WO2018038101A1 - Resin composition, uncured resin layer, resin film and production method therefor, and laminate production method - Google Patents

Abstract

Provided are a resin composition or the like that comprises a dendrimer-type multifunctional (meth)acrylate having a dendrimer structure, a reactive (meth)acrylate having a weight average molecular weight of 1,000-120,000, and surface-modified inorganic particles.

Description

Resin composition, uncured resin layer, resin film and production method thereof, laminate production method

The present invention relates to a resin composition, an uncured resin layer, a resin film, a manufacturing method thereof, and a manufacturing method of a laminate.

As a method of producing a plastic molded product by providing a hard coat layer on the surface, there are insert molding and vacuum molding.
In insert molding, a film with a hard coat layer is loaded into a mold, molten resin is injected into a cavity, the film and resin are integrated, and a plastic with a hard coat layer provided on the surface A molded product is obtained.
In vacuum forming, heat is applied to the film on which the hard coat layer is formed to soften it, and then the film is pressed against the mold of the desired shape, and the film is brought into close contact by sucking out the air between the film and the mold. This is a molding method for producing a film having a desired shape.
There is also a method of completing a molded body of the hard coat layer formed on the transfer film by a molding method such as IML (In Mold Lamination) or IMD (In Mold Deposition).

Recently, the hard coat layer has been changed from a thermosetting type to an ultraviolet curing type. And the hard-coat layer before shaping | molding is an uncured state which can be ultraviolet-cured, and the after-curing type which UV-irradiates after shaping | molding and is completely cured is known.

Since such a hard coat film is in an uncured state until its molding, stickiness (tack) may occur during handling. In addition, when the hard coat film is wound with a roll or the films are stacked, the components constituting the formed hard coat layer may adhere to the film overlapping the upper surface (blocking).

Therefore, it is common to provide a protective film on the hard coat layer in order to eliminate tack and blocking. However, if the hard coat layer itself has no tack (tack-free property) and has the property of suppressing blocking (blocking resistance), it is not necessary to provide a protective film, and the cost can be reduced.

More recently, it has been used in various applications such as personal computer and home appliance casings, car interiors, car navigation panels, computer peripherals exteriors, cosmetic containers, suitcase housings, plastic lenses and surface protection. A hard coat layer having a specific function is provided.

Therefore, depending on the application, a hard coat layer with higher hardness is required, but in that case, good moldability such as stretchability is also required. Therefore, the after cure type is advantageous for stretchability because it is molded before UV irradiation, and a hard coat layer having a high hardness inherent to the hard coat can be obtained after UV irradiation.

Under such circumstances, various techniques have been proposed for the hard coat film. For example, Patent Document 1 proposes an insert molding film having a hard coat layer formed of an active energy ray-curable resin composition containing a polyfunctional oligomer having a dendrimer structure at a specific ratio. Patent Document 2 proposes a decorative sheet having a hard coat layer formed from an ink composition containing a specific acrylic polymer, an acrylic monomer, and reactive inorganic particles.

Japanese Patent No. 4790065 Japanese Patent No. 5659538

However, Patent Document 1 does not specifically evaluate the tack-free property. Further, in Patent Document 2, a specific acrylic monomer is used in the ink composition for forming the hard coat layer. However, if the ratio of the acrylic monomer is large, there is a concern that the curing shrinkage is increased during after-curing. . When curing shrinkage occurs, problems such as cracking are likely to occur.

As described above, the present invention has been made in view of the above, and is an uncured resin layer that has no stickiness on the surface before curing and is excellent in blocking resistance and stretchability, and has surface hardness and scratch resistance after curing. It aims at providing the uncured resin layer which can be set as the cured resin layer with favorable property. Moreover, it aims at providing the manufacturing method of the resin film which has the said unhardened resin layer, its manufacturing method, and a laminated body.
Furthermore, it aims at providing the resin composition which can form the above uncured resin layers.

The present inventors have found that the above-described problems can be solved by the following present invention, and have completed the present invention.

