WO2019082529A1

WO2019082529A1 - Hard coat film

Info

Publication number: WO2019082529A1
Application number: PCT/JP2018/033547
Authority: WO
Inventors: 俊明長澤
Original assignee: リンテック株式会社
Priority date: 2017-10-23
Filing date: 2018-09-11
Publication date: 2019-05-02

Abstract

This hard coat film is applied to the outdoor-side surface of a window glass or window plastic board, and is characterized by comprising: a polyethylene terephthalate substrate; a siloxane-based hard coat layer; and a bonding layer for bonding the substrate and the hard coat layer, the bonding layer being composed of a material containing an acrylic resin and a UV absorber. According to the present invention, a hard coat film which is applied to the outdoor-side surface of a window glass or window plastic board and has excellent durability can be provided.

Description

Hard coat film

The present invention relates to a hard coat film.

Heretofore, a plastic film for the purpose of preventing ultraviolet ray cutting and scattering of glass has been used as affixing to a window glass of a building or an automobile or a plastic board for a window.

Such plastic films are often affixed to the inside (indoor side) of window glass and plastic boards for windows. This is due to the problem of durability and, depending on the location of the plastic film, it is necessary to set up a scaffold when installing the plastic film.

On the other hand, depending on, for example, the installation environment of the window glass and the plastic board for the window (the environment where the space for installing the plastic film is not sufficiently secured in the room), the window glass and the plastic board for the window It may be stuck on the outside (outdoor side).

However, when the conventional plastic film is applied to the window glass and the outdoor side of the window plastic board, sufficient durability can not be obtained.

Japanese Patent Application Laid-Open No. 11-309813

An object of the present invention is to provide a hard coat film having excellent durability, which is used by being attached to the surface of the window glass or the plastic side of a window on the outdoor side.

Such an object is achieved by the present invention described in the following (1) to (13).
(1) A hard coat film that is used by being attached to the surface of the window glass or the window side plastic board,
A substrate made of polyethylene terephthalate,
Siloxane-based hard coat layer,
A hard coat film comprising: a material containing an acrylic resin and an ultraviolet light absorber; and a bonding layer for bonding the base and the hard coat layer.

(2) The hard coat film according to the above (1), wherein the ultraviolet absorber is a polymer material having an ultraviolet absorbing functional group in the molecule.

(3) The hard coat film according to (2), wherein the ultraviolet ray absorbing functional group is contained in a monomer constituting the main chain of the polymer material.

(4) The hard coat film according to the above (2) or (3), wherein the ultraviolet light absorbing functional group is a benzotriazole functional group.

(5) The hard coat film according to any one of the above (2) to (4), wherein the polymer material has a UV-stable functional group together with the UV-absorbing functional group.

(6) The hard coat film according to (5), wherein the UV-stable functional group is contained in a monomer constituting the main chain of the polymer material.

(7) The hard coat film according to any one of the above (2) to (6), wherein the polymer material has an acrylic skeleton.

(8) In any one of the above (1) to (7), the content of the ultraviolet absorber relative to 100 parts by mass of the acrylic resin in the bonding layer is 0.01 parts by mass or more and 15 parts by mass or less Hard coat film described.

(9) The hard coat film according to any one of the above (1) to (8), wherein the content of the ultraviolet light absorber in the hard coat layer is 1.0% by mass or less.

(10) The hard coat film according to any one of the above (1) to (9), wherein the thickness of the substrate is 10 μm or more and 300 μm or less.

(11) The hard coat film according to any one of the above (1) to (10), wherein the thickness of the bonding layer is 0.01 μm or more and 15 μm or less.

(12) The hard coat film according to any one of the above (1) to (11), wherein the thickness of the hard coat layer is 0.05 μm or more and 30 μm or less.

(13) The hard coat film according to any one of the above (1) to (12), wherein an adhesive layer is provided on the side opposite to the side facing the bonding layer of the substrate.

ADVANTAGE OF THE INVENTION According to this invention, the hard-coat film excellent in durability used by sticking on the surface of the outdoor side of a window glass or the plastic board for windows can be provided.

