JP6477755B2 - Organic glass laminating film and laminated organic glass - Google Patents

Description

  The present invention relates to a film for laminating organic glass that can impart crushability to one side of organic glass and has excellent moldability, and a laminated organic glass using the film for laminating organic glass.

  For human beings, it is impossible to avoid the response to global warming, and there is a demand for socially suppressing carbon dioxide emissions to suppress global warming. In the automobile field as well, automobiles are being reduced in weight in order to reduce carbon dioxide emissions and reduce environmental impact. As a measure for reducing the weight of automobiles, attempts have been made to replace glass used in automobiles with organic glass (resin glass).

  Conventionally, polycarbonate, polyacrylate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyolefin, ABS, and the like are known as resin materials for organic glass. Among these, polycarbonate is impact resistance, heat resistance, transparency, etc. And is being studied as an organic glass for automobile windows.

  However, polycarbonate generally has the disadvantages of low surface hardness and poor scratch resistance. Furthermore, polycarbonate also has a drawback that its solvent resistance is lower than other resins. Therefore, in order to overcome such drawbacks of polycarbonate, laminated organic glass in which polycarbonate is multilayered has been developed. For example, in Patent Document 1, the surface hardness of a polycarbonate resin substrate is increased by bonding an acrylic resin plate casted thinner than the substrate with an adhesive to at least one surface of the polycarbonate resin substrate. It has been reported that the aforementioned disadvantages of polycarbonate can be overcome. Patent Document 2 discloses a hydrophilic film-coated solvent-resistant film in which a hydrophilic film having a contact angle with water of 70 ° or less is laminated on at least one surface of a solvent-resistant film. It is reported that solvent resistance can be provided by laminating at least one surface of a polycarbonate plate.

  On the other hand, automobile windows are required not only to have impact resistance that is strong against external impacts, but also to have friability so that they can be broken out in an emergency. In order to put an organic glass window for an automobile into practical use, it is indispensable to establish a technique for providing a shattering property on one side of an organic glass having excellent impact resistance such as polycarbonate. However, for organic glass, the technology for imparting physical properties such as scratch resistance and solvent resistance has been energetically studied, but the technology for imparting friability has not been sufficiently studied. Currently.

  In addition, since organic glass used for automobile windows is molded into a three-dimensional shape according to the window shape, laminated organic glass in which a covering member having desired physical properties is laminated on one surface of organic glass is used for automobiles. In the case of application as a window, it is essential that the covering member has a formability that can follow the three-dimensional shape of an automobile window. Therefore, it is also required to establish a technique for providing excellent moldability for a covering member used by being laminated on organic glass.

JP-A-9-239936 JP 2007-152848 A

  An object of this invention is to provide the film for organic glass lamination which can provide crushability with respect to the single side | surface of organic glass, and has the outstanding moldability. Furthermore, this invention aims at providing the laminated organic glass using the said film for organic glass lamination.

  The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, an organic glass laminating film having at least a surface protective layer containing a curable resin on one side of an acrylic film is one side of an organic glass such as polycarbonate. It has been found that when it is laminated, excellent crushability can be imparted to one side of the organic glass. That is, in the laminated organic glass in which the organic glass laminating film is laminated on one side of an organic glass such as polycarbonate, the film side has impact resistance while the organic glass side (the side opposite to the film) is a hammer. It has been found that excellent crushability can be provided against impacts caused by the above. Furthermore, the present inventors also found that the organic glass laminating film has excellent formability capable of following a three-dimensional shape. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
Item 1. An organic glass laminating film comprising at least a surface protective layer containing a curable resin on one side of an acrylic film.
Item 2. Item 2. The organic glass laminating film according to Item 1, wherein the acrylic film has a thickness of 50 to 300 µm.
Item 3. Item 3. The organic glass laminating film according to Item 1 or 2, wherein the curable resin is an ionizing radiation curable resin and / or a two-component reaction curable resin.
Item 4. Item 4. The organic glass laminating film according to any one of Items 1 to 3, comprising a primer layer between the acrylic film and the surface protective layer.
Item 5. Item 5. The organic glass laminating film according to any one of Items 1 to 4, which is used by laminating on polycarbonate.
Item 6. Item 6. The organic glass laminating film according to any one of Items 1 to 5, which is used by being laminated on an organic glass for automobile windows.
Item 7. A laminated organic glass comprising a surface protective layer containing at least an organic glass layer, an acrylic film, and a curable resin in this order.
Item 8. Item 8. The laminated organic glass according to Item 7, wherein the organic glass layer is formed of polycarbonate.
Item 9. Item 9. The laminated organic glass according to Item 7 or 8, which is used for automobile windows.