That is, the present invention is as follows.
[1] A resin composition comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles.
[2] An uncured resin layer comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles.
[3] A resin film having the above-mentioned uncured resin layer on a plastic substrate.
[4] A coating film comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles is formed on a plastic substrate. A resin film comprising: a coating film forming step to be formed on the substrate; and a non-cured resin layer forming step in which the coating film on the plastic substrate is subjected to a drying treatment at a room temperature to 150 ° C. to form an uncured resin layer. Method.
[5] An injection for performing an injection molding process in which the resin film according to [3] is installed in an injection mold, the molding resin is injected into the cavity, and the resin film and the molding resin are integrated. The manufacturing method of the laminated body which includes a shaping | molding process and the active energy hardening process of irradiating an active energy ray with respect to the resin film after the said injection molding process, and performing a hardening process in order.
[6] A transfer molding step in which the resin film according to [3] is heated and softened, is brought into close contact with a predetermined shape mold, and the shape of the predetermined shape mold is transferred onto the surface of the resin film, An active energy ray curing step for sequentially curing the resin film after the transfer molding treatment by irradiating active energy rays.

According to the present invention, it is an uncured resin layer having no surface stickiness before curing, excellent blocking resistance and stretchability, and after curing, a cured resin layer having good surface hardness and scratch resistance. An uncured resin layer that can be provided can be provided. Moreover, the resin film which has the said uncured resin layer, its manufacturing method, and the manufacturing method of a laminated body can be provided. Furthermore, the resin composition which can form the above uncured resin layers can be provided.

Hereinafter, each aspect of the resin composition, the uncured resin layer, the resin film and the production method thereof, and the laminate production method of the present invention will be described. In the present specification, “(meth) acryl” includes both “methacryl” and “acryl”. Furthermore, “(meth) acrylate” includes both “methacrylate” and “acrylate”.

[1] Resin Composition One aspect of the resin composition of the present invention includes a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and Contains surface-modified inorganic particles.

The dendrimer type polyfunctional (meth) acrylate can achieve both good surface hardness and crack resistance. Moreover, tack-free property and blocking resistance can be mainly imparted by reactive (meth) acrylate. Furthermore, the surface-modified inorganic particles can mainly improve tack-free properties and surface hardness.
In one embodiment of the present invention, the mixing of three components of dendrimer-type polyfunctional (meth) acrylate, reactive (meth) acrylate, and surface-modified inorganic particles exhibits different effects and synergistic effects from the case where each is independent. To do.

(1) Dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure Dendrimer-type polyfunctional (meth) acrylate is a resin in which an acrylic group is arranged on a branch part (branch molecule) of a dendrimer (including a hyperbranched polymer). In addition, since the density of the acrylic group is high, the curing rate can be improved. In addition, since the Van del Waals distance between the branch molecules is shorter than that of a normal molecule, the gap between the (meth) acrylic distance before curing and the bonding distance after curing is reduced, and the curing shrinkage unique to (meth) acrylic Can be reduced.

The dendrimer type polyfunctional (meth) acrylate is preferably represented by the following formula (1).

In the above formula (1), l is 1 to 10 and m is 0 to 10. R ^a is a hydrogen atom, an acryloyl group, or a methacryloyl group, and R ^c is either a structure represented by the following formula (1-1) or the following formula (1-2). Not all R ^a are hydrogen atoms.

In the above formulas (1-1) and (1-2), n is 1 to 10, l is 1 to 10, and m is 0 to 10. R ^a has the same meaning as ^{R a} in formula (1), ^{R d} represents a structure represented by formula (1-1).

The weight average molecular weight of the dendrimer type polyfunctional (meth) acrylate is preferably 1,000 to 100,000, more preferably 10,000 to 30,000, and 16,000 to 20,000. More preferably. When the weight average molecular weight is 1,000 to 100,000, the surface hardness and the crack resistance can be more balanced. In particular, compared to the polyfunctional monomer, the intermolecular distance of the cross-linked portion is small and the curing shrinkage is small, so that cracks are unlikely to occur.

The (meth) acryl equivalent of the dendrimer type polyfunctional (meth) acrylate is preferably 80 to 250 g / eq, more preferably 100 to 200 g / eq. By being 80 to 250 g / eq, good tack-free properties and reactivity can be maintained.