FIG. 1 is a longitudinal sectional view showing a preferred embodiment of the hard coat film of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Hard coat film]
FIG. 1 is a longitudinal sectional view showing a preferred embodiment of the hard coat film of the present invention.

The hard coat film 10 is used by being attached to the surface on the outdoor side of a window glass or a plastic board for windows.

As shown in FIG. 1, the hard coat film 10 includes a substrate 1 made of polyethylene terephthalate, a siloxane-based hard coat layer 3, and a bonding layer 2. The coat layer 3 is joined.

And the joining layer 2 is comprised by the material containing acrylic resin and a ultraviolet absorber.

Thereby, the durability of the hard coat film 10 can be made excellent, and the adhesion of the hard coat layer 3, the surface hardness, the ultraviolet ray cutting property, etc. can be stably made excellent over a long period of time. it can. Moreover, when it sticks to glass, the scattering prevention performance of the said glass can be stably made excellent over a long period of time.

Such excellent effects can be obtained by the hard coat film having the above-mentioned configuration, and another configuration, for example, when an ultraviolet absorber is contained in another portion instead of the bonding layer Or, when the hard coat layer is made of a material other than a siloxane type, the above excellent effects can not be obtained when the base material is other than polyethylene terephthalate.

<Base material>
The substrate 1 is made of polyethylene terephthalate.

Thereby, construction (adhesion) to window glass which is an adherend of hard court film 10, and a plastic board for windows can be performed easily. In addition, the shape followability to a curved adherend can be made excellent.

The base material 1 should just be mainly comprised by the polyethylene terephthalate, and may contain components other than a polyethylene terephthalate.

Such components include, for example, colorants, antioxidants, UV absorbers, light stabilizers, softeners, modifiers, rust inhibitors, fillers, surface lubricants, corrosion inhibitors, heat resistant stabilizers, A lubricant, a primer, an antistatic agent, a polymerization inhibitor, a crosslinking agent, a catalyst, a leveling agent, a thickener, a dispersing agent and the like can be mentioned.

In the present specification, "mainly" refers to the one having the highest content rate among the target portions.

In particular, the content of polyethylene terephthalate in the substrate 1 is preferably 90% by mass or more, and more preferably 95% by mass or more.

In addition, the substrate 1 may have a substantially uniform composition throughout, or may have portions with different compositions. For example, the substrate 1 may be a laminate including a plurality of layers having portions different in composition from each other (including, for example, when the molecular weight of polyethylene terephthalate is different), or the composition is along the thickness direction It may be composed of an inclined material that changes in an inclined manner.

The base material 1 may be subjected to surface treatment for enhancing the adhesion to the bonding layer 2 or the pressure-sensitive adhesive layer 4.

As such surface treatment, for example, a method of applying an easily adhesive resin such as polyester type, acrylic type and polyurethane type can be mentioned.

The thickness of the substrate 1 is not particularly limited, but is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and still more preferably 30 μm or more and 100 μm or less.

Thereby, the durability of the hard coat film 10 and the glass scattering prevention performance when the adherend is glass can be further improved, and the construction of the hard coat film 10 on the adherend Can be done more easily. In addition, the shape followability to a curved adherend can be made more excellent.

<Hard coat layer>
The hard coat layer 3 is made of a siloxane-based material. In other words, the hard coat layer 3 is a layer containing a silicon compound (siloxane compound) having a siloxane bond, and for example, at least one of an inorganic silica compound (including polysilicic acid) and a polyorganosiloxane compound. The layer which has as a main component can be mentioned preferably.

By having such a siloxane-based hard coat layer 3, the surface hardness, the abrasion resistance, the weather resistance, and the like of the hard coat film 10 can be made particularly excellent.

The inorganic silica-based compound, the polyorganosiloxane-based compound, or a mixture thereof can be produced, for example, by the following method.

