness of the film to be produced is small, and a film excellent in surface properties can be produced with high productivity, and the load of the solvent on the natural environment and the working environment and the production cost can be reduced.

When the acrylic resin composition is molded into a film by a melt processing method or a solvent casting method, it is preferable to remove environmental foreign matters, polymer dirt, deteriorated resins, and the like in the acrylic resin composition, which are causes of appearance defects, internal foreign matters, and the like of the acrylic resin film, by filtration using a filter or a screen, in view of improving the appearance quality of the acrylic resin film.

When a film is produced by melt processing, filtration of the acrylic resin composition can be performed at any time of 1 or more of the preparation of the acrylic resin composition by melt mixing, the granulation of the molten acrylic resin composition, and the film-forming step by using a T-die. In the solvent casting method, the acrylic resin, the graft copolymer particles (a) and (B) and other components may be mixed with a solvent and then filtered before casting and film-forming.

As such a filter and a screen, a known filter and a screen can be used without particular limitation as long as the filter and the screen have heat resistance and weather resistance corresponding to melt processing conditions, and resistance to a solvent, a dope, and the like for casting.

In the case of producing an acrylic resin film by melt processing, in particular, in order to obtain a high-quality acrylic resin film, a filter having a large filtration capacity and less retention of molten resin, which causes deterioration of the film quality, crosslinking, and the like, is preferable. For example, from the viewpoints of filtration efficiency and productivity, a leaf disc filter and a pleated filter are preferably used.

In order to improve the thickness accuracy of the acrylic resin film produced by the T-die extrusion method, for example, an automatic die apparatus may be used that measures the film thickness distribution in the TD direction (direction perpendicular to the extrusion direction) of the extrusion-molded film on line, and automatically adjusts the die lip gap of the T-die in the extrusion film based on the film thickness distribution. By using an appropriate control method and applying an automatic mold, the thickness accuracy of the acrylic resin film can be improved.

In the production of an acrylic resin film, when the film is molded as needed, both surfaces of the film in a molten state are brought into contact (nip) with a cooling roll or a cooling belt at the same time, whereby a film having more excellent surface properties can be obtained. In this case, the film in a molten state is preferably simultaneously brought into contact with a roll or a cooling belt maintained at a temperature of-80℃or higher, preferably-70℃or higher, of the glass transition temperature of the acrylic resin composition.

As at least one of the rollers for performing such sandwiching, it is more preferable to use a roller having a metal sleeve with elasticity as disclosed in, for example, japanese patent application laid-open No. 2000-153547 and japanese patent application laid-open No. 11-235747, and transfer the roller mirror surface or a specific surface shape with a low sandwiching pressure. Thus, a film having (a) a small residual strain and excellent smoothness and/or a film having a moderate surface roughness and excellent lubricity of the film surface and having less internal strain in which adhesion between films is suppressed can be obtained.

Further, according to the purpose, monoaxial stretching or biaxial stretching may be performed after the film is formed. The uniaxial or biaxial stretching may be performed using a known stretching device. Biaxial stretching may be performed in a known manner such as sequential biaxial stretching, simultaneous biaxial stretching, and a method of stretching in the transverse direction while relaxing the longitudinal direction after stretching in the longitudinal direction to reduce bow (Bowing) of the film.

Further, any surface shape such as a thin line, a prism, a concave-convex shape, a three-dimensional decoration, a matt surface, a rough surface having a certain surface roughness, and a knurling on the end of the film may be given to one or both surfaces of the acrylic resin film as needed for the application. Such imparting of the surface shape can be performed by a known method. For example, a method of transferring the surface shape of a roll by sandwiching both surfaces of a film in a molten state immediately after extrusion or a molded film fed from a feeding device with 2 rolls or belts having a surface shape on at least one surface is exemplified.

(hard coat)

The hard coat layer in the method for producing a 1 st laminate is a functional layer laminated on at least one side of the acrylic resin film and contains a urethane acrylate resin. The hard coat layer may be laminated on one side or both sides of the acrylic resin film.

As the hard coat layer, various hard coat layers including urethane acrylate resins conventionally provided in various functional films, resin molded articles, and the like can be used without particular limitation.

< polyurethane acrylate resin >)

The urethane acrylate resin can be obtained, for example, by mixing a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, and generating a urethane bond by the reaction of an isocyanate group and a hydroxyl group.

The various characteristics of the urethane acrylate resin may be determined according to the structure of the polyol, the kind of the polyisocyanate, and the acryl or methacryl (CH) group derived from the hydroxyl group-containing (meth) acrylate ₂ =ch-CO-or CH ₂ ＝C(CH ₃ ) The amount of-CO-) is appropriately adjusted without particular limitation. As a polyamineThe ester acrylate resin may further include urethane acrylate resins commercially available as ultraviolet-curable hard coating agents.

< others >

In the method for producing the 1 st laminate, the hard coat layer of the laminate may contain other components in addition to the urethane acrylate resin. Examples of the component other than the urethane acrylate resin include monomers, oligomers, resins, or mixtures thereof having a radical-reactive functional group such as monofunctional or polyfunctional (meth) acrylate, epoxy acrylate monomer, polyester acrylate, silicon acrylate, polycarbonate acrylate, and polyacrylic acrylate. Further, the urethane acrylate resin may be used in combination with a composition comprising, for example, (a) a hydrolysis condensate of a di-to tetrafunctional silane compound, and/or (b) a monomer, oligomer, resin or a mixture thereof having a cationically and/or anionically curable functional group such as an epoxy group and an oxetane group. The urethane acrylate resin may be used alone as a component used for forming the hard coat layer, or 1 or 2 or more of the other components may be mixed and added to the urethane acrylate resin.

The (meth) acrylate is not particularly limited as long as it has at least 1 or more (meth) acryloyl groups. Specifically, examples thereof include polyfunctional (meth) acrylates such as (a) alicyclic (meth) acrylates such as alkyl (meth) acrylate, aryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and (b) polyalkylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, hexanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate. The above-mentioned components may be used alone or in combination of 1 kind or 2 or more kinds. The (meth) acrylate may further be a commercially available product as an ultraviolet curable hard coat agent. In the present specification, (meth) acrylate is meant to include both methacrylate and acrylate. In the present specification, (meth) acryl means a compound comprising methacryl and acryl.

The epoxy acrylate monomer is not particularly limited. Specifically, glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monoxide (i.e., 1, 2-epoxy-4-vinylcyclohexane), and the like are exemplified.

As the hydroxyl group-containing (meth) acrylate, there may be added, without particular limitation, for example, in addition to 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, (a) a compound having an ethylenic unsaturated bond of at least 1 hydroxyl group, such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, allyl alcohol, ethylene glycol allyl ether, glycerol (mono, di) allyl ether, N-methylol (meth) acrylamide, etc., or (b) a mixture thereof, as required.

The polyisocyanate is not particularly limited. As the polyvalent isocyanate compound which is a compound having 2 or more isocyanate groups, for example, examples thereof include 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3' -dimethyl-4, 4' -diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate 4,4' -diphenylmethane triisocyanate, 3' -dimethylphenylene diisocyanate, 4' -biphenylene diisocyanate, 1, 6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2, 4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate 6-isopropyl-1, 3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, toluidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, trimethylolpropane adduct of triethylenediisocyanate, isocyanurate of triethylenediisocyanate, oligomer of diphenylmethane-4, 4' -diisocyanate, biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, uretdione of hexamethylene diisocyanate, isocyanurate body of isophorone diisocyanate, and the like. In addition, these polyisocyanates may be used singly or in combination of 1 or more than 2.

Specific examples of the polyhydric alcohol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 8-octanediol, 1, 4-cyclohexanedimethanol, polytetramethylene glycol, and the like. These polyols may be used alone or in combination of 1 or more than 2.

In order to promote the reaction with the isocyanate groups of the isocyanate component, an organotin-based urethanization catalyst may be used. The organotin-based urethanization catalyst may be any catalyst generally used in urethanization reaction, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmaleate, tin stearate, and tin octoate.

The composition comprising the hydrolytic condensate of the silane compound is preferably a curable composition containing a condensate (a) obtained by hydrolyzing and condensing a silane compound (Z) having a hydrolyzable silyl group represented by the following general formula (2), and if necessary, a catalyst or a curing agent (B) for reacting the reactive substituent.

R ⁴ -(SiR ⁵ _a (OR ⁶ ) _3-a )···(2)

(in the general formula (2), R ⁴ To selectAlkyl group having 1 to 10 carbon atoms, aryl group having 6 to 25 carbon atoms, and 1-valent hydrocarbon group of aralkyl group having 7 to 12 carbon atoms, which may be substituted with a reactive substituent selected from epoxy group, oxetanyl group, (meth) acryl group, vinyl group, hydroxyl group, carboxyl group, amino group protected with a functional group, from at least a part of the terminal end. R is R ⁵ Each independently is a 1-valent hydrocarbon group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R is R ⁶ Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a is an integer of 0 to 2)

The weight average molecular weight of the condensate (a) is preferably 30000 or less. The proportion of the silane compound having a reactive substituent is preferably 10% by mass or more based on the total amount of the silane compound (Z). When such a composition comprising a hydrolysis condensate of the silane compound (Z) is used in combination with a urethane acrylate resin in the hard coat layer, the hardness, chemical resistance, weather resistance, and the like of a cured product as the hard coat layer can be made excellent.

The reactive substituent of the general formula (2) is preferably an epoxy group or an oxetanyl group from the viewpoint of less cure shrinkage at the time of forming the hard coat layer and easiness of obtaining a functional film excellent in durability and suppressed in curling.

As the catalyst for carrying out the hydrolytic condensation reaction of the silane compound (Z), a neutral salt catalyst is more preferably used. This is because when the reactive substituent is an epoxy group and/or an oxetanyl group, decomposition of the reactive substituent during hydrolytic condensation is easily suppressed.

As a method for curing the resin layer (resin composition) at the time of forming the hard coat layer, a known method can be applied. As the curing method, a method of irradiating active energy rays typified by ultraviolet rays is preferable. When curing is performed by irradiation with active energy rays, a photopolymerization initiator may be used. Further, when a composition comprising (a) the hydrolysis condensate of a silane compound described above, and/or (b) a monomer, oligomer, resin or a mixture thereof having a cationic curable and/or anionic curable functional group such as an epoxy group and an oxetane group is used in combination with a urethane acrylate resin, a photo-anion generator, a photo-cation generator or the like may be suitably used.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, anisole, benzoylether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one compounds. Among these, 1-hydroxy-cyclohexyl-phenyl-ketone excellent in compatibility with the resin is preferable.

Specific examples of the photo cation generator include CPI-100P, CPI-101A, CPI-200K and CPI-200S manufactured by San-Apro corporation; and WPI-124, WPI-113, WPI-116, WPI-169, WPI-170 and WPI-124 manufactured by Wako pure chemical industries, ltd; RHODOORSIL 2074, manufactured by Rhodia Co.

Specific examples of the photocathogenic agent include acetophenone O-benzoyl oxime, nifedipine, 1,5, 7-triazabicyclo [ 4.4.0 ] dec-5-ene, 2-nitrophenylmethyl-4-methacryloxypiperidine-1-carboxylate, 1, 2-diisopropyl-3- [ bis (dimethylamino) methylene ] guanidine, 2- (9-oxoxanthen-2-yl) propionic acid2- (3-benzoylphenyl) propionate, 1, 2-dicyclohexyl-4, 5-tetramethylbiguanide +.>N-butyltriphenylborate, and the like.

When a hard coat layer is formed by curing a resin layer (coating film) composed of a curable composition, various leveling agents known in the art may be blended into the curable composition for the purpose of improving coating properties, scratch resistance after curing, stain resistance, and the like. As the leveling agent, a fluorine-based leveling agent, an acrylic leveling agent, a silicone leveling agent, and an adduct or a mixture thereof can be used. The amount of the leveling agent to be blended is not particularly limited, and is, for example, in the range of 0.03 parts by mass to 3.0 parts by mass relative to 100 parts by mass of the curable composition.

When the curable composition is applied to form a hard coat layer, various additives such as ultraviolet absorbers, light stabilizers, antifoaming agents, antioxidants, light diffusers, matting agents, antifouling agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic fine particles, antistatic agents, and the like may be added to the curable composition as necessary. The additive is not limited to these.

In order to impart an appropriate coatability to the curable composition, an organic solvent is generally blended. The organic solvent is not particularly limited as long as it imparts a desired coatability to the curable composition and forms a hard coat layer having a desired film thickness and performance. From the viewpoints of coatability and drying property of the formed resin layer (coating film), the boiling point of the organic solvent is preferably 50 to 150 ℃.

Specific examples of the organic solvent include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohols such as methanol, ethanol, isopropanol and butanol; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran, twoEthers such as alkyl, propylene glycol monoethyl ether, methyl cellosolve and ethyl cellosolve; amides such as N-methylpyrrolidone and dimethylformamide. The organic solvent may be used alone or in combination of 2 or more.

When the curable composition is applied to the main surface of the acrylic resin film as a base film, any method may be used as a coating method without any particular limitation. Examples of the coating method include a reverse coating method, a gravure coating method, a bar coating method, a die coating method, a spray coating method, a kiss coating method, a wire bar coating method, and a curtain coating method. These coating methods may be carried out 1 kind alone or in combination of plural kinds.

The curable composition for forming a hard coat layer described above is applied to the surface of the acrylic resin film as a base film, and then the organic solvent is removed from the applied film by drying, and the obtained resin layer is cured by light such as ultraviolet irradiation, thereby forming a hard coat layer.

The drying temperature at the time of removing the organic solvent from the resin layer after coating is preferably 60 to 120 ℃, more preferably 70 to 100 ℃. If the drying temperature is too low, an organic solvent may remain in the resin layer (coating film). In addition, if the drying temperature is too high, the flatness of the functional film (hard coat layer) may be impaired due to thermal deformation of the base film.

The wavelength of the ultraviolet light irradiated when curing the resin layer (coating film) is preferably in the range of 200nm to 400 nm. The Ultraviolet (UV) accumulated light amount can be preferably the conditions described in [ 4. Method for producing a laminate ], which will be described later. As the irradiation device for exposure light of ultraviolet rays, for example, (a) a lamp light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, and an excimer lamp, and/or (b) an irradiation device provided with a pulsed or continuous laser light source such as an argon ion laser and a helium-neon laser, etc. may be used.