The compounds having the structure of the formula (1) are trade names of Biscote # 1000 (Osaka Organic Chemical Co., Ltd.), SIRIUS-501 (Osaka Organic Chemical Co., Ltd.), A-HBR-5 (Shin Nakamura). Chemical Co., Ltd.), New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), SN-2301 (Sartomer Co., Ltd.) and the like.
For example, SIRIUS-501 has dipentaerythritol as a core, and is mainly composed of a multi-branched (dipentaerythritol hexaacrylate (DPHA) -linked) polyacrylate having an acrylate group at the terminal.

(2) Reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000 As the reactive (meth) acrylate, for example, (meth) acrylic acid ester is an essential component, and if necessary, (meth) It can be easily produced by copolymerizing a carboxylic acid group-containing monomer such as acrylic acid, itaconic acid or maleic anhydride, a urethane polymer or a urethane oligomer. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl. (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate And dicyclopentanyl methacrylate. From the viewpoint of obtaining tack-free properties, a reactive thermoplastic resin is preferable.

Moreover, those soluble in organic solvents are preferred from the viewpoint of handleability. Examples of organic solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, methyl cellosolve and ethyl cellosolve. Ether solvents such as toluene, hydrocarbon solvents such as toluene, hexane and cyclohexane, organic solvents such as tetrahydrofuran and mixed solvents thereof can be used, but in consideration of dissolution of thermoplastic resin, ketones, esters, ethers System solvents are preferred.

The reactive (meth) acrylate is not particularly limited as long as it is a solid tack-free and reactive (meth) acrylate resin (for example, an acrylate having a functional group reactive on the polymerized main chain in the side chain). The structure includes, for example, (meth) acryl main chain and side chain with (meth) acryloyl group and / or urethane side chain such as urethane oligomer and urethane polymer, urethane main chain and side chain with urethane oligomer Or those having a (meth) acryloyl group on the urethane main chain and side chain.

When the weight average molecular weight of the reactive (meth) acrylate is less than 1,000 and when it exceeds 120,000, good tack-free property and compatibility are hardly obtained. The weight average molecular weight is preferably 2,000 to 110,000, more preferably 2,000 to 100,000, and further preferably 2,500 to 95,000.
In addition, in this invention, a weight average molecular weight can be calculated | required by the polystyrene conversion value measured by GPC method.

The (meth) acrylic equivalent of the reactive (meth) acrylate is preferably 200 to 2000 g / eq. By being 200 to 2000 g / eq, good tack-free properties and reactivity can be maintained. Here, “(meth) acrylic equivalent” means the molecular weight per (meth) acryloyl group in the (meth) acrylic resin.

(3) Surface-modified inorganic particles The surface-modified inorganic particles have a reactive functional group on the surface of the inorganic particles. Preferred examples of the reactive functional group include ethylenically unsaturated bonds such as vinyl group, (meth) acryloyl group, and allyl group, epoxy group, silanol group, and the like. High hardness and scratch resistance (scratch resistance) From the viewpoint of improving the above, a vinyl group, a (meth) acryloyl group, and an allyl group are more preferable.

Preferred inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, etc., and high hardness and scratch resistance. From the viewpoint of improving the properties, silica particles and alumina particles are preferable, and silica particles are more preferable.

Examples of the shape of the inorganic particles include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and these shapes are preferably uniform and sized.
The average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer to be formed, but is preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.1 μm, and More preferably, the thickness is 01 to 0.03 μm. Here, the average particle diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a cumulative distribution, and is laser diffraction / scattering. It can be measured using the method.

The surface-modified inorganic particles can be obtained, for example, by decorating the surface with a silane coupling agent. Examples of the silane coupling agent include known silane coupling agents having a (meth) acryloyl group, an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group, and the like. Specifically, octenyl Trimethoxysilane, glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl Dimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-a Liloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like are preferable, among which γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, methacryloxyoctyltrimethoxysilane are preferable. More preferred.

The method of decorating the surface of the inorganic particles with the silane coupling agent is not particularly limited and may be any known method, such as a dry method of spraying the silane coupling agent or silane coupling after dispersing the inorganic particles in a solvent. Examples thereof include a wet method in which an agent is added and reacted. And among the above-mentioned, as a surface modification inorganic particle, it is preferable that it is a surface modification silica particle from a practical viewpoint.