That is, a method of partially or completely hydrolyzing an alkoxysilane compound represented by the following general formula (1) with an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as oxalic acid or acetic acid is preferably used for polycondensation. Be

R ¹ _n Si (OR ² ) _4-n (1)
[R ¹ in Formula (1) is a non-hydrolyzable group and is an alkyl group, a substituted alkyl group (substituent: halogen atom, epoxy group, (meth) acryloyloxy group, etc.), alkenyl group, aryl group or Aralkyl group and R ² are lower alkyl groups, and n is an integer of 0 or 1 or more and 3 or less. When there are a plurality of R ¹ and OR ² respectively, the plurality of R ¹ may be the same or different, and the plurality of OR ² may be the same or different. ]

In this case, inorganic compounds can be obtained by completely hydrolyzing a compound in which n is 0, that is, tetraalkoxysilane, and partial hydrolysis can give polyorganosiloxane or a mixture of inorganic silica type and polyorganosiloxane type. . On the other hand, in the compound where n is 1 or more and 3 or less, since it has a non-hydrolyzable group, polyorganosiloxane is obtained by partial or complete hydrolysis. At this time, a suitable organic solvent may be used to uniformly carry out the hydrolysis.

Specific examples of the alkoxysilane compound represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and tetraisobutoxysilane , Tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane , Butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-metac These include royloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane, trivinylethoxysilane, etc. One or two or more of them can be used in combination.

In addition, when synthesizing a silicon compound having a siloxane bond, for example, an aluminum compound (for example, aluminum chloride, trialkoxyaluminum etc.) can be used.

Furthermore, as another method, sodium metasilicate, sodium orthosilicate or water glass (sodium silicate mixture) is used as the silicon compound of the raw material, an acid such as hydrochloric acid, sulfuric acid or nitric acid or a metal compound such as magnesium chloride or calcium sulfate It is possible to use a method of acting and hydrolyzing.

This hydrolysis treatment produces free silicic acid, which is easy to polymerize and rapidly forms siloxane bonds. Depending on the type of raw material, usually, a mixture of linear, cyclic and network silicon compounds (silicon compounds having a siloxane bond) is obtained.

The polysilicic acid obtained from water glass is usually composed mainly of a chain structure represented by the following general formula (2).

(In the formula (2), m represents the degree of polymerization, and R is hydrogen, silicon or a metal such as magnesium or aluminum).

Also, the material for the hard coat layer 3, for example, silica gel _(SiO X · _nH 2 O) can also be used.

The hard coat layer 3 may be composed mainly of a siloxane compound and may contain components other than the siloxane compound.

However, the content of the ultraviolet light absorber in the hard coat layer 3 is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less Is more preferred.

Thereby, the adhesion between the bonding layer 2 and the hard coat layer 3 can be made more excellent for a longer period of time.

The content of the siloxane-based compound in the hard coat layer 3 is preferably 90% by mass or more, and more preferably 95% by mass or more.

The hard coat layer 3 is formed by coating a hard coat agent-containing coating solution on the substrate 1 using, for example, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method, etc. It can be formed by processing, heating and curing.

The thickness of the hard coat layer 3 is not particularly limited, but is preferably 0.05 μm or more and 30 μm or less, more preferably 0.2 μm or more and 25 μm or less, and still more preferably 1.0 μm or more and 20 μm or less preferable.

Thereby, the durability of the hard coat film 10 can be further improved, and the application (adhesion) of the hard coat film 10 to an adherend can be more easily performed. In addition, the shape followability to a curved adherend can be made more excellent.

<Bonding layer>
Between the substrate 1 and the hard coat layer 3 is provided a bonding layer 2 for bonding them. The bonding layer 2 is made of a material containing an acrylic resin and a UV absorber.

By having such a bonding layer 2, the durability of the hard coat film 10 can be made excellent, and the adhesion of the hard coat layer 3, the ultraviolet ray cutting property, etc. are stably excellent over a long period of time. It can be done. In particular, when using a polyethylene terephthalate base and a siloxane-based hard coat layer in combination, it has not been possible in the past to make these adhesions stably excellent over a long period of time. On the other hand, in the present invention, the bonding layer is made of a material containing an acrylic resin and a UV absorber, whereby the adhesion between the substrate made of polyethylene terephthalate and the hard coat layer of siloxane type is achieved. Can be made excellent over a long period of time, and the effects required for the hard coat film as described above can be stably exhibited over a long period of time.

Examples of the UV absorber include salicylate UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, substituted acrylonitrile UV absorbers, and the like.

Examples of salicylate type ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate and the like.