  The organic glass laminating film of the present invention is a film-like thin material by selecting an acrylic film as a base material and laminating a surface protective layer formed of a specific resin component on the base material. In addition, one side of an organic glass such as polycarbonate can be provided with friability. That is, the organic glass laminating film of the present invention is laminated on one side of the organic glass so that it is resistant to impact from the side on which the film is laminated, but on the opposite side of the film from the hammer. It can be crushed when subjected to impacts such as, and it is possible to satisfy the conflicting properties of impact resistance and friability with respect to organic glass. Therefore, the laminated organic glass obtained by laminating the organic glass laminating film of the present invention on one side of the organic glass is suitably used as a window for vehicles (particularly for automobiles), and has the impact resistance required at normal times, It can have the friability required in an emergency.

  Further, according to the organic glass laminating film of the present invention, it has excellent moldability and can follow a three-dimensional shape, so that it is possible to produce a laminated organic glass in a three-dimensional curved shape. is there. Furthermore, the organic glass laminating film of the present invention has a thin overall thickness, and can be easily trimmed at the end after being integrally formed with the organic glass. Also, an insert method or a simultaneous injection molding method (for example, thermoject) Method), and can be integrally formed with organic glass, which can contribute to the improvement of the production efficiency of laminated organic glass.

  Furthermore, the organic glass laminating film of the present invention can be provided with excellent scratch resistance by using an ionizing radiation curable resin as the curable resin for forming the surface protective layer.

It is a figure which shows the cross-section of one form of the film for organic glass lamination of this invention. It is a figure which shows the cross-section of one form of the laminated organic glass of this invention.

1. Organic Glass Laminating Film The organic glass laminating film of the present invention is characterized by having at least a surface protective layer containing a curable resin on one side of an acrylic film. In FIG. 1, the cross-sectional structure is shown about the suitable one aspect | mode of the film for organic glass lamination | stacking of this invention. Hereinafter, the organic glass laminating film of the present invention will be described in detail.

(1) Acrylic film In the organic glass laminating film of the present invention, an acrylic film is used as a substrate. In the present invention, an acrylic film is selected as a base material, and by combining and laminating a surface protective layer having a specific composition described later, it is possible to impart excellent crushability and moldability to the organic glass. .

  In the present invention, the acrylic film is a film formed of an acrylic resin. Examples of the acrylic resin include (meth) acrylic acid or (meth) acrylic acid ester homopolymer, two or more (meth) acrylic acid and / or (meth) acrylic acid ester copolymer, (meth) The copolymer of acrylic acid or (meth) acrylic acid ester and another monomer is mentioned. These copolymers may be either random copolymers or block copolymers. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and other similar ones have the same meaning.

  Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, Examples thereof include isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  Other monomers copolymerizable with (meth) acrylic acid or (meth) acrylic acid esters include styrene, maleic acid, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, and acetic acid. Vinyl, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinyl caprolactam, Citraconic anhydride, N-phenylmaleimide and the like can be mentioned. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate / ( (Meth) butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / (meth) methyl acrylate copolymer, etc. Is mentioned.

  Among these, the acrylic acrylic film used in the present invention may be formed using one kind of acrylic resin alone, or may be formed by combining two or more kinds of acrylic resins.

  Among these acrylic resins, from the viewpoint of further improving the friability imparted to the organic glass, an acrylic resin preferably containing at least a (meth) acrylic acid ester as a constituent unit is mentioned.

  Moreover, in addition to an acrylic resin, the acrylic film used by this invention may contain various additives as needed. Examples of such additives include plasticizers, stabilizers, matting agents, ultraviolet absorbers, infrared absorbers, and the like.

Although it does not restrict | limit especially about the tensile elasticity modulus of the acrylic film used by this invention, For example, about 900-2500 MPa, Preferably it is about 900-1500 MPa, More preferably, what is necessary is just about 1000-1400 MPa. In addition, in this specification, the tensile elasticity modulus of an acrylic film is a value measured with the following method.
A test piece (rectangular) cut into an acrylic film with a width of 1 inch and a length of 120 mm so that the flow direction (MD) is the long side in a temperature environment of 25 ° C. (Orientec Co., Ltd.) Using Tensilon RTC-1250A), a tensile stress-strain curve obtained by measurement under the conditions of a tensile speed of 1000 mm / min and a distance between chucks of 100 mm was calculated according to the following formula.
E = Δρ / Δε
E: Tensile modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points

  Moreover, the acrylic film used in the present invention may be subjected to surface treatment such as corona discharge, glow discharge, and UV irradiation, if necessary.