The surface-modified inorganic particles are preferably contained in an amount of 50 to 350 parts by mass with respect to 100 parts by mass in total of the dendrimer type polyfunctional (meth) acrylate (solid content) and the reactive (meth) acrylate (solid content). 100 to 350 parts by mass is more preferable, and 180 to 320 parts by mass is further preferable. By containing 50 to 350 parts by mass, tack-free properties and surface hardness can be further improved.

Furthermore, the mass ratio (A: B) of the dendrimer type polyfunctional (meth) acrylate (solid content: A) and the reactive (meth) acrylate (solid content: B) is 1: 7 to 7: 1. Is preferable, and 1: 4 to 3.5: 1 is more preferable. When the ratio is 1: 7 to 7: 1, the surface hardness can be improved without causing curing shrinkage.

(4) Additive (a) Photoinitiator As the photoinitiator, a hydrogen abstraction type photopolymerization initiator and a cleavage type photopolymerization initiator are used. Although it does not specifically limit as a kind of hydrogen abstraction type photoinitiator, Any one of a benzophenone type compound, a thioxanthone type compound, etc., or these 2 or more types of combinations can be mentioned. Although it does not specifically limit as a kind of cleavage type photoinitiator, Any one of a benzoin ether type compound, a benzyl ketal type compound, an acetophenone type compound, etc., or these 2 or more types of combinations can be mentioned.
Although a photoinitiator is not specifically limited, For example, with respect to a total of 100 mass parts of a dendrimer type polyfunctional (meth) acrylate (solid content) and a reactive (meth) acrylate (solid content), it is 0.00. It is preferable to contain 5 to 10 parts by mass.

(B) Leveling agent Examples of the leveling agent include acrylic leveling agents, silicon leveling agents, fluorine leveling agents, silicon / acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicon leveling agents, And leveling agents in which functional groups (for example, alkoxy groups such as methoxy group and ethoxy group, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. Can be mentioned.
The leveling agent is preferably contained in an amount of 0.5 to 6 parts by mass with respect to 100 parts by mass in total of the dendrimer type polyfunctional (meth) acrylate (solid content) and the reactive (meth) acrylate (solid content).

(C) Other additives In addition to the photoinitiator and the leveling agent, an active energy ray-curable monomer and urethane acrylate are added as necessary to provide various functions within the scope of the present invention. Active energy ray curable oligomers such as polyester acrylate and epoxy acrylate, active energy ray curable polymers such as acrylic acrylate, antistatic agents, colorants, silicones, plasticizers, antifoaming agents, antioxidants, UV absorbers, Examples thereof include light stabilizers, coupling agents, organic solvents and chelating agents, inorganic fillers and organic fillers for adjusting the refractive index and preventing crosslinking shrinkage, and tack-free resins having no unsaturated double bonds.

[2] Uncured resin layer One embodiment of the uncured resin layer of the present invention is a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure and a reactivity (meth) having a weight average molecular weight of 1,000 to 120,000. Contains acrylate and surface-modified inorganic particles. That is, the uncured resin layer is a dry coating film formed by applying the resin composition according to one embodiment of the present invention to a plastic substrate or the like and drying it.

Here, each component contained in the uncured resin layer is, for example, in the case of “dendrimer type polyfunctional (meth) acrylate”, in addition to the dendrimer type polyfunctional (meth) acrylate itself, the dendrimer type polyfunctional (meth) acrylate is It has a dendrimer type polyfunctional (meth) acrylate residue, such as a partially reacted reactant, a reaction product of a dendrimer type polyfunctional (meth) acrylate and another resin (for example, reactive (meth) acrylate). Also included. The same applies to “reactive (meth) acrylate” and includes those having the reactive (meth) acrylate residue in addition to the reactive (meth) acrylate itself.

By being uncured, the stretchability can be made mainly good, but the “uncured” in the present invention is a range in which there is no crosslink structure between the respective components or the stretchability is good. In a state in which a crosslinked structure is partially formed, a so-called B-stage state is also included. Specifically, when surface hardness (for example, pencil hardness) is improved by irradiation with active energy rays such as ultraviolet rays or electron beams, the state before the irradiation can be said to be an “uncured” state.
In the present invention, an uncured state can be obtained by performing a drying treatment at room temperature to 120 ° C. without irradiation with active energy rays.

[3] Resin film and production method thereof (1) Resin film One embodiment of the resin film of the present invention has the uncured resin layer described above on a plastic substrate.