As a benzophenone series ultraviolet absorber, for example, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone And 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.

As a benzotriazole type ultraviolet absorber, for example, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′- tert-Butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-amyl-5′-isobutylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5') Methylphenyl) benzotriazole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole.

Examples of the substituted acrylonitrile-based ultraviolet light absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and the like.

Also, as other UV absorbers, for example, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, N- (2-ethylphenyl) And -N '-(2-ethoxy-5-t-butylphenyl) succinic acid diamide and the like.

The UV absorber contained in the bonding layer 2 may be the low molecular weight one as described above (without the polymerization structure), but the UV absorbing functional group (UV absorbing functional group) may be a molecule. It is preferable that it is a polymeric material contained therein.

In this way, it is possible to more effectively prevent unintentional compositional variations in the bonding layer 2. In addition, it is more effectively prevented that the ultraviolet absorber bleeds out. From such a thing, the above effects are stably acquired over a long period of time.

The polymer material (polymer material having a UV-absorbing functional group in the molecule) is preferably one having an acrylic skeleton.

Thereby, the affinity between the acrylic resin forming the bonding layer 2 and the ultraviolet light absorber (the above-mentioned polymer material) can be made more excellent, and the unwilling composition at each portion in the bonding layer 2 Of the hard coat film 10 as a whole can be made more excellent, and the strength of the bonding layer 2 itself can be made more excellent. Further, since the ultraviolet light absorber (the polymer material) itself is a material having high adhesion, the adhesion strength between the base 1 and the hard coat layer 3 by the bonding layer 2 can be made more excellent.

The ultraviolet absorbing functional group may be contained in any form in the polymer material, but is preferably contained in the monomer constituting the main chain of the polymer material.

In this way, it is possible to more effectively prevent unintentional compositional variations in the bonding layer 2. In addition, bleeding out of the component having the ultraviolet absorbing ability is further effectively prevented. Moreover, the content of the functional group having the ultraviolet absorbing ability in the bonding layer 2 can be more suitably controlled by adjusting the compounding ratio of the monomer during the preparation of the ultraviolet absorber (the above-mentioned polymer material). .

Examples of the UV-absorbing functional group include functional groups (functional groups having UV-absorbing ability) possessed by the low molecular weight UV absorber as described above, and among them, benzotriazole-based functional groups are preferable.

Thereby, the durability of the hard coat film 10 can be further improved.

The benzotriazole-based functional group is a functional group having a structure in which a phenol structure is bonded to a nitrogen atom at the 2-position in the benzotriazole structure.

As a monomer which has an ultraviolet-ray absorptive functional group, the monomer etc. which are represented by following formula (3) which is a benzotriazole derivative are mentioned, for example.

In formula (3), R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and X ¹ represents a straight chain having 1 to 6 carbon atoms Represents a linear or branched alkylene group or —O—R ⁵ —, Y ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl having 1 to 4 carbon atoms Represents a group, a cyano group or a nitro group. R ⁵ represents a linear or branched alkylene group having 2 or 3 carbon atoms.

The content of the monomer having a UV-absorbing functional group in the polymer material is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and 10% by mass. It is more preferable that the content is 30% by mass or less.

Thereby, the balance of the ultraviolet ray absorbing power of the bonding layer 2 and the adhesion strength between the base 1 and the hard coat layer 3 by the bonding layer 2 can be made more preferable.

The polymer material preferably has a UV-stable functional group (UV-stable functional group) as well as a UV-absorbing functional group.

Thereby, deterioration of the resin material due to ultraviolet light can be suppressed and stabilized, and the weather resistance of the hard coat film 10 as a whole can be made more excellent. As the action to suppress and stabilize the deterioration of the resin material by the ultraviolet light, for example, it is mentioned that the resin is prevented from further deteriorating by capturing the radical generated along with the deterioration of the resin material by the ultraviolet light. Be

In addition, when the ultraviolet ray-stable functional group constitutes a part of the polymer material, it is effectively prevented that the ultraviolet ray-stable component bleeds out, and the above effects are stably achieved over a long period of time can get.

The ultraviolet light stable functional group may be contained in any form in the polymer material, but is preferably contained in the monomer constituting the main chain of the polymer material.