As the composition for forming a hard coat layer (curable composition), for example, commercially available products such as "Z-607-27L" manufactured by Aica Industrial Co., ltd., the trade name "ENS102" manufactured by DIC Co., ltd., the trade name "beam set 1200W" manufactured by Sichuan chemical Co., ltd., the trade name "Acryt 8UX-116A" manufactured by TAISEI FINE CHEMICAL Co., ltd., the trade name "NXD-004AP" manufactured by Japanese chemical paint Co., ltd., the trade name "P-5820TAH-1" manufactured by Dai-Chemie Industrial Co., ltd., the trade name "Lioduas MOL7200" manufactured by TOYOCHEM Co., ltd., can be used. Since these commercial products also have a rate of expansion after curing, the use of these commercial products can further increase the crack growth rate of the laminate at 120 ℃.

The film thickness of the hard coat layer is not particularly limited, and is, for example, 0.6 μm to 10.0. Mu.m, preferably 0.7 μm to 7.0. Mu.m, more preferably 0.8 μm to 5.0. Mu.m. If the film thickness of the hard coat layer is 0.6 μm to 10.0 μm, there is an advantage that both abrasion resistance and moldability can be achieved. The film thickness of the hard coat layer was measured by the method described in the examples.

In embodiment 1 of the present invention, inorganic particles and/or metal particles may be added to improve the hardness, abrasion resistance, antistatic properties, and the like of the hard coat layer. The inorganic particles and the metal particles are not particularly limited, and examples thereof include silica, alumina, titanium oxide, zinc oxide, zirconium oxide, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, metallic copper, and the like. These particles may be used without surface treatment, or may be subjected to surface treatment by a known method in advance to control the dispersion state, so that the affinity with the hard coat layer can be appropriately controlled.

< particle >)

The hard coat layer in the method for producing a 1 st laminate may further contain particles in addition to the urethane acrylate resin. In the method for producing the 1 st laminate, when the hard coat layer contains particles, a laminate containing an acrylic resin film excellent in antiglare property can be obtained.

The particles blended in the hard coat layer for the purpose of imparting antiglare properties and the like can be appropriately adjusted in terms of the material of the particles, the blending fraction, the type of the dispersion solvent of the particles, the particle diameter, the dispersion particle diameter, the film thickness of the hard coat layer, the relative refractive index difference with the hard coat substrate, the affinity or reactivity of the particle surface with the hard coat substrate or the solvent, and the like within a known technical range that does not impair the effect of the present invention, in order to obtain a desired balance of various properties such as antiglare properties, clarity of transmitted images, glare, black feeling of the surface, surface hardness, lubricity, antistatic properties, and the like.

The material of the particles to be blended in the hard coat layer is not particularly limited as long as the effect of the present invention is exhibited, and examples thereof include (a) inorganic particles such as silica, alumina, glass beads or glass flakes, mica, clay, titanium oxide, zinc oxide, zirconium oxide, metal particles, and/or (b) crosslinked organic resin particles mainly composed of (meth) acrylic acid alkyl ester units, aromatic vinyl units, siloxane units, and the like, and (c) core-shell type multilayer structure resin particles. From the viewpoint of easy availability and easy design of antiglare property depending on the application, the particles are preferably inorganic oxide particles (e.g., silica, alumina, titania, zinc oxide, zirconia, etc.) and/or crosslinked organic resin particles, more preferably 1 or more selected from silica, alumina, zirconia, crosslinked silicone resin, crosslinked acrylic resin, and crosslinked aromatic vinyl resin. In addition, silica particles, alumina particles and crosslinked organic resin particles are particularly preferable from the viewpoint of balance of physical properties such as antiglare property, dispersibility and surface hardness. From the viewpoint of controlling dispersibility, the particles may be subjected to a surface treatment, graft polymerization treatment, or the like by a known method such as plasma treatment or corona treatment using a silane coupling agent, a reactive monomer, or the like which may have a reactive substituent. From the viewpoint of improving the interfacial adhesion between the particles and the hard coat layer and improving the dispersibility of the particles, cracks and/or whitening during stretching, it is preferable that at least a part of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin. Examples of the reactive functional group reactive with the urethane acrylate resin include (a) a radical reactive functional group such as a vinyl group or a (meth) acryl group, (b) a plasma functional group such as an epoxy group, an oxetanyl group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyano group, a hydroxyl group, an amino group, and (c) a moisture curable functional group such as a silyl group or an alkoxysilyl group.

In the present specification, the "particles" may be dispersed in the form of primary particles or may be dispersed in the form of a plurality of aggregated particles depending on the size of the primary particles. The size of the region (dispersion domain) in which these particles or aggregates thereof are distributed is defined as "average dispersion particle diameter". The particles having a large primary particle size may have the same average dispersed particle size as the primary (basic) particle size.

The average dispersion particle diameter of the particles (e.g., silica particles) is not particularly limited as long as the effect of the present invention is exhibited, and may be, for example, 0.1 μm to 50.0 μm, 0.2 μm to 25.0 μm, 0.5 μm to 10 μm, or the like. The average dispersion particle diameter of the particles (for example, silica particles) can be measured by the method described in examples.

In the method for producing the 1 st laminate, the content of the particles in the hard coat layer is not particularly limited as long as the effect of one embodiment of the present invention is exhibited, and may be, for example, 0.1 to 30.0 wt%, 0.5 to 20.0 wt%, 1.0 to 15.0 wt%, or the like.

(Low refractive index layer)

In the method for producing a 1 st laminate, it is preferable that the hard coat layer further comprises a low refractive index layer containing an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100 nm. The low refractive index layer constitutes an anti-reflection layer.

The low refractive index layer is typically formed by curing a composition for forming a low refractive index layer (curable composition). The low refractive index layer is a layer for exhibiting an antireflection effect by utilizing a significant refractive index difference from the hard coat layer and/or a significant refractive index difference from a high refractive index layer described later. As the low refractive index layer, for example, a layer containing 40% or more of an acrylic resin containing hollow silica fine particles having a particle diameter of less than 100nm may be used, and a conventionally known layer used for an antireflection film or the like may be suitably used. As the low refractive index layer forming composition, a composition obtained by adding hollow silica fine particles as a refractive index adjusting material to an acrylic resin as a base organic material can be used.

The acrylic resin contained in the low refractive index layer contains hollow silica particles. The hollow silica particles have a particle diameter of less than 100nm, preferably 80nm or less, and more preferably 60nm or less. If the particle diameter of the hollow silica particles is less than 100nm, there is an advantage that the transparency is excellent. The lower limit of the particle diameter of the hollow silica particles is not particularly limited, but is, for example, 10nm or more, preferably 20nm or more, from the viewpoint of improving the antireflection performance. The particle size of the hollow silica particles can be measured by the method described in the examples.

The hollow silica particles in the acrylate resin in the low refractive index layer are contained in an amount of 40% or more, preferably 45% or more, and more preferably 50% or more. If the content of hollow silica particles in the acrylic resin is 50% or more, there is an advantage that the antireflection property is excellent. The upper limit of the content of the hollow silica fine particles in the acrylic resin is not particularly limited, but is, for example, 80% or less, preferably 70% or less, from the viewpoint of improving the surface hardness and abrasion resistance.

In embodiment 1 of the present invention, the low refractive index layer forming composition may contain a resin similar to the resin contained in the hard coat layer as an organic material other than the acrylate resin. In embodiment 1 of the present invention, the low refractive index layer-forming composition may contain silica particles, fluoride particles, or the like as a refractive index-adjusting material other than hollow silica particles. Examples of the fluoride constituting the fluoride fine particles include magnesium fluoride, lithium fluoride, aluminum fluoride, and calcium fluoride.

In order to impart stain resistance to the low refractive index layer, a part of the organic material may be replaced with a water-repellent material or an oil-repellent material. Examples of the water-repellent material or the oil-repellent material include (a) a compound containing a long-chain hydrocarbon skeleton, a fluorocarbon skeleton, a fluoropolyether skeleton, a polysiloxane skeleton, and the like, and (b) a resin having each of the above-mentioned skeletons. They may have, for example, a functional group reactive with urethane acrylate resin, and in addition, two or more of these backbones may be contained in one molecule. In addition, a plurality of them may be used in combination.

Various additives may be added as other components to the low refractive index layer within a range not to impair the effect of one embodiment of the present invention. Examples of such additives include photopolymerization initiators, dispersants, surfactants, ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, leveling agents, antifouling agents, anti-fingerprint agents, lubricity imparting agents, and the like.

As the composition for forming the low refractive index layer, for example, commercially available products such as "Z-824" manufactured by Aica Industrial Co., ltd., "TU-2359" manufactured by Sichuan chemical Co., ltd., and "ELCOM P-5062" manufactured by Nitro catalyst chemical Co., ltd may be used. Since these commercial products have a rate of expansion after curing, the use of these commercial products can increase the 120 ℃ crack growth rate of the 1 st laminate.

< other functional layers >)

The 1 st laminate may have other functional layers than the above. The other functional layers are not particularly limited, and various functional layers known in the related art may be used, for example. Specific examples of the other functional layer include an antiglare layer, an antifouling layer, an antiglare layer, an antistatic layer, an ultraviolet shielding layer, an infrared shielding layer, a surface roughness layer, a light diffusion layer, a matting layer, a polarizing layer, a coloring layer, a design layer, an embossing layer, a conductive layer, a gas barrier layer, a gas absorbing layer, a high refractive index layer, and the like. These functional layers may be provided in combination of 2 or more. Further, one functional layer may have two or more functions.

(others)

In the step (A1), ultraviolet (UV) rays are used as active energy rays. In the step (A1), the cumulative amount of active energy ray irradiation (for example, the cumulative amount of Ultraviolet (UV) irradiation) is 150mJ/cm, for example ² ～500mJ/cm ² Preferably 180mJ/cm ² ～450mJ/cm ² More preferably 200mJ/cm ² ～400mJ/cm ² . If the cumulative light amount of the UV irradiation is 150mJ/cm ² ～500mJ/cm ² The hardness of the hard coat layer can be appropriately obtained while ensuring moldability. If the cumulative light amount of the UV irradiation is 150mJ/cm ² As described above, the degree of crosslinking of the hard coat layer is improved, and the surface hardness and scratch resistance can be improved. If the cumulative light amount of the UV irradiation is 500mJ/m ² Hereinafter, the low refractive index layer forming composition is appropriately impregnated into the hard coat layer and the hard coat layer remains in the hard coat layer during the coating of the low refractive index layer forming compositionThe alkenoate groups are moderate. As a result, after curing the low refractive index layer forming composition (resin layer), the adhesion between the hard coat layer and the low refractive index layer can be maintained, and whitening of the resulting laminate when 80% stretching is performed at 120 ℃ can be suppressed.

In the step (A1), the cooling roll temperature is, for example, 20 to 70 ℃, preferably 25 to 60 ℃, more preferably 30 to 55 ℃. When the cooling roll temperature in the step (A1) is 20 to 70 ℃, the resin layer of the composition for forming a hard coat layer can be cured while suppressing the temperature rise of the resin layer during irradiation with ultraviolet rays, and a laminate having desired physical properties can be produced.

The conditions other than those described above in the step (A1) and the like may be applied to the conditions described above (hard coat layer).

In the step (B1), an acrylic resin (low refractive index layer forming composition) containing 40% or more of hollow silica fine particles having a particle diameter of less than 100nm is applied to the hard coat layer obtained in the step (A1), and the obtained resin layer (low refractive index layer forming composition) containing the acrylic resin is irradiated with an active energy ray to cure the resin layer containing the acrylic resin, thereby forming a low refractive index layer.

In the step (B1), ultraviolet (UV) rays are used as active energy rays. In the step (B1), the cumulative amount of active energy ray irradiation (for example, the cumulative amount of Ultraviolet (UV) irradiation) may be the same as that in the step (A1).

In the step (B1), the cooling roll temperature is, for example, 20 to 70 ℃, preferably 25 to 60 ℃, more preferably 30 to 55 ℃. When the temperature of the cooling roll in the step (B1) is 20 to 70 ℃, the resin layer of the composition for forming a low refractive index layer can be cured while suppressing the temperature rise of the resin layer during irradiation with ultraviolet rays, and a laminate having desired physical properties can be produced.

The conditions other than those described above in step (B1) and the like may be applied to the conditions described above (hard coat layer) and (low refractive index layer).

Further, embodiment 1 of the present invention provides a method for producing a laminate, comprising (B1') a step of adding a solvent to the acrylic resin as a material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm, wherein the solvent contains at least 1 or more solvents, and the highest boiling point solvent is a boiling point of 115 ℃ to 180 ℃. In the step (B1) and the step (B1'), the "acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm" is also said to be "a composition for forming a low refractive index layer".

In the step (B1'), the solvent having the highest boiling point has a boiling point of, for example, 115℃to 180℃and preferably 120℃to 170℃and more preferably 125℃to 160 ℃. When the boiling point of the solvent having the highest boiling point is 115 to 180 ℃, the adhesion between the hard coat layer and the low refractive index layer is good, and a laminate having lower whitening (a smaller degree of whitening) at the time of stretching can be obtained.

The solvent used in the step (B1') is not particularly limited as long as it contains a solvent having the boiling point described above. The solvent having a boiling point of 115℃to 180℃is not particularly limited, and examples thereof include propylene glycol monomethyl ether (PGM), cyclohexanone, butyl acetate, propylene glycol monomethyl ether acetate (PGMA), and the like. Among them, PGM is preferable from the viewpoints of compatibility with resins and drying efficiency. They may be used in 1 kind, or may be used in combination of 2 or more kinds.

In the step (B1'), a method for preparing an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm by adding a solvent to the acrylic resin is not particularly limited, and a known method can be used. For example, the acrylic resin containing the hollow silica fine particles can be prepared by the method described in examples.

[ 1-3. Laminate ]

The 1 st laminate comprises an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. More specifically, the 1 st laminate is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the tensile elongation at break of the acrylic resin film is 170% or more at 120 ℃, the hard coat layer comprises a urethane acrylate resin, the pencil hardness of the laminate is H or more, and the crack growth rate at 120 ℃ is 80% or more. In a preferred embodiment of embodiment 1 of the present invention, the 1 st laminate further includes a low refractive index layer on the hard coat layer.

(laminate)

The 1 st laminate is composed of at least a specific acrylic resin film and a specific hard coat layer as described above. In a preferred embodiment of embodiment 1 of the present invention, the 1 st laminate is composed of a specific acrylic resin film, a specific hard coat layer, and a specific low refractive index layer.