  The thickness of the acrylic film used in the present invention is usually 50 to 300 μm, preferably 75 to 200 μm, and more preferably 75 to 150 μm. Although the film for organic glass lamination of the present invention uses such a thin acrylic resin as a base material, it can impart friability to the organic glass in combination with a surface protective layer having a specific composition described later.

  The method for producing the acrylic film used in the present invention is not particularly limited. For example, after the acrylic resin is formed by a melt film forming method or a solution film forming method, longitudinal stretching (MD stretching), transverse stretching (TD) It can be produced by subjecting it to a stretching treatment such as stretching.

(2) Primer layer In the organic glass laminating film of the present invention, in order to improve the adhesion between the acrylic film and the surface protective layer, a primer layer may be provided between them as necessary.

  The primer layer is formed using a binder resin. Although it does not restrict | limit especially as binder resin, For example, curable resin is mentioned. Specific examples include urethane resins, (meth) acrylic resins, (meth) acrylic / urethane copolymer resins, vinyl chloride / vinyl acetate copolymers, polyester resins, butyral resins, chlorinated polypropylene, and chlorinated polyethylene. It is done. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these binder resins, a urethane resin is preferable.

  As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be any compound having two or more hydroxyl groups in the molecule, and specific examples include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule; aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, Examples include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

  Among the urethane resins, acrylic polyol or polyester is preferably used as the polyol from the viewpoints of improving adhesion with the surface protective layer after crosslinking, reducing interaction after laminating the surface protective layer, and improving moldability. A combination of a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a crosslinking agent; and a combination of an acrylic polyol and hexamethylene diisocyanate is more preferable.

  Although it does not restrict | limit especially about the thickness of a primer layer, For example, 0.5-20 micrometers, Preferably it is 1-10 micrometers.

  The primer layer is gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat with silk screen, wire bar coat, flow coat, comma coat, pouring It is formed by coating a resin composition for forming a primer layer containing a binder resin on an acrylic film by an ordinary coating method such as coating, brush coating, spray coating, or the like, or a transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the acrylic film surface is coated.

(3) Surface protective layer In the organic glass laminating film of the present invention, a surface protective layer containing a curable resin is provided on the acrylic film or when the primer layer is provided. Thus, by using a curable resin as the resin for forming the surface protective layer, it is possible to impart friability to the organic glass while providing excellent moldability based on the interaction with the acrylic film. It becomes possible.

<Resin component>
The curable resin used for forming the surface protective layer is not particularly limited as long as it is a resin that is cured by crosslinking. Examples of the curable resin used for forming the surface protective layer include a thermosetting resin, a room temperature curable resin, a one-component reaction curable resin, a two-component reaction curable resin, and an ionizing radiation curable resin.

  Among the curable resins used for the surface protective layer, the thermosetting resin, the room temperature curable resin, the one-component reaction curable resin, or the two-component reaction curable resin specifically includes epoxy resins and phenol resins. , Urea resin, thermosetting polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, thermosetting acrylic resin, polyurethane resin and the like. Although there is no restriction | limiting in particular as an aspect of hardening reaction of these resin, For example, there exist the following aspects. Epoxy resin is a reaction with amine, acid catalyst, carboxylic acid, acid anhydride, hydroxyl group, dicyandiamide or ketimine; phenol resin is a reaction between base catalyst and excess aldehyde; urea resin is a polycondensation under alkaline or acidic conditions Reaction; Non-thermosetting polyester resin is a co-condensation reaction between maleic anhydride and diol; Melamine resin is a heat polycondensation reaction of methylol melamine; Alkyd resin is an air oxidation of unsaturated groups introduced into side chains, etc. Reaction with polyimide; reaction in the presence of an acid or weak alkali catalyst, or reaction with an isocyanate compound (in the case of a two-component type); condensation reaction in the presence of an acid catalyst of a silanol group; In the case of a hydroxyl-functional acrylic resin, a thermosetting acrylic resin is a reaction between a hydroxyl group and an amino resin that it has (one-pack type In the case of a carboxyl functional acrylic resin, a reaction of a carboxylic acid such as acrylic acid or methacrylic acid with an epoxy compound; a urethane resin is a resin containing a hydroxyl group-containing polyester resin, polyether resin, acrylic resin, etc. And the reaction of an isocyanate compound or a modified product thereof. In the thermosetting resin, a crosslinking agent, a polymerization initiator, a polymerization accelerator, and the like are used as necessary in order to advance the curing reaction as necessary. These curable resins may be used alone or in a combination of two or more.