In this way, it is possible to more effectively prevent unintentional compositional variations in the bonding layer 2. In addition, bleeding out of the UV-stable component is more effectively prevented. In addition, the content ratio of the UV-stable functional group in the bonding layer 2 can be more suitably controlled by adjusting the compounding ratio of the monomers at the time of preparation of the UV absorber (the above-mentioned polymer material).

Examples of the monomer having a UV-stable functional group include those having a structure of a piperidinyl group having a sterically hindered nitrogen atom. Examples of the piperidinyl group having a sterically hindered nitrogen atom include a piperidinyl group in which the nitrogen atom is bonded to at least two quaternary carbon atoms.

As a monomer which has a structure of the piperidinyl group which has the nitrogen atom which received the said steric hindrance, the monomer etc. which are represented by following General formula (4) which is a piperidine derivative are mentioned, for example.

In formula (4), R ⁶ represents a hydrogen atom or a cyano group. R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms, X ² represents an oxygen atom or an imino group, and Y ² is a hydrogen atom having one or more carbon atoms 18 or less hydrocarbon group, or -CO-CR ⁹ = CHR ¹⁰ is represented. R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms.

The content of the monomer having a UV-stable functional group in the polymer material is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 0.2% by mass or more and 10% by mass or less Preferably, the content is 0.5% by mass or more and 10% by mass or less.

Thereby, the balance such as the weather resistance of the hard coat film 10 and the adhesion strength between the base 1 and the hard coat layer 3 by the bonding layer 2 can be made more suitable.

When the content of the monomer having a UV-absorbing functional group in the polymer material is A [mass%], and the content of the monomer having a UV-stable functional group in the polymer material is B [mass%] It is preferable to satisfy the relation of 1.5 ≦ A / B ≦ 40, more preferably to satisfy the relation of 2.0 ≦ A / B ≦ 30, and the relation of 2.5 ≦ A / B ≦ 25. It is further preferable to be satisfied.

Thereby, the weather resistance of the hard coat film 10 can be made more excellent.

The acrylic resin (acrylic resin contained together with the ultraviolet absorber) contained in the bonding layer 2 has an acrylic skeleton, and has a structure in which acrylic monomers such as acrylic acid, methacrylic acid and esters thereof are polymerized. As long as it has one, it may be one that has been subjected to other chemical modifications, but one that does not have a UV-stable functional group as described above.

The content of the ultraviolet absorber relative to 100 parts by mass of the acrylic resin in the bonding layer 2 is preferably 0.01 parts by mass or more and 15 parts by mass or less, and is 0.05 parts by mass or more and 10 parts by mass or less Is more preferable, and more preferably 0.08 parts by mass or more and 5 parts by mass or less.

The bonding layer 2 may be made of mainly an acrylic resin and an ultraviolet absorber, and may contain components other than the acrylic resin and the ultraviolet absorber.

Examples of such components include plasticizers, colorants, antioxidants, light stabilizers and the like.

The thickness of the bonding layer 2 is not particularly limited, but is preferably 0.01 μm to 15 μm, more preferably 0.05 μm to 10 μm, and still more preferably 0.1 μm to 10 μm. .

<Pressure-sensitive adhesive layer>
In the illustrated configuration, the hard coat film 10 is provided with the pressure-sensitive adhesive layer 4 on the side opposite to the side facing the bonding layer 2 of the base 1 in addition to the above-described configuration.

Thereby, the hard coat film 10 can be more suitably stuck on a window glass or a plastic board for windows.

Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 include natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives.

Among these, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives are particularly preferable in terms of weather resistance and the like.

Specific examples of synthetic rubber-based pressure-sensitive adhesives include styrene-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block copolymer, etc. Can be mentioned.

Specific examples of the acrylic pressure-sensitive adhesive include copolymers of acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like.

Specific examples of the urethane-based pressure-sensitive adhesive include those obtained by reacting a polyester polyol or polyether polyol with a polyisocyanate compound.

Specific examples of silicone pressure-sensitive adhesives include those made of silicone rubber and silicone resin.
These pressure-sensitive adhesives can be used alone or in combination of two or more.