In embodiment 1 of the present invention, the 1 st laminate is composed of the acrylic resin film described in the above (acrylic resin film) and the hard coat layer described in the above (hard coat layer). In a preferred embodiment of embodiment 1 of the present invention, the 1 st laminate is composed of the acrylic resin film described in the above (acrylic resin film), the hard coat layer described in the above (hard coat layer), and the low refractive index layer described in the above (low refractive index layer). The 1 st laminate is preferably obtained by the production method described in [ 1-2. The production method of the 1 st laminate ].

The pencil hardness of the 1 st laminate is H or more, preferably 2H or more, and more preferably 3H or more. If the pencil hardness of the 1 st laminate is H or more, there is an advantage that scratch is not easy. In the present specification, "pencil hardness" is an index of abrasion resistance, and abrasion resistance is evaluated based on the degree of scratch formed at the time of scratch. In the present specification, pencil hardness of the laminate can be measured by the method described in examples.

The "elongation at break at 120℃and" crack growth at 120℃ "of the 1 st laminate can be referred to as the values described in the above [ 1-2. Method for producing a laminate ].

The haze of the 1 st laminate is, for example, 1.0% or less, preferably 0.8% or less, and more preferably 0.5% or less. If the haze of the 1 st laminate is 1.0% or less, there is an advantage that transparency is excellent. In the present specification, haze of the laminate can be measured by the method described in examples.

The delta haze of the 1 st laminate after 80% stretching at 120 ℃ is, for example, 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less. If the delta haze of the 1 st laminate after 80% stretching at 120 ℃ is 3.0% or less, there is an advantage that whitening at the time of molding can be suppressed. The delta haze of the 1 st laminate after 80% stretching at 120℃can be measured by the method described in examples.

In the 1 st laminate, the laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a delta haze after 20% stretching at 120 ℃ (hereinafter, also simply referred to as "20% delta haze after stretching at 120 ℃), of preferably 30% or less, more preferably 20% or less. In order to increase the crack growth rate of the 1 st laminate at 120 ℃ and/or to suppress whitening at 120 ℃ during stretching, the low refractive index layer in the 1 st laminate is preferably a low refractive index layer with little whitening at stretching. When the laminated film formed by laminating the low refractive index layer on the acrylic resin film has a delta haze of 30% or less after 20% stretching at 120 ℃, whitening of the 1 st laminate after 80% stretching at 120 ℃ is reduced, and a laminate having more excellent moldability can be produced. In the present specification, the Δhaze after 20% stretching at 120 ℃ is measured by the method described in the examples, using a laminated film obtained by laminating a low refractive index layer on an acrylic resin film as a measurement target.

The light reflectance of the 1 st laminate is, for example, 2.0% or less, preferably 1.8% or less, and more preferably 1.6% or less. If the light reflectance of the 1 st laminate is 2.0% or less, there are advantages in that the antireflection performance is excellent and the visibility at the time of lamination on the display surface is excellent. The lower the light reflectance of the 1 st laminate, the better, and may be 0.0%. The light reflectance of the 1 st laminate was measured by the method described in examples.

The in-plane retardation (Re) of the 1 st laminate is, for example, 10nm or less, preferably 9nm or less, more preferably 8nm or less, still more preferably 7nm or less, and particularly preferably 6nm or less. If the in-plane retardation (Re) is 10nm or less, a decrease in contrast in the liquid crystal display device can be suppressed. In this specification, the in-plane retardation (Re) can be measured by the method described in examples.

The absolute value of the thickness direction retardation (Rth) of the 1 st laminate is, for example, 30nm or less, preferably 25nm or less, and more preferably 20nm or less. If the absolute value of the retardation in the thickness direction (Rth) is 30nm or less, the decrease in contrast in the liquid crystal display device can be suppressed. In the present specification, the thickness direction retardation (Rth) can be measured by the method described in examples.

The microcrack width in the direction parallel to the tensile stress at 80% elongation of the 1 st laminate at 120 ℃ (hereinafter also referred to simply as "microcrack width of the 1 st laminate") is, for example, 2.0 μm or less, preferably 1.5 μm or less, and more preferably 1.0 μm or less. If the microcrack width of the 1 st laminate is 2.0 μm or less, there is an advantage that the change in appearance at the time of molding can be suppressed. The microcrack width of the 1 st laminate was measured by the method described in examples. In the present specification, "80% elongation at 120 ℃ may be described as" 80% elongation at 120 ℃. The "elongation" in this case indicates only the elongation.

The depth of the groove of the microcrack from the surface of the low refractive index layer side of the laminate (hereinafter, also simply referred to as "depth of the groove of the microcrack of the 1 st laminate") at the microcrack portion in the direction parallel to the tensile stress at 80% elongation at 120 ℃ is, for example, 1.0 μm or less, preferably 0.8 μm or less, and more preferably 0.5 μm or less. If the depth of the groove of the microcrack of the 1 st laminate is 1.0 μm or less, there is an advantage that the change in appearance at the time of molding can be suppressed. The depth of the groove of the microcrack of the 1 st laminate was measured by the method described in examples.

The width of the microcracks and the depth of the grooves of the microcracks in the 1 st laminate will be described with reference to fig. 1. Fig. 1 is a drawing showing TEM images after a tensile test is performed on a laminate according to embodiment 1 of the present invention. The laminate 4 of fig. 1 is composed of an acrylic resin film 1, a hard coat layer 2, and a low refractive index layer 3. In the laminate 4, if a tensile test is performed by applying a force in a direction perpendicular to the lamination direction at 120 ℃, microcracks 5 are generated on the surface of the laminate 4 according to the tensile stress. The crack width of the generated microcrack 5 in the direction parallel to the tensile stress is referred to as a microcrack width 6, and the crack width in the stacking direction is referred to as a groove depth 7 of the microcrack.

The 1 st laminate may have an undercoat layer on the surface (both surfaces) of the acrylic resin film opposite to the surface on which the hard coat layer is provided. As the composition of the primer layer, (a) ink used for printing in the post-processing step, (b) injection resin used for injection molding, (c) resin having good adhesion to metal used for metal vapor deposition, and the like can be used. For example, as the resin component, polyurethane-based resins, acrylic resins, polyester-based resins, polycarbonates, epoxy-based resins, melamine-based resins, copolymers of vinyl acetate and vinyl chloride, vinyl acetate resins, and the like can be used. These resin components may suitably contain functional groups such as acid groups, amino groups, epoxy groups, oxetane groups, vinyl groups, hydroxyl groups, mercapto groups, isocyano groups, silyl groups, salts, and the like. Alternatively, the resin component may be used in combination with a compound having these functional groups. By providing such a primer layer, adhesion between the injection resin, ink, or the like and the acrylic resin of the 1 st laminate can be enhanced.

The thickness of the undercoat layer is preferably 0.5 to 10. Mu.m, more preferably 0.5 to 5. Mu.m, most preferably 0.5 to 3. Mu.m. If the thickness of the primer layer is 0.5 μm or more, the adhesion between the injection resin, the ink, and the like and the acrylic resin of the 1 st laminate can be ensured, and if it is 10 μm or less, the productivity is better.

[ 1-4. Shaped articles ]

Embodiment 1 of the present invention provides a molded article comprising a 1 st laminate (hereinafter referred to as "1 st molded article"). In embodiment 1 of the present invention, the 1 st molded article is obtained by laminating the 1 st laminate on at least a part of the surface of a molded article having a non-planar shape.

Specific examples of the use of the 1 st molded article include automotive interior applications such as dashboards, front panels for vehicle-mounted displays, control boxes, covers, door lock shutters, steering wheels, power window switch bases, center combination meters, and control panels; (a) Weather strips, bumpers, bumper bumpers, side fenders, body panels, spoilers, front grilles, suspension supports, hubcaps, body center pillars, rear view mirrors, center trim, side trim, door trim, window trim, and the like, and (b) automotive exterior applications for windows, roof hoods, tail hoods, windshield components, and the like; a case, a display window, a button, etc. of a portable electronic device such as a smart phone, a mobile phone, and a tablet personal computer; television, DVD player, audio equipment, electric cooker, washing machine, refrigerator, air conditioner, humidifier, dehumidifier, electric fan, other household electronic and electric equipment; (a) A housing for furniture articles and the like, a front panel, a key, a logo, a surface decorative material and the like, and (b) an exterior decorative material for furniture; use of building interior materials such as wall surfaces, ceilings, floors, bathtubs, toilet seats and the like; external finishing materials for construction such as external walls of wall panels, enclosing walls, roofs, door leaves, gable boards, etc.; use of surface decorative materials for furniture such as window frames, doors, armrests, doorsills, and lintels; optical component applications such as various displays, lenses, mirrors, goggles, and window glasses; and interior and exterior applications of various vehicles other than automobiles such as electric cars, airplanes, and ships.

When the 1 st laminate is used, a molded article having (a) a complicated three-dimensional shape and (b) excellent surface hardness, scratch resistance, chemical resistance, stain resistance, reflection characteristics, antiglare properties, and the like can be easily produced. Therefore, the 1 st molded article is preferably used for applications such as a front panel of a vehicle-mounted display having a planar shape, a curved shape, and/or a three-dimensional shape, among the above applications. Therefore, embodiment 1 of the present invention provides an in-vehicle display front panel including the 1 st molded body.

[ 2. Embodiment 2 ]

Embodiment 2 of the present invention relates to a laminate comprising an acrylic resin film as a base material and a method for producing the laminate.

As described above, as a method for further imparting functionality to a decorative and protective film including an acrylic resin film, a method of forming a functional layer on a film substrate by a method such as coating has been performed.

For example, patent document 4 describes an antiglare antireflection film for insert molding, which has an antiglare hard coat layer on a thermoplastic transparent base film and a low refractive index layer containing a specific component at a specific concentration as an outermost layer on the antiglare hard coat layer side on the thermoplastic transparent base film.

Patent document 5 describes a laminated film or the like comprising a support, an easily adhesive layer provided on one surface of the support, and a transparent layer made of a light-transmitting resin provided on the other surface of the support, wherein the transparent layer contains light-transmitting particles having a volume average particle diameter r of 0.4 μm or less and r of 3.0 μm or less, and the sum S of the light-transmitting particles is 30mg/m ² ≤S≤500mg/m ² And the average film thickness t of the transparent layer satisfies r/4.ltoreq.t < r.

However, the techniques described in patent documents 4 and 5 cannot be said to have sufficient performance from the viewpoint of the formability of the laminate and the functionality of the laminate such as the surface hardness of the laminate surface and antiglare properties, and there is room for further improvement.

Accordingly, an object of one embodiment (embodiment 2) of the present invention is to provide a laminate containing an acrylic resin film excellent in moldability, surface hardness, and antiglare properties, and a method for producing the laminate.

As a result of intensive studies to solve the above problems, the present inventors have found for the first time that a laminate excellent in moldability, surface hardness and antiglare properties can be obtained by using a hard coat layer containing specific particles and having specific physical properties in a laminate composed of an acrylic resin film, a hard coat layer and the like, and completed an embodiment (embodiment 2) of the present invention.

Accordingly, one embodiment of embodiment 2 of the present invention is a method for producing a laminate, comprising (A2) a step of irradiating a resin layer containing a urethane acrylate resin and particles applied to at least one surface of an acrylic resin film with an active energy ray, curing the resin layer containing the urethane acrylate resin and the particles to form a hard coat layer, wherein the tensile elongation at break of the acrylic resin film at 120 ℃ is 170% or more, the content of the particles is 2.0 to 5.0% by weight relative to the hard coat layer after curing, the average dispersion particle diameter of the particles is r (μm), the film thickness of the hard coat layer is d (μm), d.ltoreq.r is satisfied, the pencil hardness of the laminate is H or more, the haze is 3% or more, and the crack growth rate at 120 ℃ is 170% or more, and the crack growth rate at 120 ℃ of a laminate film formed by laminating a resin layer containing no particles on the acrylic resin film is 80% or more.

Further, in embodiment 2 of the present invention, a laminate is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the tensile elongation at break of the acrylic resin film is 170% or more at 120 ℃, the hard coat layer comprises a urethane acrylate resin and particles, the average dispersion particle diameter of the particles is r (μm), d.ltoreq.r is satisfied when the film thickness of the hard coat layer is d (μm), the pencil hardness of the laminate is H or more, the haze is 3% or more, and the crack growth rate of the laminate film obtained by laminating a resin layer containing no particles on the acrylic resin film is 80% or more at 120 ℃.

According to one embodiment of embodiment 2 of the present invention, a laminate including an acrylic resin film excellent in moldability, surface hardness, and antiglare properties and a method for producing the same can be provided.

Embodiment 2 will be described below, and the description of embodiment 1 will be appropriately applied, except for the details described below.

[ 2-1. Summary of embodiment 2 of the invention ]

The method for producing a laminate according to embodiment 2 of the present invention (hereinafter referred to as "the method for producing a laminate of embodiment 2") is characterized by comprising (A2) a step of irradiating a resin layer containing a urethane acrylate resin and particles applied to at least one surface of an acrylic resin film with an active energy ray, curing the resin layer containing the urethane acrylate resin and the particles to form a hard coat layer, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, the content of the particles is 2.0 to 5.0% by weight relative to the hard coat layer after curing, the average dispersion particle diameter of the particles is r (μm), the film thickness of the hard coat layer is d (μm), d.ltoreq.r is satisfied, the pencil hardness of the laminate is H or more, the haze is 3% or more, the crack growth rate at 120 ℃ is 170% or more, and the crack growth rate of the film obtained by laminating a resin layer containing no particles on the acrylic resin film is 80% or more at 120 ℃. The laminate of embodiment 2 of the present invention (hereinafter referred to as "laminate 2") is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, the hard coat layer comprises a urethane acrylate resin and particles, the average dispersion particle diameter of the particles is r (μm), the film thickness of the hard coat layer is d (μm), d.ltoreq.r is satisfied, the pencil hardness of the laminate is H or more, the haze is 3% or more, and the crack growth rate of the laminate film obtained by laminating a resin layer containing no particles on the acrylic resin film is 80% or more at 120 ℃.

In this specification, both the laminate obtained by the method for producing a laminate of embodiment 2 and the laminate of embodiment 2 are sometimes referred to as "2 nd laminate".

The laminate obtained by the above-described method for producing a 2 nd laminate has a surface hardness, and is also said to be excellent in surface hardness. The laminate obtained by the method for producing a 2 nd laminate has antiglare properties, and is also said to be excellent in antiglare properties. The method for evaluating the antiglare property of the laminate in the present specification is described in detail in examples below. Further, the laminate obtained by the method for producing a 2 nd laminate is excellent in moldability.