  Among the curable resins used for the surface protective layer, as the ionizing radiation curable resin, specifically, a prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule is appropriately used. What mixed is mentioned. Here, the ionizing radiation refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually an ultraviolet ray or an electron beam is used. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, and the like. Is mentioned. Here, the polycarbonate (meth) acrylate can be obtained, for example, by esterifying a polycarbonate polyol with (meth) acrylic acid. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylate acid to the side chain of the polybutadiene oligomer. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  These curable resins may be used individually by 1 type, and may be used in combination of 2 or more type.

<Preferred resin component>
Among the curable resins described above, from the viewpoint of further improving the crushability imparted to the organic glass and the moldability, it is preferably a two-component reaction curable resin, an ionizing radiation curable resin, more preferably an ionizing radiation curable. Resin.

(Preferred two-component reaction curable resin)
In the case of using a two-component reaction curable resin for forming the surface protective layer, a two-component reaction curable urethane resin may be mentioned as a preferred embodiment. As the two-component reaction curable urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be any compound having two or more hydroxyl groups in the molecule, and specific examples include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule; aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, Examples include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate. Among these two-component reaction curable urethane resins, from the viewpoint of further improving the friability imparted to the organic glass, preferably, an acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate as a crosslinking agent, A combination of 4-diphenylmethane diisocyanate; and a combination of acrylic polyol and hexamethylene diisocyanate is more preferable.

(Preferable ionizing radiation curable resin)
When an ionizing radiation curable resin is used for forming the surface protective layer, as a preferred embodiment, a mixed resin combining a polyfunctional (meth) acrylate oligomer and a polyfunctional (meth) acrylate monomer; ionizing radiation containing at least polycarbonate methacrylate Curable resins; and mixed resins combining ionizing radiation curable resins and thermoplastic resins. Hereinafter, usage modes of these ionizing radiation curable resins will be described.

[Mixed resin combining polyfunctional (meth) acrylate oligomer and polyfunctional (meth) acrylate monomer]
When the surface protective layer is formed by combining a polyfunctional (meth) acrylate oligomer and a polyfunctional (meth) acrylate monomer, the combination mode is not particularly limited, but for example, 2 to 10 functional (meth) acrylate Combination of oligomer and 2-6 functional (meth) acrylate monomer, preferably 3-8) Combination of functional urethane (meth) acrylate oligomer and 2-4 functional (meth) acrylate monomer, more preferably 3-4 functional And a combination of a urethane (meth) acrylate oligomer and a bifunctional (meth) acrylate monomer.

  Moreover, when combining a polyfunctional (meth) acrylate oligomer and a polyfunctional (meth) acrylate monomer, as these ratios, for example, the mass ratio of polyfunctional (meth) acrylate oligomer: polyfunctional (meth) acrylate monomer is 90 : 10 to 10:90, preferably 60:40 to 10:90.

[Ionizing radiation curable resin containing at least polycarbonate methacrylate]
When polycarbonate methacrylate is used for forming the surface protective layer, polycarbonate methacrylate may be used alone as the ionizing radiation curable resin, or it contains a combination of polycarbonate methacrylate and other ionizing radiation curable resins. May be. From the viewpoint of further improving the friability imparted to the organic glass, a combination of polycarbonate methacrylate and polyfunctional (meth) acrylate is preferable.

  As the polyfunctional (meth) acrylate used in combination with the polycarbonate methacrylate, either the above-mentioned polyfunctional (meth) acrylate monomer or oligomer may be used, or both of them may be used. Preferably, the polyfunctional (meth) acrylate oligomer is used. Is mentioned. In particular, a polyfunctional urethane (meth) acrylate oligomer is preferable, a trifunctional or higher functional urethane (meth) acrylate oligomer, and a hexafunctional urethane (meth) acrylate oligomer is particularly preferable.

  Moreover, when combining polycarbonate methacrylate and polyfunctional (meth) acrylate, as these ratios, for example, the mass ratio of polycarbonate methacrylate: polyfunctional (meth) acrylate is 98: 2 to 50:50, preferably 95. : 5-60: 40 is mentioned.

Hereinafter, polycarbonate methacrylate will be described.
The polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Moreover, the said (meth) acrylate is 2 or more normally as a number of the functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable, Preferably 2-10 pieces are mentioned.

  The polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

  The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R ¹ —OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide is added to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compound (C) used as a raw material of the polycarbonate polyol, which is a carbonyl component, is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Examples include esters. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), the trihydric or higher polyhydric alcohol (B), and the compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. What is necessary is just to set the preparation molar ratio of a diol compound (A) and a polyhydric alcohol (B) in the range of 50: 50-99: 1, for example. Further, the charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl group of the diol compound and the polyhydric alcohol. What is necessary is just to set to the range of an equivalent.