The thickness of the uncured resin layer is preferably 0.5 to 100 μm, and more preferably 1 to 20 μm.

Examples of plastic base materials include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, and ethylene / vinyl alcohol copolymer; polyethylene terephthalate, polybutylene Polyester resins such as terephthalate; Acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate; Styrene resins such as polystyrene, acrylonitrile / butadiene / styrene copolymers, cellulose triacetate, cellophane, polycarbonate, Examples include polyurethane-based elastomeric resins; allyl resins such as diethylene glycol bisallyl carbonate, and polysulfide resins.

The thickness of the plastic substrate is preferably 25 to 2000 μm, more preferably 50 to 300 μm, from the viewpoint of moldability and handleability.

(2) Manufacturing method of resin film The one aspect | mode which concerns on the manufacturing method of the resin film of this invention includes the following process one by one.
(I) A coating film comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 200,000, and surface-modified inorganic particles is formed on a plastic substrate. A coating film forming step to be formed.
(Ii) Drying is performed at room temperature (for example, 5 to 35 ° C., more specifically about 25 ° C. The same applies to “room temperature” below) to 150 ° C., and the coating film on the plastic substrate is not yet formed. An uncured resin layer forming step for forming a cured resin layer.
Hereafter, each said process is demonstrated.

(I) Coating film forming step:
A coating film containing a dendrimer type polyfunctional (meth) acrylate, a reactive (meth) acrylate, and surface-modified inorganic particles is first mixed while stirring these three components, and further a photoinitiator, a leveling agent, etc. A resin composition for forming an uncured resin layer is prepared by mixing with an additive.

Details of the dendrimer type polyfunctional (meth) acrylate, reactive (meth) acrylate, and surface-modified inorganic particles are as described above.

Next, an uncured resin layer forming composition is applied onto a plastic substrate to form a coating film. The coating method is not particularly limited, and methods such as dipping, spin coating, bar coating, gravure coating, roll coating, comma coating, die coating, gravure printing, and screen printing can be applied.

(Ii) Uncured resin layer forming step:
There are no particular restrictions on the drying conditions of the uncured resin layer. After forming a coating film from the viewpoint of the type of substrate film and productivity, for example, a drying process is performed at room temperature to 150 ° C. (preferably 50 to 100 ° C.) in a hot air drying furnace equipped with a rotating fan inside the apparatus. Apply. Thereby, the coating film on the plastic substrate becomes an uncured resin layer.
The resin film which concerns on 1 aspect of this invention is manufactured through the above processes.

[4] Manufacturing method of laminated body One aspect | mode which concerns on the manufacturing method of the laminated body of this invention includes the following process one by one.
(I) Injection molding for performing an injection molding process in which the resin film according to one aspect described above is installed in an injection mold, the molding resin is injected into the cavity, and the resin film and the molding resin are integrated. Process.
(Ii) An active energy ray curing step in which an active energy ray is irradiated to the resin film after the injection molding treatment to perform a curing treatment.
Hereafter, each said process is demonstrated.

(I) Injection molding process:
Specifically, the resin film is fed into an injection mold composed of a movable mold and a fixed mold so that the plastic substrate is on the fixed mold side. At this time, the resin films may be fed one by one, or necessary portions of the long resin film may be intermittently fed.

When placing the resin film in the injection mold, (i) simply heat the mold and place it so that it adheres by vacuum suction to the mold, or (ii) a heating plate from the plastic substrate side of the resin film The resin film can be heated and softened, preformed so that the resin film follows the shape in the mold, and clamped to adhere to the inner surface of the mold, and then placed. The heating temperature in (ii) is preferably in the range of not less than the glass transition temperature of the plastic substrate and less than the melting temperature (or melting point), and is usually performed at a temperature in the vicinity of the glass transition temperature. In addition, said glass transition temperature vicinity is the range of about glass transition temperature +/- 5 degreeC. In the case of (ii), vacuum suction may be performed when the resin film is heated and softened with a hot plate for the purpose of bringing the resin film into close contact with the molding die surface.