As described above, as films for in-vehicle displays in recent years, which have been increasingly enlarged and curved, antiglare films and antireflection films having higher moldability than ever have been demanded.

However, patent document 4 discloses only a large and planar film, and does not disclose a technique for solving the problem of embodiment 2, namely "moldability". Patent document 5 discloses a component having a larger dispersion particle diameter of the antiglare particles than the film thickness of the antiglare particle-containing layer, but does not disclose a component having a large crack growth rate of the resin layer, and does not disclose a constitution such as "moldability" and "stretch whitening". That is, in the prior art, a laminate satisfying requirements such as moldability, surface hardness, and antiglare properties has not been found, and there is room for further improvement.

Accordingly, the present inventors have studied mainly on improvement of moldability, surface hardness, and antiglare properties of a laminate, and have found for the first time that a laminate excellent in moldability, surface hardness, and antiglare properties can be obtained by (i) bringing a hard coat layer, a refractive index adjusting layer (e.g., a low refractive index layer), and the like in the laminate into specific physical properties and states, and (ii) controlling the dispersion state of particles in the hard coat layer, so that peeling, cracking, and the like of a functional layer do not occur even when the laminate is laminated on a three-dimensional surface of a large-sized molded article. The inventors of the present invention have found that the laminate obtained by the above method can solve the problem of whitening of the stretched portion in addition to moldability.

Conventionally, in a laminate for molding having a functional layer having surface hardness, antiglare properties, and antireflection properties, there are problems such as peeling of a coating layer at a stretched portion, cracking of a film, and the like accompanying molding, and whitening of a stretched portion. (1) In the hard coat layer containing antiglare particles in the laminate, the hard coat layer may be significantly whitened when the laminate is stretched in accordance with molding. (2) The low refractive index layer located on the outermost surface of the laminate may whiten during stretching.

The present inventors have succeeded in obtaining the following findings in the course of research for these problems.

It was found that (1) the resin used for the hard coat layer in the laminate was a resin having a high crack growth rate when stretched, and the film thickness of the hard coat layer, the amount of the particles and the dispersion state were controlled. This suppresses micro-cracking of the hard coat layer surface around the particles dispersed in the hard coat layer during stretching of the laminate, and prevents significant whitening of the hard coat layer during stretching. More specifically, it was found that (a) the resin used for the hard coat layer in the laminate was a resin having a high crack growth rate when stretched, and (b) (b-1) the size of the region (dispersion domain) in which particles (antiglare particles) contained in the hard coat layer are distributed in a state where single particles or a plurality of particles are aggregated was the same as or designed to be larger than the film thickness of the hard coat layer, and (b-2) a dispersion form was adopted in which at least a part of the dispersion domain of particles (antiglare particles) was previously exposed at the surface portion of the hard coat layer. In this way, during stretching of the laminate, the occurrence of cracks, and the like on the hard coat layer surface in the peripheral portion of the dispersion domain of particles (antiglare particles) can be suppressed, and significant whitening during stretching can be prevented.

It was found that (2) the occurrence of micro microcracks on the surface of the low refractive index layer located on the outermost surface of the laminate, which are not recognized as cracks of a size that can be recognized when the laminate is seen, is one cause of whitening during stretching. The whitening of the low refractive index layer can be improved by making the resin used for the hard coat layer in the laminate a resin having a high crack growth rate when stretched and appropriately adjusting the conditions at the time of producing the hard coat layer. Surprisingly, although the cause of whitening is microcracks in the low refractive index layer, the hard coating layer located below the low refractive index layer can improve not only the formability of the laminate but also whitening of the stretched portion due to microcracks in the low refractive index layer.

As described above, a laminate having excellent moldability, surface hardness, and antiglare properties, which is composed of an acrylic resin film and a hard coat layer, or an acrylic resin film, a hard coat layer, and a low refractive index layer, has not been reported so far, and the method for producing the 2 nd laminate is an extremely excellent technique. Hereinafter, a method for producing the present laminate will be described in detail.

In embodiment 2, the term "laminate" refers to a product (laminate) including a hard coat layer containing particles, and a product (laminate) not including a hard coat layer or a product (laminate) not including particles is referred to as a "laminate film". More specifically, in embodiment 2, for example, the "laminate" means (1) a laminate composed of an acrylic resin film and a particle-containing hard coat layer, or (2) a laminate composed of an acrylic resin film, a particle-containing hard coat layer, and a low refractive index layer, and the "laminate" means (3) a laminate composed of an acrylic resin film and a particle-free hard coat layer, or (4) a laminate composed of an acrylic resin film and a low refractive index layer.

The curable resin composition constituting the hard coat layer in the 2 nd laminate is required to have a high crack growth rate while improving the surface hardness of the hard coat layer, and is not required to undergo fracture or significant whitening due to stretching when the laminate is subjected to secondary molding into the shape of the molded article. However, as described above, conventionally, the surface hardness and scratch resistance are properties opposite to the deformability and stretchability, and it is difficult to achieve both properties.

As a method for imparting high stretchability in the secondary molding to such a curable resin for a hard coat layer while maintaining the hardness, for example, the methods (1) to (3) described above are given. The methods (1) to (3) may be used alone or in combination with each other as appropriate, for example, for the hard coat layer in the 2 nd laminate.

[ 2-2. Method for producing 2 nd laminate ]

The method for producing the 2 nd laminate includes the following step (A2).

Step (A2): and a step of forming a hard coat layer by irradiating a resin layer containing urethane acrylate resin and particles applied to at least one surface of the acrylic resin film with an active energy ray and curing the resin layer containing urethane acrylate resin and particles.

In embodiment 2 of the present invention, the method for producing a2 nd laminate preferably further includes the following step (B2).

Step (B2): and (b) a step of applying a coating liquid containing 40% or more of an acrylic resin containing hollow silica fine particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step (A2), drying the coating liquid, and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin, thereby forming a low refractive index layer.

In the step (A2), the resin layer containing urethane acrylate resin and particles applied to at least one surface of the acrylic resin film is irradiated with an active energy ray, and the resin layer containing urethane acrylate resin and particles is cured to form a hard coat layer. In the step (B2), a resin layer containing an acrylic resin is applied in a solution state to the cured hard coat layer containing a urethane acrylic resin formed in the step (A2), and the resin layer is irradiated with an active energy ray to cure the resin layer, thereby forming a low refractive index layer.

The method for producing A2 nd laminate further includes the following constitution in addition to the above step (A2) and the optional step (B2).

The acrylic resin film has a tensile elongation at break at 120 ℃ of 170% or more.

The content of the particles is 2.0 to 5.0 wt% relative to the hard coat layer after curing, and d.ltoreq.r is satisfied when the average dispersion particle diameter of the particles is r (μm) and the film thickness of the hard coat layer is d (μm).

The laminate has a pencil hardness of H or more, a haze of 3% or more, and a crack growth rate of 170% or more at 120 ℃.

The laminated film obtained by laminating the resin layer containing no particles on the acrylic resin film has a crack growth rate of 80% or more at 120 ℃.

In order to provide the laminate obtained by the method for producing the laminate of item 2 with high surface hardness, high crack growth rate at 120 ℃ and less whitening of the stretched portion, it is preferable that the hard coat layer and the low refractive index layer adhere well. In general, the low refractive index layer contains a hard filler such as hollow silica, and the crack growth rate is much lower than that of the hard coating layer. It is possible that cracks and microcracks are generated at a lower elongation than the crack growth rate of the hard coat layer alone. In this case, if the adhesion between the hard coat layer and the low refractive index layer is good, the opening width of the micro-cracks generated in the low refractive index layer becomes a fine size of, for example, 1 μm or less, and whitening due to stretching is less likely to occur.

In order to improve the adhesion between the hard coat layer and the low refractive index layer, for example, the following (a) and/or (b) are preferable: (a) When the resin layer to be the low refractive index layer is applied in the solution state in the step (B2), the applied resin layer (low refractive index layer) is impregnated into the hard coat layer to a certain extent within a range where the interface between the final 2 layers does not become unclear and the antireflection property is not impaired; (b) The acrylate group remaining after curing of the hard coat layer is reacted and cured together with the resin layer (low refractive index layer) when the resin layer (low refractive index layer) after coating is cured by irradiation of active energy rays, and a chemical bond is formed at the interface between the finally obtained hard coat layer and the low refractive index layer.

Therefore, for example, in the step (A2), it is preferable that the resin layer containing urethane acrylate resin forming the hard coat layer is not completely cured, the crosslinking density is slightly low, and unreacted acrylate groups remain partially. Further, in the step (B2), in order to impregnate the resin layer containing the acrylic resin to the hard coat layer surface to a certain extent in the step of coating the resin layer containing the acrylic resin forming the low refractive index layer in a solution state and optionally drying, it is preferable to (a) appropriately adjust the coating conditions and the drying conditions of the solvent and/or (B) use a certain amount of a solvent having a high boiling point which dries slowly as the solvent used in the solution, or the like.

In the method for producing the 2 nd laminate, the elongation at break at 120℃of the acrylic resin film in the laminate is 170% or more, preferably 180% or more, more preferably 190% or more. If the tensile elongation at break at 120℃of the acrylic resin film is 170% or more, there is an advantage that the molded shape-following property is excellent. In the method for producing the 2 nd laminate, the upper limit of the tensile elongation at break is not particularly limited, but is, for example, 350% or less, preferably 300% or less, from the viewpoint of improving the tensile strength.

In the method for producing the 2 nd laminate, the pencil hardness of the laminate is H or more, preferably 2H or more, and more preferably 3H or more. If the pencil hardness of the laminate is H or more, there is an advantage that scratch is not easy.

In the method for producing the 2 nd laminate, the haze of the laminate is 3.0% or more, preferably 3.5% or more, more preferably 4.0% or more, and still more preferably 4.5% or more. If the haze of the laminate is 3.0% or more, there is an advantage that the antiglare property is excellent. The haze of the laminate was measured by the method described in examples.

In the method for producing the 2 nd laminate, the crack growth rate of the laminate at 120 ℃ is 80% or more, preferably 90% or more, and more preferably 100% or more. If the crack growth rate of the laminate at 120 ℃ is 80% or more, there is an advantage that shape following property at the time of molding is excellent. In the method for producing the 2 nd laminate, the upper limit of the crack growth rate is not particularly limited, but is, for example, 350% or less, preferably 300% or less, from the viewpoint of improving the surface hardness and the abrasion resistance. In the present specification, the term "crack growth rate of the laminate at 120" means the growth rate of cracks in the coating layer when the laminate is subjected to a tensile test in a constant temperature bath at 120 ℃. In the present specification, the crack growth rate of the laminate at 120 ℃ can be measured by the method described in examples.

In the method for producing the 2 nd laminate, a laminate film in which the resin layer containing no particles is laminated on the acrylic resin film (hereinafter, also referred to as "particle-free laminate film") has a crack growth rate of 80% or more, preferably 90% or more, more preferably 100% or more at 120 ℃. If the crack growth rate of the particle-free laminated film at 120 ℃ is 80% or more, there is an advantage that shape following property is excellent at the time of molding the laminated body and whitening of a portion stretched by the molding is suppressed. The upper limit of the crack growth rate of the particle-free laminated film at 120 ℃ is not particularly limited, but is, for example, 200% or less, preferably 180% or less, from the viewpoint of improving the surface hardness and/or abrasion resistance. The crack growth rate of the laminated film containing no particles at 120℃can be measured by the method described in the examples.

(acrylic resin film)

Since each mode of the acrylic resin film in embodiment 2 is the same as that described in the (acrylic resin film) item of embodiment 1, this description is incorporated by reference, and the description thereof is omitted here.

(hard coat)

The hard coat layer in the method for producing a 2 nd laminate is a functional layer laminated on at least one side of the acrylic resin film, and includes urethane acrylate resin and particles. The hard coat layer may be laminated on one side or both sides of the acrylic resin film.

In the hard coat layer of the method for producing a laminate of item 2, the content of the particles is 2.0 to 5.0 wt% relative to the hard coat layer after curing, and d.ltoreq.r is satisfied when the average dispersion particle diameter of the particles is r (μm) and the film thickness of the hard coat layer is d (μm).

< polyurethane acrylate resin >)

Since the mode of urethane acrylate resin is the same as that described in the item < urethane acrylate resin > of embodiment 1, this description is incorporated herein by reference, and the description thereof is omitted.

< particle >)

In the method for producing the 2 nd laminate, the hard coat layer contains particles, whereby a laminate containing an acrylic resin film excellent in antiglare property can be obtained.

The material of the particles to be blended in the hard coat layer is not particularly limited as long as the effect of the present invention is exhibited, and examples thereof include (a) inorganic particles such as silica, alumina, glass beads or glass flakes, mica, clay, titanium oxide, zinc oxide, zirconium oxide, metal particles and/or (b) crosslinked organic resin particles containing an alkyl (meth) acrylate unit, an aromatic vinyl unit, a siloxane unit and the like as a main component, and (c) core-shell type multilayer structure resin particles and the like. From the viewpoint of easy availability and easy design of antiglare property depending on the application, the particles are preferably inorganic oxide particles (e.g., silica, alumina, titania, zinc oxide, zirconia, etc.) and/or crosslinked organic resin particles, more preferably 1 or more selected from silica, alumina, zirconia, crosslinked silicone resin, crosslinked acrylic resin, and crosslinked aromatic vinyl resin. In addition, silica particles, alumina particles and crosslinked organic resin particles are particularly preferable from the viewpoint of balance of physical properties such as antiglare property, dispersibility and surface hardness. From the viewpoint of controlling dispersibility, the particles may be subjected to a surface treatment, graft polymerization treatment, or the like by a known method such as plasma treatment or corona treatment using a silane coupling agent, a reactive monomer, or the like which may have a reactive substituent. From the viewpoint of improving the interfacial adhesion between the particles and the hard coat layer and improving the dispersibility of the particles, cracks and/or whitening during stretching, it is preferable that at least a part of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin. Examples of the reactive functional group reactive with the urethane acrylate resin include (a) a radical reactive functional group such as a vinyl group or a (meth) acryl group, (b) a plasma functional group such as an epoxy group, an oxetanyl group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyano group, a hydroxyl group, an amino group, and (c) a moisture curable functional group such as a silyl group or an alkoxysilyl group.