  The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charge ratio is, for example, 3 or more on average in one molecule, preferably 3 to 50, more preferably 3-20 are mentioned. When such an equivalent number is satisfied, a necessary amount of (meth) acrylate groups are formed by an esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

  The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

  The molecular weight of the polycarbonate (meth) acrylate is not particularly limited. For example, the weight average molecular weight is 500 or more, preferably 1,000 or more, and more preferably more than 2,000. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but may be, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of further improving the moldability, the weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and not more than 50,000, and more preferably 5,000 to 20,000.

  In addition, the weight average molecular weight of the polycarbonate (meth) acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[Combination of ionizing radiation curable resin and thermoplastic resin]
Examples of the thermoplastic resin used in combination with the ionizing radiation curable resin include acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; Polyolefin such as polypropylene, styrene resin such as polystyrene and α-methylstyrene, polyamide, polycarbonate, acetal resin such as polyoxymethylene, fluorine resin such as ethylene-4 fluoroethylene copolymer, polyimide, polylactic acid, polyvinyl Examples include acetal resins; liquid crystalline polyester resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these thermoplastic resins, an acrylic resin is preferably used from the viewpoint of further improving the friability imparted to the organic glass. In particular, an acrylic resin having at least a (meth) acrylic acid ester as a structural unit is preferably used.

  Specific examples of the acrylic resin used in combination with the ionizing radiation curable resin include a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid esters, and (meth) acrylic. A copolymer of an acid ester and another monomer may be mentioned. Specific examples of the (meth) acrylic acid ester and specific examples of other monomers copolymerized with the (meth) acrylic acid ester are the same as those of the acrylic resin forming the acrylic film.

  In the case of using a combination of an ionizing radiation curable resin and a thermoplastic resin, examples of these combinations include, for example, a combination of a polyfunctional (meth) acrylate monomer and an acrylic resin, and more preferably pentaerythritol tri (meth) acrylate. The combination of the acrylic resin which contains (meth) acrylic acid ester as a structural unit is mentioned.

  In addition, when the ionizing radiation curable resin and the thermoplastic resin are used in combination, the mixing ratio is not particularly limited. For example, the mass ratio of the ionizing radiation curable resin to the thermoplastic resin is 10:90 to 75:25, preferably 25:75 to 75:25.

<Other additive components>
Various additives can be blended in the surface protective layer according to desired physical properties to be provided. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

<Thickness of surface protective layer>
Although it does not restrict | limit especially about the thickness of a surface protective layer, For example, 1-100 micrometers, Preferably it is 5-75 micrometers, More preferably, 10-60 micrometers is mentioned. When the thickness in such a range is satisfied, it is possible to effectively provide crushability and formability to the organic glass.
<Formation of surface protective layer>
The surface protective layer may be formed by a method corresponding to the type of curable resin to be used.

  For example, if a thermosetting resin, room temperature curable resin, one-component reaction curable resin, or two-component reaction curable resin is used, surface protection is possible by mixing these resins and various additives as required. The resin composition for the layer is applied to the release layer by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., and the resin composition is heated by heating as necessary. What is necessary is just to harden.

  If ionizing radiation curable resin is used, or if ionizing radiation curable resin and thermoplastic resin are used in combination, ionizing radiation curable resin, and optionally thermoplastic resin, and if necessary The resin composition mixed with various additives is applied to the release layer by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and the resin composition is subjected to electron beam, ultraviolet light, etc. The ionizing radiation may be irradiated and cured.

  When an electron beam is used for curing the ionizing radiation curable resin, the accelerating voltage can be appropriately selected according to the type of ionizing radiation curable resin used, the thickness of the surface protective layer, and the like. About 300 kV. The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. Can be used.

  By adding various additives to the surface protective layer thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared ray You may perform the process which provides functions, such as a shielding coat function.

(4) Thickness of organic glass laminating film, application, production method The thickness of the organic glass laminating film of the present invention varies depending on the thickness of the acrylic film, the thickness of the surface protective layer, the presence or absence of a primer layer, and the like. However, it is usually 50 to 300 μm, preferably 75 to 250 μm, and more preferably 100 to 200 μm. As described above, the organic glass laminating film of the present invention is crushed against organic glass such as polycarbonate by adopting a combination of an acrylic film and a surface protective layer having a specific composition, even though it is a thin film. Sex can be imparted. Moreover, in addition to being excellent in the moldability at the time of shaping | molding laminated organic glass, since the film for organic glass lamination of this invention is a thin film form, there also exists an advantage that the trimming after shaping | molding can be performed easily.