The pressure-sensitive adhesive layer 4 may be composed mainly of a pressure-sensitive adhesive, and may contain components other than the pressure-sensitive adhesive.

Such components include, for example, tackifiers, fillers, softeners, antioxidants, UV absorbers, light stabilizers, crosslinking agents, colorants, modifiers, rust inhibitors, flame retardants, hydrolysis Examples include inhibitors, surface lubricants, corrosion inhibitors, heat stabilizers, lubricants, primers, antistatic agents, polymerization inhibitors, catalysts, leveling agents, thickeners, dispersants, antifoam agents, and the like.

Examples of the tackifier include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, coumarone / indene resins, styrene resins, phenol resins, xylene resins and the like.

Examples of the filler include zinc oxide, titanium oxide, silica, calcium carbonate, barium sulfate and the like.
As a softening agent, process oil, liquid rubber, a plasticizer etc. are mentioned, for example.

As an antioxidant, an anilide type antioxidant, a phenol type antioxidant, a thioester type antioxidant etc. are mentioned, for example.

The pressure-sensitive adhesive layer 4 may be, for example, various coating methods such as roll coating, gravure coating, reverse coating, spray coating, knife coating, die coating, bar coating, etc. of a liquid composition (coating liquid) for forming the pressure sensitive adhesive layer 4 It can carry out by apply | coating on the base material 1 by this.
The adhesive layer 4 can be formed by solidifying the coating film of the coating liquid.

The coating liquid may have a composition different from that of the pressure-sensitive adhesive layer 4. For example, after the coating liquid is applied, the contained solvent may be removed, or the degree of polymerization and the degree of crosslinking may be made different by advancing the curing reaction and the crosslinking reaction.

Alternatively, the pressure-sensitive adhesive layer 4 may be formed on a release liner and then bonded to the substrate 1.

The thickness of the pressure-sensitive adhesive layer 4 is not particularly limited, but is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 60 μm or less.

The thickness of the hard coat film 10 is not particularly limited, but is preferably 17 μm or more and 450 μm or less, more preferably 25 μm or more and 300 μm or less, and still more preferably 35 μm or more and 150 μm or less.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these.

For example, the hard coat film may have a configuration other than that described above (for example, at least one intermediate layer).

In addition, the surface of the pressure-sensitive adhesive layer (the surface opposite to the surface facing the substrate) may be coated with a release liner. This makes it more effective that dust or the like adheres to the pressure-sensitive adhesive layer during storage, transport, etc. of the hard coat film, or that the pressure-sensitive adhesive layer adheres to an unintended site. It can be prevented. When the hard coat film is attached to a window glass or a plastic board for windows, the release liner may be peeled off to expose the pressure-sensitive adhesive layer.

Hereinafter, the present invention will be described in more detail by way of specific examples, but the present invention is not limited to these examples. In addition, in the following description, the process which has not shown temperature conditions in particular is performed at room temperature (23 degreeC) and 50% of relative humidity. Moreover, as for various measurement conditions, values not particularly indicating temperature conditions are values at room temperature (23 ° C.) and 50% relative humidity.

[1] Production of Hard Coat Film (Example 1)
First, a 50 μm-thick polyethylene terephthalate film is prepared as a substrate, and a composition containing an acrylic resin (an acrylic resin having no ultraviolet absorbing functional group) and an ultraviolet absorber on one side of the film (Denki Kenken Co., Ltd.) Product (Surcoat primer SCP 531) and a mixture of acrylic resin (acrylic resin not having an ultraviolet absorbing functional group) and a composition containing an ultraviolet absorber (Surcoat primer SCP 500) ) Was applied with a Meyer bar so that the dry film thickness would be 5 μm, and dried at 100 ° C. for 1 minute to provide a bonding layer. The UV absorber contained in the coat primer SCP 531 and the UV absorber contained in the coat primer SCP 500 are both a monomer having a benzotriazole-based functional group as a UV-absorbing functional group and a UV-stable functional group It is an acrylic polymer material containing in its molecule a monomer having the The UV absorber contained in the coat primer SCP 531 and the UV absorber contained in the coat primer SCP 500 each have a content of the monomer having a UV-absorbing functional group in the UV absorber as A [mass%]. The relationship of 2.5 ≦ A / B ≦ 25 was satisfied when the content of the monomer having an ultraviolet ray-stabilizing functional group in the ultraviolet ray absorber was B [mass%].