The particles contained in the hard coat layer satisfy d.ltoreq.r when the average dispersion particle diameter of the particles is r (μm) and the film thickness of the hard coat layer is d (μm). That is, the particles contained in the hard coat layer have an average dispersed particle diameter that is the same as the film thickness of the hard coat layer or larger than the film thickness of the hard coat layer. When the average dispersion particle diameter of the particles contained in the hard coat layer is smaller than the film thickness of the hard coat layer, local cracks and/or flaws of the hard coat layer may occur in the thin portion of the hard coat layer in the peripheral portion of the dispersion particles during stretching, and the dispersion particles are exposed on the hard coat layer surface. This increases the state change (color difference, haze, smoothness, etc.) of the hard coat layer surface before and after stretching, which is considered to be observed as whitening of the stretched portion. On the other hand, as described above, when the average particle diameter of the particles contained in the hard coat layer is equal to or larger than the film thickness of the hard coat layer, at least a part of the particles are exposed on the hard coat layer surface from before stretching, and therefore, the state change (color difference, haze, gloss, smoothness, etc.) of the hard coat layer surface before and after stretching tends to be small, and there is an advantage that whitening after stretching is reduced.

The average dispersion particle diameter of the particles (e.g., silica particles) is not particularly limited as long as the effect of the present invention is exhibited, and may be, for example, 0.1 μm to 50.0 μm, 0.2 μm to 25.0 μm, 0.5 μm to 10 μm, 1.0 μm to 4.0 μm, 1.2 μm to 3.8 μm, 1.4 μm to 3.6 μm, and the like. The average dispersion particle diameter of the particles (for example, silica particles) can be measured by the method described in examples.

In the method for producing the laminate, the content of the particles in the hard coat layer is not particularly limited as long as the effect of one embodiment of the present invention is exhibited, and may be, for example, 0.1 to 30.0 wt%, 0.5 to 20.0 wt%, 1.0 to 15.0 wt%, 2.0 to 5.0 wt%, 2.2 to 4.8 wt%, 2.4 to 4.6 wt%, or the like.

In the method for producing the 2 nd laminate, the film thickness of the hard coat layer is not particularly limited as long as the effect of the present invention is exhibited, and may be, for example, 0.2 to 3.0 μm, 0.3 to 2.9 μm, 0.4 to 2.8 μm, or the like. The film thickness of the hard coat layer can be measured by the method described in the examples.

< others >

In the method for producing the 2 nd laminate, the hard coat layer of the laminate may contain other components in addition to the urethane acrylate resin. Examples of the component other than the urethane acrylate resin include monomers, oligomers, resins, or mixtures thereof having a radical-reactive functional group such as monofunctional or polyfunctional (meth) acrylate, epoxy acrylate monomer, polyester acrylate, silicon acrylate, polycarbonate acrylate, and polyacrylic acrylate. Further, the urethane acrylate resin may be used in combination with a composition comprising, for example, (a) a hydrolysis condensate of a di-to tetrafunctional silane compound, and/or (b) a monomer, oligomer, resin or a mixture thereof having a cationically and/or anionically curable functional group such as an epoxy group and an oxetane group. The urethane acrylate resin may be used alone as a component used for forming the hard coat layer, or 1 or 2 or more of the other components may be mixed and added to the urethane acrylate resin.

The respective modes of the composition comprising the (meth) acrylate, the epoxy acrylate monomer, the hydroxyl group-containing (meth) acrylate, the polyisocyanate, the polyol, the organotin-based urethane catalyst and the hydrolysis condensate of the silane compound are the same as those described in the item < other > of embodiment 1, and therefore, the description thereof is omitted herein by reference.

Since the modes of the method for curing the resin composition (for example, the photopolymerization initiator, the photo cation generator, and the photo anion generator) when forming the hard coat layer are also the same as those described in the item < other > of embodiment 1, the description is incorporated herein by reference.

When a hard coat layer is formed by curing a resin layer (coating film) composed of a curable composition, various leveling agents known in the art may be blended into the curable composition for the purpose of improving coating properties, scratch resistance after curing, stain resistance, and the like. Since the leveling agent is the same as that described in the item < other > of embodiment 1, this description is incorporated herein by reference, and the description thereof is omitted.

When the curable composition is applied to form a hard coat layer, various additives such as ultraviolet absorbers, light stabilizers, antifoaming agents, antioxidants, light diffusers, matting agents, antifouling agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic fine particles, and antistatic agents may be added to the curable composition as needed. The additive is not limited to these.

In order to impart an appropriate coatability to the curable composition, an organic solvent is generally blended. Since the organic solvent is the same as that described in the item < other > of embodiment 1, the description is incorporated herein by reference, and the description thereof is omitted.

The method of applying the curable composition to the main surface of the acrylic resin film as the base film is the same as that described in the item < other > in embodiment 1, and therefore the description thereof is omitted here for the sake of brevity.

The curable composition for forming a hard coat layer described above is applied to the surface of the acrylic resin film as a base film, and then the obtained resin layer is cured by irradiation with light such as ultraviolet rays, thereby forming a hard coat layer. After the curable composition for forming a hard coat layer is applied to the surface of the acrylic resin film, the organic solvent may be optionally removed from the resin layer (coating film) by drying.

Since the drying temperature of the resin layer (coating film) when the organic solvent is removed by drying is the same as that described in the item < other > of embodiment 1, the description is incorporated herein by reference.

The wavelength of ultraviolet light to be irradiated when curing the resin layer (coating film), the cumulative amount of ultraviolet light (UV) and the irradiation means for exposing ultraviolet light are the same as those described in the item < other > of embodiment 1, and therefore, this description is incorporated herein by reference.

As the composition for forming a hard coat layer, commercially available ones can be used. Since the commercial product is the same as that described in the item < other > of embodiment 1, the description is incorporated herein by reference, and the description thereof is omitted.

In embodiment 2 of the present invention, inorganic particles and/or metal particles may be further added. Examples of such inorganic particles and metal particles include, but are not particularly limited to, silica, alumina, titanium oxide, zinc oxide, zirconium oxide, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, metallic copper, and the like. These particles may be added for the purpose of improving the abrasion resistance of the hard coat layer or for the purpose of further imparting antiglare properties. In addition, inorganic particles and/or metal particles having a function of improving abrasion resistance may be used in combination with inorganic particles and/or metal particles having an antiglare function. These particles may be used without surface treatment, or may be subjected to surface treatment by a known method in advance to control the dispersion state, so that the affinity with the hard coat layer can be appropriately controlled.

(Low refractive index layer)

In the method for producing a2 nd laminate, it is preferable that the hard coat layer further comprises a low refractive index layer containing 40% or more of an acrylic resin containing hollow silica fine particles having a particle diameter of less than 100 nm. The low refractive index layer constitutes an anti-reflection layer. Since the modes of the low refractive index layer are the same as those described in the item (low refractive index layer) of embodiment 1, this description is incorporated herein by reference, and the description thereof is omitted.

< other functional layers >)

The 2 nd laminate may have other functional layers than those described above. Since the other functional layers are the same as those described in the item < other functional layers > of embodiment 1, the description is incorporated herein by reference, and the description thereof is omitted.

(others)

In embodiment 2, the manner of accumulating the Ultraviolet (UV) light amount in step (A2) and the manner of cooling roller temperature in step (A2) are the same as those in step (A1) and the manner of accumulating the Ultraviolet (UV) light amount in step (A1) and the manner of cooling roller temperature in step (A1) described in (other) of embodiment 1, and therefore, this description is omitted here. In embodiment 2, conditions other than those described above in step (A2) and the like can be applied to the conditions described in the (hard coat) item described in embodiment 2.

In the step (B2) of embodiment 2, an acrylic resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100nm is applied to the hard coat layer obtained in the step (A2), and the obtained resin layer containing the acrylic resin is irradiated with an active energy ray to cure the resin layer containing the acrylic resin, thereby forming a low refractive index layer.

In embodiment 2, the manner of accumulating the Ultraviolet (UV) light amount in step (a) and the cooling roller temperature in step (B2) is the same as the manner of accumulating the Ultraviolet (UV) light amount in step (a) and the cooling roller temperature in step (B1) described in (other) item (1), and therefore, this description is omitted here. In embodiment 2, conditions other than those described above in step (B2) and the like can be applied to the conditions described in the (hard coat) item described in embodiment 2.

Further, embodiment 2 of the present invention provides a method for producing a laminate, comprising (B2') a step of adding a solvent to the acrylic resin as a material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm, wherein the solvent contains at least 1 or more solvents, and the highest boiling point solvent is a boiling point of 115 ℃ to 180 ℃. In the step (B2) and the step (B2'), the "acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm" is said to be "a composition for forming a low refractive index layer".

In embodiment 2, the boiling point of the solvent having the highest boiling point in step (a) (B) 2 '), the solvent used in step (B2 '), and the method of adding a solvent to an acrylic resin in step (B2 ') to prepare an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm are the same as those of the method of adding a solvent to an acrylic resin in step (B2 '), and the method of adding a solvent to an acrylic resin in step (B1 ') to prepare an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm in step (a) (other) described in embodiment 1, and therefore description thereof will be omitted.

[ 3. Laminate ]

The 2 nd laminate comprises an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. More specifically, the 2 nd laminate is a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, the hard coat layer comprises a urethane acrylate resin and particles, the average dispersion particle diameter of the particles is r (μm), the film thickness of the hard coat layer is d (μm) satisfies d.ltoreq.r, the pencil hardness of the laminate is H or more, the haze is 3% or more, and the crack growth rate of the laminate film formed by laminating a resin layer containing no particles on the acrylic resin film is 80% or more at 120 ℃. In a preferred embodiment of embodiment 2 of the present invention, the 2 nd laminate further includes a low refractive index layer on the hard coat layer.

(laminate)

The 2 nd laminate is composed of at least a specific acrylic resin film and a specific hard coat layer as described above. In a preferred embodiment of embodiment 2 of the present invention, the 2 nd laminate is composed of a specific acrylic resin film, a specific hard coat layer, and a specific low refractive index layer.

In embodiment 2 of the present invention, the 2 nd laminate is composed of the acrylic resin film described in the above (acrylic resin film) and the hard coat layer described in the above (hard coat layer). In a preferred embodiment of embodiment 2 of the present invention, the 2 nd laminate is composed of the acrylic resin film described in the above (acrylic resin film), the hard coat layer described in the above (hard coat layer), and the low refractive index layer described in the above (low refractive index layer). The 2 nd laminate is preferably obtained by the production method described in [ 2-2. The production method of the 2 nd laminate ].

The matters not described in the items such as "pencil hardness", "tensile elongation at break at 120", "crack growth at 120" and "haze" of the 2 nd laminate are applicable to the matters described in the above [ 2-2. Method for producing the 2 nd laminate ].

When the 2 nd laminate is composed of an acrylic resin film and a hard coat layer, the delta haze of the 2 nd laminate after 80% stretching at 120 ℃ is, for example, 8.0% or less, preferably 7.5% or less, and more preferably 7.0% or less. If the delta haze of the 2 nd laminate after 80% stretching at 120 ℃ is 8.0% or less, there is an advantage of suppressing whitening at the time of molding. The delta haze of the 2 nd laminate after 80% stretching at 120℃can be measured by the method described in examples.

When the 2 nd laminate is composed of an acrylic resin film, a hard coat layer, and a low refractive index layer, the delta haze of the 2 nd laminate after 80% stretching at 120 ℃ is, for example, 10% or less, preferably 9.5% or less, more preferably 9.0% or less, and even more preferably 8.5% or less. If the delta haze of the 2 nd laminate after 80% stretching at 120 ℃ is 10% or less, there is an advantage of suppressing whitening at the time of molding. The delta haze of the 2 nd laminate after 80% stretching at 120℃can be measured by the method described in examples.

The light reflectance of the 2 nd laminate is, for example, 3.0% or less, preferably 2.8% or less, and more preferably 2.6% or less. If the light reflectance of the 2 nd laminate is 3.0% or less, there is an advantage that the antireflection performance is excellent and the visibility at the time of lamination on the display surface is excellent. The lower the light reflectance of the 2 nd laminate, the better, may be 0.0%. The light reflectance of the 2 nd laminate was measured by the method described in examples.

The respective modes of the absolute values of the (a) delta haze after 20% stretching of the laminated film obtained by laminating the low refractive index layer on the acrylic resin film, (b) in-plane retardation (Re), and (c) thickness direction retardation (Rth) in the 2 nd laminated body are the same as those of the (a) delta haze after 20% stretching of the laminated film obtained by laminating the low refractive index layer on the acrylic resin film, (b) in-plane retardation (Re), and (c) thickness direction retardation (Rth) in the 1 st laminated body described in the (laminated body) of embodiment 1, and therefore, the description thereof is omitted here.

The 2 nd laminate may have an undercoat layer on the side (both sides) of the acrylic resin film opposite to the side on which the hard coat layer is provided. The manner of the undercoat layer in the 2 nd laminate is the same as that of the undercoat layer in the 1 st laminate described in the (laminate) item 1, and therefore, this description is incorporated by reference, and the description thereof is omitted here.

[ 2-3. Shaped articles ]

Embodiment 2 of the present invention provides a molded article comprising a 2 nd laminate (hereinafter referred to as "2 nd molded article"). In embodiment 2 of the present invention, the 2 nd molded article is obtained by laminating the 2 nd laminate on at least a part of the surface of a molded article having a non-planar shape.

The specific example of the use of the 2 nd molded article is the same as the use of the 1 st molded article described in [ 1-4. Molded article ] of embodiment 1, and therefore, this description is incorporated herein by reference.

When the 2 nd laminate is used, a molded article having (a) a complicated three-dimensional shape and (b) excellent surface hardness, scratch resistance, chemical resistance, stain resistance, reflection characteristics, antiglare properties, and the like can be easily produced. Therefore, the 2 nd molded article can be preferably used for the applications described in [ 1-4. Molded article ] of embodiment 1, for example, applications such as a front panel of a vehicle-mounted display having a planar shape, a curved shape and/or a three-dimensional shape. Therefore, embodiment 2 of the present invention provides a vehicle-mounted display front panel including the molded body of embodiment 2.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope indicated by the scope of patent claims, and embodiments in which the technical means disclosed in the different embodiments are appropriately combined are also included in the technical scope of the present invention.

One embodiment of the present invention may be configured as follows.