  The organic glass laminating film of the present invention can impart friability to one side of the organic glass by laminating on one side of the organic glass. In the organic glass laminating film of the present invention, the type of organic glass to be applied, the laminating method on the organic glass, and the like are as described later.

  The organic glass laminating film of the present invention is produced by applying and curing a resin composition containing a curable resin after forming a primer layer on one side of an acrylic film as necessary. The components used for forming each layer, the specific conditions for forming each layer, and the like are as described above.

2. Laminated Organic Glass The laminated organic glass of the present invention is produced by integrating the organic glass and the organic glass laminating film of the present invention, and includes at least an organic glass layer, an acrylic film, and a surface protection containing a curable resin. It is characterized by having layers in order. FIG. 2 shows a cross-sectional structure of a preferred embodiment of the laminated organic glass of the present invention.

  The laminated organic glass of the present invention has strong resistance to impact from the organic glass laminating film side (surface protective layer side), and gives impact to the organic glass layer side with a safety hammer for car escape. It can be crushed and has excellent crushability.

  In the laminated organic glass of the present invention, the type of organic glass used in the organic glass layer is not particularly limited as long as it can have a function as glass, for example, polycarbonate, polyacrylate, polymethyl methacrylate, Examples thereof include polyethylene terephthalate, polyethylene naphthalate, polyolefin, and ABS. Among these organic glasses, polycarbonate is excellent in impact resistance and transparency and is preferably used.

When using polycarbonate as the organic glass layer, as its melt volume rate (MVR), usually 6~25cm ^3/10 min, preferably about may be about 6~12cm ^3/10 min. The lower the melt volume rate, the better the impact resistance, so it excels in compatibility with the crushability caused by the impact of a safety hammer. For automobile windows (eg front door windows, rear door windows, sunroofs, etc.) Is preferably used. The melt volume rate is a value measured in accordance with JIS K 7210-1999 under conditions of a temperature of 300 ° C. and a load of 1.2 kgf.

  The thickness of the organic glass layer is appropriately set according to the use of the laminated organic glass, but from the viewpoint of achieving both excellent impact resistance and friability, for example, 2 to 7 μm, preferably 3 to 5 μm. Is mentioned.

  The use of the laminated organic glass of the present invention is not particularly limited, but in view of the effect of having both impact resistance and crushability, windows for vehicles such as automobiles and railways, preferably windows for automobiles can be mentioned. Specific examples of automobile windows include side windows, rear windows, and sunroofs. In addition, when using the laminated organic glass of this invention as a window for vehicles, it arrange | positions so that the film side (surface protection layer side) for organic glass lamination | stacking may become an outer side of a vehicle, and an organic glass layer may become an inside of a vehicle.

  The laminated organic glass of the present invention is produced by integrating the organic glass with the organic glass laminating film of the present invention by injection molding. Specifically, the laminated organic glass of the present invention uses the film for laminating organic glass of the present invention, and is a simultaneous injection molding method (for example, thermoject method), insert molding method, blow molding method, gas injection molding. It is produced by various injection molding methods such as the method. Among these injection molding methods, the injection molding simultaneous decoration method and the insert molding method are preferable, the injection molding simultaneous decoration method is more preferable, and the thermoject molding method is particularly preferable.

  Specifically, if the laminated organic glass of the present invention is produced using the simultaneous injection molding method, the following first to third steps may be performed.

First step: The organic glass laminating film of the present invention is supplied and fixed between a pair of male and female molds in an open state so that the surface protective layer surface of the organic glass laminating film faces the cavity. . In the case of the thermoject molding method, the acrylic film side of the decorative sheet is further heated and softened, and the softened organic glass laminate is vacuum-sucked from the mold side facing the surface protective layer side. A decorative sheet is preformed by bringing the film for use into close contact with the shape of the movable mold.
Second step: After clamping both molds, the organic glass in a fluid state is injected into the cavity formed by both molds, filled, and solidified to solidify the formed organic glass. The film is laminated and integrated.
Third step: The movable mold is separated from the fixed mold, and the laminated organic glass in which the organic glass and the organic glass laminating film are integrated is taken out.

Moreover, what is necessary is just to implement the following I-III process, when manufacturing the laminated organic glass of this invention using an insert molding method.
Step I: The organic glass laminating film of the present invention is molded into a three-dimensional shape in advance by a vacuum mold.
Step II: Trimming excess portions of the vacuum-formed organic glass laminating film to obtain a molded sheet, and Step III: Using the molded organic glass laminating film obtained in Step II as an injection mold Insert (insert the surface protection layer on the organic glass side), close the injection mold, and inject the fluidized organic glass into the mold to integrate the organic glass and the organic glass laminating film.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. In addition, the tensile elasticity modulus of the acrylic film shown below and MVR of a polycarbonate are the values measured on the measurement conditions mentioned above.