Next, on the surface of the bonding layer, a siloxane-based hard coating agent (Surcoat SCH 720, manufactured by Mikiken Co., Ltd.) was applied by Meyer bar so that the dry film thickness would be 3 μm, and dried at 130 ° C. for 3 minutes .

Next, an acrylic adhesive is coated with a comma coater on the surface opposite to the surface provided with the bonding layer of the substrate and the hard coat layer, and then dried at 100 ° C. for 3 minutes to obtain a 15 μm adhesive A layer was formed, and a silicone-coated surface of a polyethylene terephthalate release liner having a thickness of 38 μm was attached to the pressure-sensitive adhesive layer to obtain a hard coat film (73 μm in thickness) having the configuration shown in FIG.

(Example 2)
A hard coat film was produced in the same manner as in Example 1 except that the composition of the hard coat film was as shown in Table 1 by adjusting the composition of the composition used for forming the bonding layer.

(Comparative example 1)
A hard coat film was produced in the same manner as in Example 1 except that a polycarbonate film (thickness 50 μm) was used instead of the polyethylene terephthalate film as the substrate.

(Comparative example 2)
A hard coat film was produced in the same manner as in Example 1 except that an acrylic hard coat agent was used as a composition for forming the hard coat layer. As an acrylic hard coat agent, a solution comprising 100 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone and toluene was used.

(Comparative example 3)
A hard coat film was produced in the same manner as in Example 1 except that a composition containing no ultraviolet light absorber was used as the composition used for forming the bonding layer.

(Comparative example 4)
A hard coat was prepared in the same manner as in Comparative Example 3 except that a siloxane-based hard coat agent (Surcoat SCH 730, manufactured by Gakuen Co., Ltd.) as a composition containing an ultraviolet light absorber was used as a composition for forming a hard coat layer. A film was produced.

The constitutions of the hard coat films of the respective Examples and Comparative Examples are summarized in Table 1 below.
In Table 1, polyethylene terephthalate is PET, polycarbonate is PC, and the acrylic resin contained in the surcoat primer SCP 531 (made by RIKEN) is Ac1, the acrylic resin contained in the surcoat primer SCP 500 (made by RIKEN) Ac2, an acrylic resin (an acrylic resin having no ultraviolet light absorbing functional group) contained in the surface coat primer SCP 521 (manufactured by KOKEN CO., LTD.) Ac3; a polyester resin having no ultraviolet light absorbing functional group, Ac5 UVA contained in UVA1 and UVA2 contained in UVA2 and Surcoat Primer SCP500 (available from KOKEN CO., LTD.), And UVCA2 UVCA included in UVcoat and SCP250 (manufactured by KOKEN CO., LTD.). UV absorber contained UVA3, siloxane The hard coat agent (manufactured by RIKEN CHEMICAL CO., LTD., SURCOAT SCH 720) is indicated by HC1, the siloxane-based hard coat agent (manufactured by ROKken Co., Ltd., by Sircoat SCH 730) is indicated HC2, the acrylic hard coat agent is indicated by HC1 ′, and the acrylic adhesive is indicated by A1. .

In addition, the UV absorber contained in the coat coat primer SCP 521 (made by KOKEN CO., LTD.) And the UV absorber contained in the coat coat primer SCP 500 (made by KOKEN CO., LTD.) Are all low molecular weight benzotriazole based UV absorbers. And had no polymerized structure. SURCOAT SCH730 (manufactured by KOKEN CO., LTD.) Contained a low molecular weight benzotriazole-based ultraviolet absorber as well as a siloxane-based compound.

[2] Evaluation The following evaluations were made on the hard coat films of the respective Examples and Comparative Examples.

<Haze value after weathering>
A haze meter (in accordance with JIS K 7136: 2000) is applied to the surface of the hard coat film on which the hard coat layer is provided, in the initial state (before accelerated weathering) and after accelerated weathering for 500 hours and 1000 hours. The haze (%) was measured using Nippon Denshoku Kogyo Co., Ltd., NDH 2000).