A method for producing a laminate, wherein X1 is greater than one, comprises:

a step (A1) of irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer, and

a step (B1) of applying an acrylic resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step (A1), and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin to form a low refractive index layer;

the acrylic resin film has a tensile elongation at break at 120 ℃ of 170% or more,

the hard coat layer described above contains a urethane acrylate resin,

the laminate has a crack growth rate of 80% or more at 120 ℃.

< X2 > the method for producing a laminate according to < X1 >, wherein the cumulative amount of light irradiated with active energy rays in the step (A1) is 150 to 500mJ/cm ² 。

A method for producing a laminate according to the above-mentioned item < X3 > and < X1 > or < X2 >, wherein the method comprises (B1') a step of adding a solvent to the acrylic resin as the material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica particles having a particle diameter of less than 100nm,

The solvent contains at least 1 or more solvents, and the highest boiling point solvent among the solvents has a boiling point of 115 to 180 ℃.

The method for producing a laminate according to any one of < X1 > - < X3 >, wherein the laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a delta haze of 30% or less after 20% stretching at 120 ℃.

A method for producing a laminate, which comprises (A1) a step of irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer,

the acrylic resin film has a tensile elongation at break of 170% or more at 120 ℃, and the hard coat layer comprises a urethane acrylate resin,

the laminate has a crack growth rate of 80% or more at 120 ℃.

X6 > a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer described above contains a urethane acrylate resin,

The laminate has a pencil hardness of H or more and a crack growth rate of 80% or more at 120 ℃.

The laminate according to the above-mentioned item < X7 > and < X6 >, wherein the hard coat layer further comprises a low refractive index layer,

the low refractive index layer contains an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100 nm.

The laminate according to < X8 > and < X7 > has a light reflectance of 2.0% or less.

The laminate according to < X9 > or < X7 > or < X8 > wherein the in-plane retardation (Re) of the laminate is 10nm or less and the absolute value of the retardation in the thickness direction (Rth) is 30nm or less.

The laminate according to any one of < X10 > to < X6 > - < X9 >, wherein the delta haze at 120 ℃ at 80% is 3.0% or less.

The laminate according to any one of < X11 > < X7 > < X10 >, wherein the low refractive index layer has a microcrack width of 2.0 μm or less in a direction parallel to the tensile stress when the elongation at 120 ℃ is 80%.

The laminate according to any one of < X12 > to < X7 > - < X11 >, wherein the depth of the groove of the microcrack from the surface of the laminate on the low refractive index layer side is 1.0 μm or less at the microcrack portion of the low refractive index layer in the direction parallel to the tensile stress when the tensile ratio at 120 ℃ is 80%.

A molded article of < X13 > comprising the laminate of any one of < X6 > - < X12 >.

The molded article according to < X14 > and < X13 > is obtained by laminating any of the laminated articles of < X6 > < X12 > on at least a part of the surface of a molded article having a non-planar shape.

In addition, one embodiment of the present invention may have the following configuration.

A method for producing a laminate, which comprises (A) a step of irradiating a resin layer comprising a urethane acrylate resin and particles applied to at least one side of an acrylic resin film with an active energy ray to cure the resin layer comprising the urethane acrylate resin and particles to form a hard coat layer,

the content of the particles is 2.0 to 5.0 wt% relative to the hard coating after curing,

when the average dispersion particle diameter of the particles is r (μm) and the film thickness of the hard coat layer is d (μm), d.ltoreq.r is satisfied,

the laminate has a pencil hardness of H or more, a haze of 3% or more, and a crack growth rate of 170% or more at 120 ℃,

The laminated film formed by laminating the resin layer containing no particles on the acrylic resin film has a crack growth rate of 80% or more at 120 ℃.

< Y2 > the method for producing a laminate according to < Y1 >, further comprising the following step (B):

and (B) applying a coating liquid containing an acrylic resin to the hard coat layer obtained in the step (A), and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100nm to form a low refractive index layer.

< Y3 > the method for producing a laminate according to < Y1 > or < Y2 >, wherein the cumulative amount of light irradiated with active energy rays in the step (A) is 150 to 500mJ/cm ² 。

A method for producing a laminate according to claim < Y4 > or < Y2 > wherein, before the step (B), a step (B') of adding a solvent to the acrylic resin as a material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm,

The method for producing a laminate according to any one of < Y1 > < Y4 >, wherein the laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a delta haze of 30% or less after 20% stretching at 120 ℃.

< Y6 > a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer contains urethane acrylate resin and particles,

the laminate has a pencil hardness of H or more and a haze of 3% or more,

The laminate according to the above-mentioned item < Y7 > and < Y6 >, wherein the particles are silica particles.

< Y8 > the laminate according to < Y7 >, wherein the hard coat layer contains 2.0 to 5.0 wt% of the silica particles,

The average dispersion particle diameter of the silica particles is 1.0 to 4.0. Mu.m.

The laminate according to any one of < Y9 > to < Y6 > wherein the hard coat layer has a film thickness of 0.2 to 3.0 μm.

The laminate according to any one of < Y10 > to < Y6 > wherein the delta haze at 120 ℃ at a stretch ratio of 80% is 8.0% or less.

The laminate according to any one of < Y11 > to < Y6 > - < Y10 >, wherein the hard coat layer further comprises a low refractive index layer,

The laminate according to < Y12 > and < Y11 > has a light reflectance of 3.0% or less.

The laminate according to < Y13 > or < Y11 > or < Y12 > has a crack growth rate of 170% or more at 120 ℃.

The laminate according to any one of < Y14 > < Y11 > < Y13 >, wherein the delta haze at 120 ℃ at 80% is 10% or less.

A molded article of < Y15 > comprising the laminate of any one of < Y6 > - < Y14 >.

A method for producing a laminate, wherein Z1 is greater than one, comprises:

the laminate has a crack growth rate of 80% or more at 120 ℃.

The method for producing a laminate according to Z2 > and Z1 > wherein the acrylic resin film is formed by molding an acrylic resin composition comprising a thermoplastic acrylic polymer and polymer particles, the polymer particles comprising a crosslinked elastomer, the thermoplastic acrylic polymer comprising 50 to 100 mass% of methyl methacrylate units and 0 to 50 mass% of other constituent units, and the total amount of the methyl methacrylate units and the other constituent units in the thermoplastic acrylic polymer being 100 mass%.

The method for producing a laminate according to Z3 & lt Z2 & gt, wherein the crosslinked elastomer contains 50 mass% or more of acrylate units in 100 mass% of the crosslinked elastomer, and the polymer particles are graft copolymer particles comprising the crosslinked elastomer and a graft polymer layer located on the surface layer side of the crosslinked elastomer.

A method for producing a laminate according to any one of < Z1 > < Z3 >, wherein the resin layer containing the urethane acrylate resin further contains particles.

A method for producing a laminate according to Z5 & lt Z4 & gt, wherein the particles are inorganic oxide particles and/or crosslinked organic resin particles.

The method for producing a laminate according to < Z6 > or < Z4 > wherein the particles are 1 or more selected from the group consisting of silica, alumina, zirconia, a crosslinked silicone resin, a crosslinked acrylic resin and a crosslinked aromatic vinyl resin.

The method for producing a laminate according to any one of < Z7 > to < Z4 > - < Z6 >, wherein at least some of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin.

A method for producing a laminate according to any one of < Z8 > to < Z7 >, wherein the content of the particles is 2.0 to 5.0% by weight relative to the hard coat layer after curing,

A method for producing a laminate according to any one of < Z9 > to < Z8 >, wherein the cumulative light amount of the active energy ray irradiation in the step (A1) is 150 to 500mJ/cm ² 。

A method for producing a laminate according to any one of < Z10 > and < Z1 > - < Z9 >, wherein the method comprises, before the step (B1), a step (B1') of adding a solvent to the acrylic resin as a material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm,

The method for producing a laminate according to any one of < Z1 > < Z10 >, wherein the laminate film obtained by laminating the low refractive index layer on the acrylic resin film has a delta haze of 30% or less after 20% stretching at 120 ℃.

the laminate has a crack growth rate of 80% or more at 120 ℃.

A method for producing a laminate according to Z13 & lt Z12 & gt, wherein the laminate has a delta haze of less than 8.0% at a stretching ratio of 80% at 120 ℃.

The method for producing a laminate according to < Z14 > or < Z13 > wherein the acrylic resin film is formed by molding an acrylic resin composition comprising a thermoplastic acrylic polymer and polymer particles, the polymer particles comprising a crosslinked elastomer, the thermoplastic acrylic polymer comprising 50 to 100 mass% of methyl methacrylate units and 0 to 50 mass% of other constituent units, and the total amount of the methyl methacrylate units and the other constituent units in the thermoplastic acrylic polymer being 100 mass%.

The method for producing a laminate according to Z15 & lt Z14 & gt, wherein the crosslinked elastomer contains 50 mass% or more of the acrylate unit in 100 mass% of the crosslinked elastomer, and the polymer particles are graft copolymer particles comprising the crosslinked elastomer and a graft polymer layer located on the surface layer side of the crosslinked elastomer.

Z16 > a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer described above contains a urethane acrylate resin,

< Z17 > the laminate according to < Z16 >, wherein the hard coat layer further comprises particles.

The laminate according to Z18 > Z17, wherein the particles are inorganic oxide particles and/or crosslinked organic resin particles.

The laminate according to < Z19 > to < Z17 > or < Z18 >, wherein the particles are 1 or more selected from the group consisting of silica, alumina, zirconia, a crosslinked silicone resin, a crosslinked acrylic resin and a crosslinked aromatic vinyl resin.

The laminate according to any one of < Z20 > < Z17 > < Z19 >, wherein at least some of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin.

The laminate according to any one of < Z21 > < Z16 > < Z20 >, wherein the hard coat layer further comprises a low refractive index layer,

The laminate according to Z22 > and Z21 > has a light reflectance of 2.0% or less.

The laminate according to < Z23 > or < Z21 > or < Z22 > wherein the in-plane retardation (Re) of the laminate is 10nm or less and the absolute value of the retardation in the thickness direction (Rth) is 30nm or less.

The laminate according to any one of < Z24 > < Z16 > < Z23 >, wherein the delta haze at 120 ℃ at 80% is less than 8.0%.

The laminate according to any one of < Z25 > to < Z24 >, wherein the delta haze at 120 ℃ at 80% is 3.0% or less.

The laminate according to any one of < Z26 > and < Z21 > - < Z25 >, wherein the low refractive index layer has a microcrack width of 2.0 μm or less in a direction parallel to the tensile stress when the elongation at 120 ℃ is 80%.

The laminate according to any one of < Z27 > and < Z21 > - < Z26 >, wherein the depth of the groove of the microcrack from the surface of the laminate on the low refractive index layer side is 1.0 μm or less at the microcrack portion of the low refractive index layer in the direction parallel to the tensile stress when the tensile ratio at 120 ℃ is 80%.

A molded article of < Z28 > comprising the laminate of any one of < Z16 > - < Z27 >.

The molded article according to < Z29 > and < Z28 > is obtained by laminating any of < Z16 > < Z27 > on at least a part of the surface of a molded article having a non-planar shape.

A method for producing a laminate, which comprises (A2) a step of irradiating a resin layer comprising a urethane acrylate resin and particles applied to at least one side of an acrylic resin film with an active energy ray to cure the resin layer comprising the urethane acrylate resin and particles to form a hard coat layer,

A method for producing a laminate according to Z31 > and Z30, wherein the laminate has a delta haze of less than 8.0% at a stretching ratio of 80% at 120 ℃.

Z32 > a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer contains urethane acrylate resin and particles,

The laminate has a pencil hardness of H or more and a haze of 3% or more,

The laminate according to Z33 > Z32, wherein the laminate has a delta haze of less than 8.0% at a stretch of 80% at 120 ℃.

Examples

[ example A ]

Hereinafter, embodiment 1 of the present invention will be described in more detail based on example a, but the present invention is not limited to these example a. In the following examples a and comparative examples a, "part" and "%" refer to parts by mass or% by mass.

[ method of measurement and evaluation ]

The measurement and evaluation in example a and comparative example a were performed by the following methods.

(measurement of average particle diameter)

The average particle diameter of the crosslinked elastomer or graft copolymer particles dispersed in the aqueous latex was measured using a laser diffraction particle size distribution measuring apparatus (Microtrac particle size distribution measuring apparatus MT3000, manufactured by daily nectar corporation).

(glass transition temperature (Tg))

Differential Scanning Calorimeter (DSC) SSC-5200, manufactured by Seiko Instruments, was used. After the sample (acrylic resin film) was temporarily heated to 200℃at a rate of 25℃per minute, the temperature was maintained at 200℃for 10 minutes, and then the temperature was lowered to 50℃at a rate of 25℃per minute (pre-conditioning). Thereafter, the sample was heated to 200℃at a heating rate of 10℃per minute, and DSC measurement was performed during this period. The differential value (SSDC) was obtained from the obtained DSC curve, and the glass transition temperature of the acrylic resin film was obtained from the maximum point thereof.

(elongation at Break under tension)

The acrylic resin film was cut out to 10mm (width) ×100mm (length) as a test piece. The test piece was measured using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a waste heat time of 2 minutes, an inter-jig distance of 40mm and a tensile speed of 200 mm/min. The elongation at break of the acrylic resin film was defined as the tensile elongation at break.

The value of the tensile elongation at break is an arithmetic average of 3 values remaining from the measurement results obtained using 5 test pieces, excluding the highest value and the lowest value.

(crack growth Rate at 120 ℃ C.)

The crack growth rate was measured by forming a hard coat layer or a laminate of a hard coat layer and a low refractive index layer on one surface of an acrylic resin film. Specifically, the laminate was cut out to 10mm (width) ×100mm (length) as a sample. The sample was measured using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a residual heat time of 2 minutes, an interval between clamps of 40mm, and a tensile speed of 200 mm/min. The crack growth rate at 120℃was defined as the crack growth rate at the time of cracking of the hard coat layer. The value of the crack growth rate is an arithmetic average of test results (3) obtained by measuring 3 samples. The results are reported in Table 5.

(whitening after 80% stretching at 120 ℃ C.)

The whitening after 80% stretching at 120℃was measured on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. Specifically, the laminate was cut out to 10mm (width) ×100mm (length) as a sample. The sample was subjected to 80% stretching using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a residual heat time of 2 minutes, an interval between clamps of 40mm and a stretching speed of 200 mm/min, and the whitening degree was visually observed. The evaluation criterion was @ (excellent): no whitening, good (good) at both reflection and transmission: no whitening at reflection, slight whitening at transmission, delta (optional): light whitening, x (bad) both in reflection and transmission: both reflective and transmissive whitening.