[Manufacture of organic glass laminated film]
Examples 1 and 3-5
A resin composition for forming a surface protective layer containing an ionizing radiation curable resin on an acrylic film A (tensile elastic modulus 1362 MPa, thickness 125 μm) or acrylic film B (tensile elastic modulus 1088 MPa, thickness 125 μm) is a bar coder. Then, the resin composition was cured by irradiating the resin composition with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer. Thus, an organic glass laminating film having a surface protective layer laminated on an acrylic film was produced. In each example, the resin composition used for forming the surface protective layer and the thickness of the surface protective layer after curing are as shown in Table 1.

Example 2
On the acrylic film A (tensile elastic modulus 1362 MPa, thickness 125 μm) or acrylic film B (tensile elastic modulus 1088 MPa, thickness 125 μm), a primer layer-forming resin composition is applied by a bar coater. Formed. Next, a resin composition for forming a surface protective layer is applied onto the primer layer with a bar coater, and the resin composition is irradiated with an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad). The composition was cured to form a surface protective layer. Thus, an organic glass laminating film in which a primer layer and a surface protective layer were sequentially laminated on an acrylic film was produced. In Example 2, the resin composition used for forming the primer layer, the thickness of the primer layer, the resin composition used for forming the surface protective layer, and the cured thickness of the surface protective layer are shown in Table 1. As shown in

Example 6
A resin composition for forming a surface protective layer is applied on an acrylic film A (tensile elastic modulus 1362 MPa, thickness 125 μm) with a bar coder, and then cured by curing at 50 ° C. for 24 hours. To form a surface protective layer. Thus, an organic glass laminating film having a surface protective layer laminated on an acrylic film was produced. In Example 6, the resin composition used for forming the surface protective layer and the thickness of the surface protective layer after curing are as shown in Table 1.

Comparative Example 1
Acrylic film A (tensile elastic modulus 1362 MPa, thickness 125 μm) or acrylic film B (tensile elastic modulus 1088 MPa, thickness 125 μm) was used as an organic glass laminating film (single layer film).

Comparative Example 2
By applying a resin composition for forming a surface protective layer on the acrylic film A (tensile elastic modulus 1362 MPa, thickness 125 μm) or acrylic film B (tensile elastic modulus 1088 MPa, thickness 125 μm) with a bar coder, An organic glass laminating film having a surface protective layer laminated on an acrylic film was produced. In Comparative Example 2, the resin composition used for forming the surface protective layer and the thickness of the surface protective layer are as shown in Table 1.

[Manufacture of laminated organic glass]
A laminated organic glass was produced by the thermoject method using each organic glass laminating film of Examples 1 to 6 and Comparative Examples 1 and 2 and the following polycarbonate resin A or B. Specifically, first, the acrylic film side of the organic glass laminating film is arranged facing the inside of the mold (injection resin side), the hot platen temperature is set to 350 ° C., and the film becomes 100 ° C. Then, the film was preformed (vacuum molding) so as to conform to the inner shape of the mold, and was tightly attached to the inner surface of the mold. The mold used was a tray-shaped one with a size of 80 mm square, an aperture of 3 mm, and a corner portion 11R. Next, the polycarbonate resin was melted at 310 ° C. and then injected into the mold cavity. Thereafter, after the mold temperature reached 90 ° C., the laminated organic glass in which the polycarbonate layer (thickness 3 mm) and the organic glass laminating film were integrated was taken out.

  In the case of each organic glass laminating film using the acrylic film A, a laminated organic glass is produced using the following polycarbonate resin A as the injection resin, and the organic glass laminating film using the acrylic film B. A laminated organic glass was produced using the following polycarbonate resin B as an injection resin.

Polycarbonate resin A: "Panlite L-1250Z100", MVR: 8cm ^3/10 minutes, Teijin Kasei Co., Ltd. polycarbonate resin B: "Panlite L-1225Z100", MVR: 12cm ^3/10 minutes, Teijin Kasei Co., Ltd.

[Performance evaluation of laminated organic glass]
About the laminated organic glass obtained by each Example and the comparative example, the crushability, moldability, and scratch resistance were evaluated by the method shown below. In addition, about the crushability, it evaluated about the laminated organic glass which used polycarbonate resin A and B as organic glass, and about the moldability and scratch resistance, it evaluated about the laminated organic glass using polycarbonate resin A as organic glass.