The accelerated weathering test was performed using a sunshine weather meter (WEL-SUN-HCH manufactured by Suga Test Instruments Co., Ltd.) in a state where the surface provided with the hard coat layer faced the light source side.

<Adhesiveness of hard coat layer after weathering test>
The hard coat film attached to the glass plate is in the initial state (before accelerated weathering) and after being subjected to accelerated weathering for 500 hours and 1000 hours, adhesion according to JIS K 5600-5-6: 1999 The test (cross-cut method) was performed, and the occurrence of peeling between the substrate and the bonding layer and the occurrence of peeling between the bonding layer and the hard coat layer were evaluated according to the following criteria.

The accelerated weathering test was conducted using a sunshine weather meter (WEL-SUN-HCH manufactured by Suga Test Instruments Co., Ltd.) in a state where the surface provided with the hard coat layer faced the light source side.

A: The percentage of squares which did not cause peeling is 100%.
B: The proportion of squares which did not cause peeling is 75% or more and less than 100%.
C: The proportion of squares which did not cause peeling is 50% or more and less than 75%.
D: The percentage of squares which did not cause peeling is 25% or more and less than 50%.
E: The percentage of squares which did not cause peeling is less than 25%.
These results are summarized in Table 2.

As is apparent from Table 2, while excellent results were obtained in the present invention, satisfactory results were not obtained in the comparative example.

The hard coat film of the present invention is a hard coat film used by being attached to the surface of the window glass or the plastic side of a window on the outdoor side, and is made of a polyethylene terephthalate base, a siloxane hard coat layer, and acrylic. It is comprised by the material containing base resin and a ultraviolet absorber, and it is characterized by providing the joining layer which joins the said base material and the said hard-coat layer. Therefore, it is possible to provide a hard coat film excellent in durability, which is used by being attached to the surface of the window glass or the plastic side of the window on the outdoor side. Therefore, the hard coat film of the present invention has industrial applicability.

10 ... hard coat film 1 ... base material 2 ... bonding layer 3 ... hard coat layer 4 ... adhesive layer

Claims

A hard coat film that is used by being attached to the surface of the window glass or the plastic side of a window on the outdoor side,
A substrate made of polyethylene terephthalate,
Siloxane-based hard coat layer,
A hard coat film comprising: a material containing an acrylic resin and an ultraviolet light absorber; and a bonding layer for bonding the base and the hard coat layer.
The hard coat film according to claim 1, wherein the ultraviolet absorber is a polymer material having an ultraviolet absorbing functional group in a molecule.
The hard coat film according to claim 2, wherein the ultraviolet absorbing functional group is contained in a monomer constituting the main chain of the polymer material.
The hard coat film according to claim 2 or 3, wherein the ultraviolet absorbing functional group is a benzotriazole-based functional group.
The hard coat film according to any one of claims 2 to 4, wherein the polymer material has a UV-stable functional group together with the UV-absorbing functional group.
The hard coat film according to claim 5, wherein the ultraviolet light stable functional group is contained in a monomer constituting the main chain of the polymer material.
The hard coat film according to any one of claims 2 to 6, wherein the polymer material has an acrylic skeleton.
The hard coat according to any one of claims 1 to 7, wherein the content of the ultraviolet absorber relative to 100 parts by mass of the acrylic resin in the bonding layer is 0.01 parts by mass or more and 15 parts by mass or less. the film.
The hard coat film according to any one of claims 1 to 8, wherein the content of the ultraviolet absorber in the hard coat layer is 1.0% by mass or less.
The thickness of the said base material is 10 micrometers or more and 300 micrometers or less, The hard coat film of any one of Claims 1-9.
The hard coat film according to any one of claims 1 to 10, wherein the thickness of the bonding layer is 0.01 μm or more and 15 μm or less.
The hard coat film according to any one of claims 1 to 11, wherein the thickness of the hard coat layer is 0.05 μm or more and 30 μm or less.
The hard coat film according to any one of claims 1 to 12, wherein a pressure-sensitive adhesive layer is provided on the side of the base opposite to the side facing the bonding layer.