(film thickness)

The film thickness of the acrylic resin film was measured by PEACOCK dial No. 25 (manufactured by Kawasaki Co., ltd.).

The film thickness of the hard coat layer was measured by an F20 film thickness measuring system (manufactured by Filmetrics Co., ltd.). The opposite side of the hard coat layer was blackened with a sign pen, and the refractive index of the acrylic resin film was measured to be 1.49 and the refractive index of the hard coat layer was measured to be 1.50.

(haze)

Haze of the laminate was measured by using a haze meter NDH4000 (manufactured by japan electric color industry Co., ltd.) in accordance with ISO 14782.

(80% delta haze after stretching at 120 ℃ C.)

The delta haze of the laminate after 80% stretching at 120 ℃ was measured on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. Specifically, the laminate was cut out to 10mm (width) ×100mm (length) as a sample. The sample was subjected to 80% stretching using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a waste heat time of 2 minutes, an inter-clamp distance of 40mm and a stretching speed of 200 mm/min, and the haze of the stretched laminate was measured by using a haze meter NDH4000 (manufactured by Nippon electric industries Co., ltd.) according to ISO 14782. The difference between the haze of the laminate before stretching and the haze of the laminate after 80% stretching was regarded as "80% delta haze after stretching at 120 ℃.

(20% after stretching Δhaze at 120 ℃ C.)

The measurement of the delta haze of the laminate after 20% stretching at 120 ℃ was performed on a laminate film in which a hard coat layer was not formed on one side of the acrylic resin film and a low refractive index layer was directly formed on one side of the acrylic resin film. Specifically, the laminated film was cut out to 10mm (width) ×100mm (length) as a sample. The sample was subjected to 20% stretching using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a waste heat time of 2 minutes, an inter-clamp distance of 40mm and a stretching speed of 200 mm/min, and the haze of the stretched laminate was measured according to ISO14782 using a haze meter NDH4000 (manufactured by Nippon electric industries Co., ltd.). The difference between the haze of the laminate before stretching and the haze of the laminate after 20% stretching was regarded as "20% delta haze after stretching at 120 ℃.

(light reflectance)

The light reflectance of the laminate was measured on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. The surface of the acrylic resin film opposite to the surface on which the hard coat layer and the low refractive index layer were formed was blackened with a black oily marker (registered trademark) and a black plastic tape was attached thereto to prepare a sample. The light reflectance of this sample was measured by using a colorimeter SC-P (manufactured by Suga Test Instruments Co., ltd.) in accordance with JIS Z8722.

(Pencil hardness)

The pencil hardness of the laminate was measured in accordance with JIS K5600-5-4.

(width of microcracks and depth of grooves of microcracks)

The width of the microcracks and the depth of the grooves of the microcracks were measured on a laminate having a hard coat layer and a low refractive index layer formed on one surface of an acrylic resin film. Specifically, the laminate was cut out to 10mm (width) ×100mm (length) as a sample. The sample was subjected to 80% stretching using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a residual heat time of 2 minutes, an inter-clamp distance of 40mm and a stretching speed of 200 mm/min. The stretched sample was observed with a transmission microscope, and the width of the microcracks and the depth of the grooves of the microcracks were measured.

(particle diameter of hollow silica particles)

The particle size of the hollow silica fine particles was obtained by observing a cross-sectional photograph of a laminate of 1200nm×800nm at a magnification of 200000 times as measured by an electron microscope (Hitachi High-Technologies, H7650). An arithmetic average value of the particle diameters of 10 hollow silica particles was calculated, and the obtained value was used as the particle diameter of the hollow silica particles.

(average particle diameter of particles in hard coating layer)

The average particle diameter of the particles in the hard coat layer was obtained by observing a photograph of a cross section of a laminate of 1200nm×800nm at 200000 times magnification measured by an electron microscope (Hitachi High-Technologies, H7650). An arithmetic average value of particle diameters of 10 dispersed domains of particles in the hard coat layer was calculated, and the obtained value was taken as an average dispersed particle diameter of the particles in the hard coat layer.

(in-plane phase Difference (Re))

The in-plane retardation was measured on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. Specifically, the laminate was cut out 40mm×40mm to obtain a sample. The sample was measured using an automatic birefringence meter (KOBRA-WR, manufactured by Emotion measurement Co., ltd.) at a temperature of 23.+ -. 2 ℃ and a humidity of 50.+ -. 5%, at a wavelength of 590nm, and at an incident angle of 0 ℃.

(retardation in thickness direction (Rth))

The thickness-direction retardation was measured on a laminate in which a hard coat layer and a low refractive index layer were formed on one surface of an acrylic resin film. Specifically, the laminate was cut out 40mm×40mm to obtain a sample. The sample was measured using an automatic birefringence meter (KOBRA-WR, manufactured by Emotion measurement Co., ltd.) at a temperature of 23.+ -. 2 ℃ and a humidity of 50.+ -. 5%, at a wavelength of 590nm, and at an incident angle of 0 ℃.

(average particle diameter of particles)

The average particle diameter of the particles was obtained from a cross-sectional photograph of 48 μm×32 μm at a magnification 10000 times as measured by an electron microscope (Hitachi High-Technologies, H7650), and the average value of the dispersed particles at 5 sites in the field of view was calculated by observation of the cross-sectional photograph.

(antiglare property)

The antiglare property is measured by forming a hard coat layer or a laminate of a hard coat layer and a low refractive index layer on one surface. Specifically, a black adhesive PET film was bonded to the opposite surface of the laminate from the side on which the hard coat layer was formed, and the reflection of the fluorescent lamp was visually observed in a bright room environment. And (2) the following steps: the pinout of the fluorescent lamp was blurred and not confirmed, x: the pinout of the fluorescent lamp can be clearly confirmed.

(gloss)

The gloss of the laminate was measured on a laminate in which a hard coat layer and a low refractive index layer were formed on one side of an acrylic resin film. The sample was subjected to measurement of specular gloss at 60℃using a gloss meter VG7000 (manufactured by Nippon Denshoku Co., ltd.) in accordance with JIS Z8741.

[ production example 1: graft copolymer particles (A)

The following materials were charged into an 8L polymerization apparatus equipped with a stirrer.

200 parts of deionized water

Dioctyl sulfosuccinate sodium 0.24 parts

Formaldehyde sodium bisulphite 0.15 parts

0.001 part of ethylenediamine tetraacetic acid 2-sodium salt

Ferrous sulfate 0.00025 parts

The gas in the polymerization apparatus was sufficiently replaced with nitrogen gas to form a substantially oxygen-free state. Thereafter, the internal temperature of the polymerization apparatus was set to 60 ℃. Next, the following monomer mixture was continuously added into the polymerization apparatus at a rate (speed) of 10 parts by mass/hr. After the addition of the monomer mixture was completed, polymerization was further continued for 0.5 hour to obtain particles (average particle diameter 90 nm) of the crosslinked elastomer (A1). The polymerization conversion was 99.5%.

Monomer mixture:

30 parts of a vinyl monomer mixture (n-Butyl Acrylate (BA) 90% and Methyl Methacrylate (MMA) 10%)

Allyl methacrylate (AlMA) 1 part

0.2 part of Cumene Hydroperoxide (CHP).

Thereafter, 0.05 parts by mass of dioctyl sodium sulfosuccinate was charged into the above-mentioned polymerization apparatus containing the particles of the crosslinked elastomer (A1). Next, a monomer mixture composed of 70 parts of a vinyl monomer mixture (MMA 98%, BA1% and RUVA 1%) for forming the graft polymer layer (A2), 0.5 part of t-dodecyl mercaptan (t-DM) and 0.5 part of CHP was continuously added to the polymerization apparatus at a rate of 10 parts per hour at an internal temperature of 60 ℃. The polymerization was further continued for 1 hour to obtain graft copolymer particles (average particle diameter 90 nm). The polymerization conversion was 98.2%. Li Liyong calcium chloride is used to salt out and coagulate the latex obtained, and then the coagulated solid component is washed with water and dried to obtain a powder of the graft copolymer particles (A). The amounts of the components are shown in Table 1.

In addition, RUVA is a reactive ultraviolet absorber (2- (2 '-hydroxy-5' -methacryloxyethylphenyl) -2-H-benzotriazole (manufactured by Otsuka chemical Co., ltd., RUVA-93)).

TABLE 1

[ production example 2: graft copolymer particles (B)

180 parts of deionized water

Polyoxyethylene lauryl ether phosphate 0.002 parts

Boric acid 0.4725 parts

0.04725 parts of sodium carbonate

Sodium hydroxide 0.0098 part

The gas in the polymerization apparatus was sufficiently replaced with nitrogen gas to form a substantially oxygen-free state. Thereafter, the internal temperature of the polymerization apparatus was set to 80 ℃. After 0.027 part of potassium persulfate was put into a polymerization apparatus as a 2% aqueous solution, a mixed solution composed of 27 parts of a vinyl monomer mixture (MMA 97% and BA 3%) and 0.036 part of allyl methacrylate was continuously added into the polymerization apparatus over 81 minutes.

The polymerization was further continued for 60 minutes, whereby particles of the polymer of layer 1 which became the core (crosslinked elastomer (B1)) were obtained. The polymerization conversion was 99.0%.

Thereafter, 0.0267 parts of sodium hydroxide was added to the polymerization apparatus in the form of a 2% aqueous solution. Next, 0.08 parts of potassium persulfate was added to the polymerization apparatus in the form of a 2% aqueous solution. Thereafter, a mixed solution composed of 50 parts of a vinyl monomer mixture (BA 83% and styrene (St) 17%) and 0.375 parts of allyl methacrylate was continuously added to the polymerization apparatus over 150 minutes. After the addition, 0.015 parts of potassium persulfate was added to the polymerization apparatus as a 2% aqueous solution. Next, polymerization was continued for 120 minutes to obtain a core (crosslinked elastomer (B1)) composed of layer 1 and layer 2. The polymerization conversion was 99.0% and the average particle diameter was 230nm.

Thereafter, 0.023 parts of potassium persulfate was added to the polymerization apparatus in the form of a 2% aqueous solution. Next, 23 parts of a vinyl monomer mixture (MMA 80% and BA 20%) was continuously added to the polymerization apparatus over 45 minutes. The polymerization was further continued for 30 minutes, whereby a latex of graft copolymer particles (B1) composed of a core (crosslinked elastomer (B1)) and a shell (graft polymer layer (B2)) having a 2-layer structure was obtained. The polymerization conversion was 100.0%. After salting out and coagulating the obtained latex with magnesium sulfate, the coagulated solid component was washed with water and dried to obtain white powdery graft copolymer particles (B). The average particle diameter of the graft copolymer particles (B) was 250nm. The amounts of the components are shown in Table 2.

TABLE 2

[ production example 3 ]

The obtained powdery graft copolymer particles (A) and (B) and PARAPET HM (polymethyl methacrylate; 100% by weight of methyl methacrylate, manufactured by KURARAY Co., ltd.) and AO60 (manufactured by ADEKA Co., ltd.) were blended in the amounts (parts) shown in Table 3, respectively. The resulting mixture was mixed using a henschel mixer. Next, a 58mm phi vented type co-directional twin screw extruder (TEM 58L/D=41.7, toshiba machinery Co., ltd.) having a barrel temperature adjusted to 190℃to 250℃was used, and the mixture was melt kneaded at a screw speed of 150rpm at a discharge amount of 180 kg/hr. The obtained melt-kneaded product was drawn out from the extruder in the form of a strand, cooled in a water tank, and then cut by a granulator to obtain pellets. The die used had 4.5X115 holes, and a leaf disc filter (manufactured by Length Co., ltd., filtration accuracy: 10. Mu., size: 7 inches, and 33 sheets) was set between the die and the head of the extruder as a polymer filter. The obtained pellets were melt kneaded at a cylinder set temperature of 180 to 240℃and a discharge amount of 150kg/hr using a 90mm phi single-screw extruder with a T die, and then discharged from the T die at a die temperature of 240℃to obtain an acrylic film (acrylic resin film) having a thickness of 175. Mu.m while being cooled and solidified by bringing both surfaces into contact with a metallic casting roll having a temperature of 90℃and a touch roll having an elastic metal sleeve having a temperature of 60℃to obtain a film (acrylic resin film)

TABLE 3

[ example A1 ]

Coating 1 shown in table 4 was applied to the acrylic film (acrylic resin film) obtained in production example 3 using a bar coater, and a resin layer was formed on the acrylic film. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV accumulated light amounts shown in table 5, and the resin layer was cured to form a hard coat layer. The temperature of the chill roll at the time of forming the hard coat layer was 50 ℃. The obtained laminate was evaluated for various characteristics. The results are shown in Table 5. In example 1, a laminate composed of an acrylic film and a hard coat layer was produced. In example 1, the obtained laminate was measured and evaluated for various physical properties described in the column "laminate (hard coat layer, low refractive index layer formed)" in table 5, and the results thereof are described in the column "laminate (hard coat layer, low refractive index layer formed)" in table 5. The coating 1 shown in table 4 is a curable composition for forming a hard coat layer, and can be said to be a composition for forming a hard coat layer.

[ examples A2 to A12, comparative examples A1 to A2 ]

The coating materials 1 to 5 shown in table 4 were applied to the acrylic film (acrylic resin film) obtained in production example 3 in accordance with the combinations shown in table 5 by using a bar coater, and a resin layer was formed on the acrylic film. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV accumulated light amounts shown in table 5, and the resin layer was cured to form a hard coat layer. The temperature of the chill roll at the time of forming the hard coat layer was 50 ℃. Next, the coatings 6 to 9 described in table 4 were applied to the obtained hard coat layer in the combinations described in table 5 using a bar coater, and a resin layer was formed on the hard coat layer. The particle diameters of the hollow silica particles in the paints 6 to 9 (particle diameters of the hollow silica particles in the low refractive index layer) were all about 50nm. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) under a nitrogen atmosphere and with the UV accumulated light amounts described in table 5, and the resin layer was cured to form a low refractive index layer on the hard coat layer. The obtained laminate was evaluated for various characteristics. The results are shown in Table 5. The coatings 1 to 5 shown in table 4 are curable compositions for forming a hard coat layer, and may be referred to as compositions for forming a hard coat layer. The coatings 6 to 9 shown in table 4 are curable compositions for forming a low refractive index layer, and may be said to be compositions for forming a low refractive index layer.