<Evaluation of friability>
From the polycarbonate plate side of each laminated organic glass (on the side opposite to the organic glass laminated film), impact is applied using a safety hammer for car escape (commercially available), and the state of the laminated organic glass is observed. The friability was evaluated according to
(Criteria for friability)
○: A crack was observed in the polycarbonate plate.
X: The polycarbonate plate was not cracked.

<Evaluation of formability>
The appearance shape of each laminated organic glass was observed, and the formability was evaluated according to the following criteria.
◎: No appearance defects such as cracking or whitening were observed in the maximum extension part (part with 100% elongation) ○: Although fine cracking or whitening was confirmed in the maximum extension part, shallow drawing Cracks and whitening were not confirmed in the shape part (part having an elongation of 50%), and it was practically acceptable.
X: Appearance defects such as remarkable cracks and whitening were confirmed, which were not acceptable in practice.

<Evaluation of scratch resistance>
Each laminate organic glass was reciprocated 10 times within a range of 10 cm in a state where a load of 1.5 kgf was applied and # 0000 steel wool was pressed against the organic glass lamination film side. Thereafter, the appearance of the laminated organic glass was observed, and scratch resistance was evaluated according to the following criteria.
(Scratch resistance criteria)
○: No scratches were observed on the surface, or fine scratches were observed on the surface, but no significant change in appearance occurred.
Δ: Scratch resistance was improved, but scratches were observed on the surface.
X: Remarkable scratches were generated on the surface, and the appearance was remarkably deteriorated.

[Evaluation results]
The obtained results are shown in Table 1. From this result, the film for laminating an organic glass in which a surface protective layer containing a curable resin is formed on an acrylic film can be provided with crushability in the laminated organic glass, and the moldability when integrally molded with the organic glass Were also confirmed to be good (Examples 1 to 6). Furthermore, it has been clarified that when a surface protective layer is formed using an ionizing radiation curable resin, excellent scratch resistance can be provided (Examples 1, 2, 4 and 5). On the other hand, in the case where the surface protective layer is not formed on the acrylic film (Comparative Example 1) and the case where the surface protective layer made of a plastic resin is formed (Comparative Example 2), crushability can be provided. However, they did not have the physical properties required for automobile windows. In addition, all the laminated organic glass which laminated | stacked the organic glass lamination film of Examples 1-6 on the polycarbonate board was equipped with the intensity | strength strong against the impact from the said film side.

[Footnotes in Table 1]
Resin composition for forming surface protective layer The composition of each resin composition used for forming the surface protective layer is as follows.
(EB1)
Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000): 94 parts by mass Hexafunctional urethane acrylate (weight average molecular weight: 6,000): 6 parts by mass (EB2)
Pentaerythritol tri (meth) acrylate (molecular weight: 298): 40 parts by mass acrylic polymer (weight average molecular weight: 120,000): 60 parts by mass (two-component curable resin)
Acrylic polyol (glass transition temperature: about 90 ° C.): 100 parts by mass xylylene diisocyanate curing agent: 10 parts by mass The above acrylic polyol and xylylene diisocyanate curing agent were mixed and used.
(Thermoplastic resin)
Acrylic resin (containing methyl methacrylate as a constituent monomer): 100 parts by mass

Resin composition for forming primer layer The composition of the two-component curable resin used for forming the primer layer is as follows.
(Two-component curable resin)
Acrylic polyol (glass transition temperature: about 90 ° C.): 100 parts by mass xylylene diisocyanate curing agent: 10 parts by mass The above acrylic polyol and xylylene diisocyanate curing agent were mixed and used.

1 Acrylic film 2 Surface protective layer 3 Injection resin

Claims (5)

At least a surface protective layer containing a curable resin on one side of the acrylic film,
The curable resin is an ionizing radiation curable resin and / or a two-component reaction curable resin,
A film for laminating organic glass, wherein the film is laminated on organic glass for automobile windows.   The film for organic glass lamination of Claim 1 whose thickness of the said acrylic film is 50-300 micrometers. The film for organic glass lamination of Claim 1 or 2 containing a primer layer between the said acrylic film and a surface protective layer. An organic glass and an organic glass laminating film according to any one of claims 1 to 3 are integrated, and at least an organic glass layer, an acrylic film, and a surface protective layer containing a curable resin are sequentially provided. A method for producing laminated organic glass, comprising obtaining laminated organic glass for windows. The manufacturing method of the laminated organic glass of Claim 4 whose thickness of the said acrylic film is 50-300 micrometers.

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