In order to evaluate the delta haze after 20% stretching at 120 ℃, the acrylic films (acrylic resin films) obtained in production example 3 were coated with the paints 6 to 9 described in table 4 using a bar coater, and a resin layer was formed on the acrylic films. After coating, the resin layer was dried at 80℃for 1 minute to evaporate the solvent. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) under a nitrogen atmosphere and with the UV accumulated light amount described in table 5, and the resin layer was cured to produce a laminated film in which only a low refractive index layer was formed on the acrylic film. The resultant laminated film was evaluated for delta haze after 20% stretching at 120℃and the results are shown in Table 5.

TABLE 4

TABLE 5

[ results ]

From table 5, it is found that the laminate of example a is excellent in moldability. In addition, it was found that the laminate of examples A1 to A7, a10 and a11 was excellent in formability and also excellent in whitening after 80% stretching at 120 ℃. Further, it was found that the layered bodies of examples A2 to a12 were excellent in antireflection effect. On the other hand, it was found that the laminate of comparative example a was poor in moldability.

[ examples A13 to A21 ]

First, particles 1 to 12 shown in table 6 were mixed with Methyl Ethyl Ketone (MEK) and stirred sufficiently to prepare a 20 mass% particle dispersion. Next, the 20 mass% particle dispersion was mixed with the paint 1 so as to be a predetermined amount (the amount of particles contained in the hard coat layer in the finally obtained laminate was an amount as shown in table 7), and the mixture was sufficiently stirred to prepare a composition for forming a hard coat layer containing particles. Next, the particle-containing hard coat layer-forming composition prepared as described above was applied to the acrylic film (acrylic resin film) obtained in production example 3 using a bar coater so as to form a combination of table 7, and a resin layer was formed on the acrylic film. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV accumulated light amounts shown in table 7, and the resin layer was cured to form a hard coat layer containing particles. The temperature of the chill roll at the time of forming the hard coat layer was 50 ℃. Next, the coating 6 described in table 4 was applied to the obtained hard coat layer using a bar coater, and a resin layer was formed on the hard coat layer. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) under a nitrogen atmosphere and with the UV accumulated light amounts described in table 7, and the resin layer was cured to form a low refractive index layer on the hard coat layer. The obtained laminate was evaluated for various characteristics. The results are shown in Table 7. The term "crack growth at 120℃of the laminated film containing no particles" is shown in Table 7. The numerical values of the items are obtained by measuring the crack growth rate at 120 ℃ using a laminate obtained by forming a hard coat layer composed of the particle-free paint 1 on the acrylic film (acrylic resin film) obtained in production example 3 by the above-described method as a sample.

TABLE 6

TABLE 7

[ example B ]

Hereinafter, embodiment 2 of the present invention will be described in more detail based on example B, but the present invention is not limited to these example B. In example B and comparative example B, the terms "part" and "%" refer to parts by mass or% by mass.

[ method of measurement and evaluation ]

The measurement and evaluation in example B and comparative example B were performed by the following methods.

(crack propagation Rate of particle-free laminate film at 120 ℃ C.)

The crack growth rate of the particle-free laminated film at 120℃was measured on a laminated film having a particle-free hard coat layer formed on one surface of an acrylic resin film. Specifically, the laminated film was cut out to 10mm (width) ×100mm (length), and the film was measured using a Tensilon tensile tester (AG-2000D, shimadzu corporation) equipped with a high temperature tank set at 120℃under conditions of a waste heat time of 2 minutes, an interval between jigs of 40mm, and a tensile speed of 200 mm/min. The crack growth rate at 120℃of the laminated film containing no particles was defined as the crack growth rate at the time of cracking of the hard coat layer.

(others)

The measurement and evaluation methods of the glass transition temperature (Tg), tensile elongation at break, crack growth, film thickness, haze, 20% after stretching at 120 ℃, Δhaze, light reflectance, pencil hardness, antiglare property, average particle diameter of particles, and particle diameter of hollow silica fine particles are the same as those described in the above [ example a ], and therefore, the description thereof is incorporated herein by reference. Further, the measurement of the formability (whitening), the delta haze after 80% stretching at 120 ℃, the in-plane retardation (Re), and the thickness direction retardation (Rth) was performed on a laminate having a hard coat layer or a hard coat layer and a low refractive index layer formed on one surface, and the description thereof was omitted by the description of the same as that described in the above [ example a ].

[ manufacturing example B ]

In example B, graft copolymer particles (A) and graft copolymer particles (B) produced by the same methods as in [ production example 1 ] and [ production example 2 ] of [ example A ] were used. In example B, a film produced by the same method as in [ example a ] [ production example 3 ] was used as the acrylic film.

In comparative example B7, a laminate film (film thickness 200 μm) of a PMMA resin layer and a PC resin layer (manufactured by AW-10U Shine Techno) was used instead of an acrylic film as a base film.

[ examples B1 to B10, comparative examples B1 to B7 ]

First, particles 1 to 12 shown in table 6 were mixed with MEK and stirred sufficiently to prepare a 20 mass% particle dispersion. Next, the particle dispersion liquid of 20 mass% and the paints 1 to 5 described in table 4 were mixed so as to be a predetermined amount (the amount of particles contained in the hard coat layer in the finally obtained laminate was an amount described in tables 8 and 9), and the mixture was sufficiently stirred to prepare a composition for forming a hard coat layer containing particles. Next, the composition for forming a hard coat layer containing particles prepared as described above was applied to the acrylic film (acrylic resin film) obtained in production example 3 or the laminate film of a PMMA resin layer and a PC resin layer in accordance with the combination described in tables 8 and 9 using a bar coater, and a resin layer was formed on the acrylic film. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV accumulated light amounts described in tables 8 and 9, and the resin layer was cured to form a hard coat layer. The temperature of the chill roll at the time of forming the hard coat layer was 50 ℃. The obtained laminate was evaluated for various characteristics. The results are shown in tables 8 and 9.

[ examples B11 to B15, comparative examples B8 to B9 ]

The hard coat layer was formed on the acrylic film (acrylic resin film) obtained in production example 3 by the same method as in the above [ examples B1 to B10, comparative examples B1 to B7 ] using the composition for forming a hard coat layer containing particles. Next, the coating materials 6, 8, or 9 described in table 4 were applied to the obtained hard coat layer in the combinations described in tables 8 and 9 using a bar coater, and a resin layer was formed on the hard coat layer. After coating, the resin layer was dried at 80 ℃ for 1 minute, and the solvent was volatilized from the resin layer. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) under the UV accumulated light amounts and nitrogen atmosphere described in tables 8 and 9, and the resin layer was cured to form a low refractive index layer on the hard coat layer. The obtained laminate was evaluated for various characteristics. The results are shown in tables 8 and 9.

In order to evaluate the delta haze after 20% stretching at 120 ℃, the coating materials 6, 8, or 9 described in table 4 were applied to the acrylic film (acrylic resin film) obtained in production example 3 or the laminate film of the PMMA resin layer and the PC resin layer using a bar coater, and the resin layer was formed on the acrylic film. After coating, the resin layer was dried at 80℃for 1 minute to evaporate the solvent. Next, the resin layer was irradiated with ultraviolet rays (active energy rays) under the UV accumulated light amounts and nitrogen atmosphere described in tables 8 and 9, and the resin layer was cured, whereby a laminated film having only a low refractive index layer formed on the acrylic film was produced. The resultant laminated film was evaluated for delta haze after 20% stretching at 120℃and the results are shown in tables 8 and 9.

TABLE 8

TABLE 9

[ results ]

From tables 9 and 10, it is clear that the laminate of example B is excellent in moldability and surface hardness, and antiglare property. On the other hand, it was found that the laminate of comparative example B was inferior in moldability and/or antiglare property, surface hardness, and the like.

Industrial applicability

The method for producing the 1 st laminate can obtain a laminate excellent in moldability and low in whitening. Further, the method for producing the 2 nd laminate can provide a laminate excellent in moldability and surface hardness and antiglare property. Therefore, one embodiment of the present invention can be applied to various fields including automotive interior applications such as in-vehicle displays.

Symbol description

1 acrylic resin film

2 hard coat layer

3 Low refractive index layer

4 laminate

5 microcracks

6 width of microcracks

Depth of groove of microcrack 7

Claims

1. A method of manufacturing a laminate, comprising:

a step A1 of irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with active energy rays to cure the resin layer containing the urethane acrylate resin to form a hard coat layer, and

a step B1 of applying an acrylic resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100nm to the hard coat layer obtained in the step A1, and irradiating the obtained resin layer containing the acrylic resin with an active energy ray to cure the resin layer containing the acrylic resin to form a low refractive index layer;

the laminate has a crack growth rate of 80% or more at 120 ℃.

2. The method for producing a laminate according to claim 1, wherein the acrylic resin film is formed by molding an acrylic resin composition comprising a thermoplastic acrylic polymer and polymer particles comprising a crosslinked elastomer,

the thermoplastic acrylic polymer is composed of 50 to 100 mass% of methyl methacrylate units and 0 to 50 mass% of other constituent units, and the total amount of the methyl methacrylate units and the other constituent units in the thermoplastic acrylic polymer is 100 mass%.

3. The method for producing a laminate according to claim 2, wherein the crosslinked elastomer contains 50 mass% or more of acrylate units in 100 mass% of the crosslinked elastomer,

the polymer particles are graft copolymer particles comprising the crosslinked elastomer and a graft polymer layer located on the surface layer side of the crosslinked elastomer.

4. The method for producing a laminate according to any one of claims 1 to 3, wherein the resin layer containing the urethane acrylate resin further contains particles.

5. The method for producing a laminate according to claim 4, wherein the particles are inorganic oxide particles and/or crosslinked organic resin particles.

6. The method for producing a laminate according to claim 4 or 5, wherein the particles are 1 or more selected from silica, alumina, zirconia, a crosslinked silicone resin, a crosslinked acrylic resin, and a crosslinked aromatic vinyl resin.

7. The method for producing a laminate according to any one of claims 4 to 6, wherein at least a part of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin.

8. The method for producing a laminate according to any one of claims 4 to 7, wherein the content of the particles is 2.0 to 5.0 wt% relative to the hard coat layer after curing,

when the average dispersion particle diameter of the particles is r and the film thickness of the hard coat layer is d, d.ltoreq.r is satisfied, wherein the units of r and d are μm,

The laminated film in which the resin layer containing no particles is laminated on the acrylic resin film has a crack growth rate of 80% or more at 120 ℃.

9. The method for producing a laminate according to any one of claims 1 to 8, wherein the cumulative amount of light irradiated with active energy rays in the step A1 is 150 to 500mJ/cm ² 。

10. The method for producing a laminate according to any one of claims 1 to 9, wherein the step B1 is preceded by a step B1' of adding a solvent to the acrylic resin as a material of the low refractive index layer to produce an acrylic resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100nm,

the solvent comprises at least more than 1 solvent, and the boiling point of the solvent with the highest boiling point is 115-180 ℃.

11. The method for producing a laminate according to any one of claims 1 to 10, wherein a laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a delta haze of 30% or less after 20% stretching at 120 ℃.

12. A method for producing a laminate, comprising A1 a step of irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with active energy rays to cure the resin layer containing the urethane acrylate resin to form a hard coat layer,

the laminate has a crack growth rate of 80% or more at 120 ℃.

13. The method for producing a laminate according to claim 12, wherein the laminate has a delta haze of less than 8.0% at a stretching ratio of 80% at 120 ℃.

14. The method for producing a laminate according to claim 12 or 13, wherein the acrylic resin film is formed by molding an acrylic resin composition comprising a thermoplastic acrylic polymer and polymer particles comprising a crosslinked elastomer,

15. The method for producing a laminate according to claim 14, wherein the crosslinked elastomer contains 50 mass% or more of acrylate units in 100 mass% of the crosslinked elastomer,

16. A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer comprises a urethane acrylate resin,

17. The laminate of claim 16, wherein the hard coat layer further comprises particles.

18. The laminate of claim 17, wherein the particles are inorganic oxidized particles and/or crosslinked organic resin particles.

19. The laminate according to claim 17 or 18, wherein the particles are 1 or more selected from silica, alumina, zirconia, a crosslinked silicone resin, a crosslinked acrylic resin, and a crosslinked aromatic vinyl resin.

20. The laminate according to any one of claims 17 to 19, wherein at least a part of the particles contain a reactive functional group on the surface of the particles, the reactive functional group being reactive with the urethane acrylate resin.

21. The laminate according to any one of claims 16 to 20, further comprising a low refractive index layer on the hard coat layer,

the low refractive index layer comprises an acrylic resin containing 40% or more of hollow silica particles having a particle diameter of less than 100 nm.

22. The laminate according to claim 21, wherein the laminate has a light reflectance of 2.0% or less.

23. The laminate according to claim 21 or 22, wherein an in-plane retardation Re of the laminate is 10nm or less and an absolute value of a thickness direction retardation Rth is 30nm or less.

24. The laminate of any one of claims 16-23, wherein the delta haze at 120 ℃ at 80% is less than 8.0%.

25. The laminate according to any one of claims 16 to 24, wherein the delta haze at 120 ℃ at a stretch of 80% is 3.0% or less.

26. The laminate according to any one of claims 21 to 25, wherein the low refractive index layer has a microcrack width of 2.0 μm or less in a direction parallel to the tensile stress when the tensile ratio at 120 ℃ is 80%.

27. The laminate according to any one of claims 21 to 26, wherein when the elongation at 120 ℃ is 80%, the depth of the groove of the microcrack at the microcrack portion in the direction parallel to the tensile stress from the surface of the laminate on the low refractive index layer side is 1.0 μm or less.

28. A molded article comprising the laminate according to any one of claims 16 to 27.

29. The molded article according to claim 28, which is obtained by laminating the laminate according to any one of claims 16 to 27 on at least a part of the surface of a molded article having a non-planar shape.

30. A method for producing a laminate, comprising A2 a step of irradiating a resin layer containing urethane acrylate resin and particles applied to at least one surface of an acrylic resin film with active energy rays, and curing the resin layer containing urethane acrylate resin and particles to form a hard coat layer,

the content of the particles is 2.0 to 5.0 wt% with respect to the hard coating after curing,

31. The method for producing a laminate according to claim 30, wherein the laminate has a delta haze of less than 8.0% at a stretching ratio of 80% at 120 ℃.

32. A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,

the hard coat layer comprises urethane acrylate resin and particles,

the laminate has a pencil hardness of H or more and a haze of 3% or more,

33. The laminate of claim 32, wherein the laminate has a delta haze of less than 8.0% at a stretch of 80% at 120 ℃.