Next, a molding resin (molten resin) is injected into the cavity, cooled and solidified, and the molding resin and the resin film are laminated and integrated. When the molding resin to be injected is a thermoplastic resin, it is made into a fluid state by heating and melting, and when it is a thermosetting resin, the uncured liquid composition is appropriately heated and injected in a fluid state, and then cooled. And solidify. Thereby, the resin film is laminated and integrated with the formed resin molded body. The heating temperature of the molding resin is generally about 180 to 280 ° C. depending on the type of the resin.

The injection molding resin may be any injection-moldable thermoplastic resin or thermosetting resin (including a two-component curable resin), and various resins can be used. Examples of such thermoplastic resin materials include polystyrene resins, polyolefin resins, acrylonitrile / butadiene / styrene resins (ABS resins) resins (including heat-resistant ABS resins), acrylonitrile / styrene resins (AS resins), acrylonitrile resins ( AN resin), polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, polyphenylene sulfide resins, and the like. Examples of the thermosetting resin include a two-component reaction curable polyurethane resin and an epoxy resin. These resins may be used alone or in combination of two or more.

(Ii) Active energy ray curing process:
After the lamination and integration, the molded body is taken out from the mold and subjected to a curing process using an active energy ray (such as an electron beam and an ultraviolet ray). That is, the uncured resin layer is cured with active energy rays to form a laminate in which a cured resin layer is formed.

When an electron beam is used as the active energy ray, the acceleration voltage can be appropriately selected according to the type and thickness of the resin to be used, but usually about 70 to 300 kV is preferable. The irradiation dose 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). Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. Can be used.

When ultraviolet rays are used as the active energy rays, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted, and the irradiation dose is about 200 to 1500 mJ / cm ² . There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

The other one aspect | mode which concerns on the manufacturing method of the laminated body of this invention includes the following process one by one.
(I) A transfer molding process in which the resin film according to one aspect described above is heated and softened so as to be in close contact with the predetermined shape mold, and the shape of the predetermined shape mold is transferred to the surface of the resin film.
(Ii) An active energy ray curing step in which the resin film after the transfer molding treatment is irradiated with an active energy ray to perform a curing treatment.

In the step (i), the heating temperature for heating the resin film is preferably in the range of near or above the glass transition temperature of the plastic substrate and less than the melting temperature (or melting point). Perform at a temperature near the temperature. In addition, said glass transition temperature vicinity is the range of about glass transition temperature +/- 5 degreeC.

In addition, as a treatment method for closely attaching the resin film to the predetermined shape mold, a vacuum molding process for bringing the resin film and the mold into a vacuum state and bringing the resin film into close contact with the mold, and the resin film with the force of compressed air. An example is a compressed air molding process for tightly contacting the mold.

The step (ii) is the same as the active energy ray curing step of the above-described “one aspect according to the method for producing a laminate of the present invention”.

In either of the one aspect and the other aspect according to the method for producing a laminate of the present invention, the pencil hardness of the cured resin layer after curing is preferably F or more, although it varies depending on the material used. More preferably.

Laminates manufactured as described above take advantage of their superior properties to make the casing of PCs and home appliances, car interiors, car navigation panels, computer peripherals exteriors, cosmetic and pharmaceutical containers, suitcases It can be used for a wide variety of applications such as housings and plastic lenses. Various functional layers such as an antireflection layer and an antiglare layer can also be provided.

Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

(Example 1)
(1) Preparation of composition for forming uncured resin layer Dendrimer polyfunctional (meth) acrylate (SIRIUS-501, manufactured by Osaka Organic Chemical Industry Co., Ltd., weight average molecular weight: 18,700) in a glass container equipped with a magnetic stirrer. , Solid content: 50.5%, dispersion medium: propylene glycol monomethyl ether acetate) 50 parts by mass, reactive (meth) acrylate (SMP-550AP manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight: 30,000, solid content : 49.3%, Dispersion medium: PGME (propylene glycol monomethyl ether), acrylic equivalent: 540 to 560) parts by mass and surface modified silica particles (ELCOM V-8804 JGC Catalysts & Chemicals Co., Ltd.) Manufactured, average particle size: 12 nm, solid content: 40.5%, dispersion medium: PGME) 18 3 parts by mass of Irgacure 184 (manufactured by BASF) as a photoinitiator, and KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 20.4%) as a leveling agent, 6 parts by mass Part was added and stirring was further continued to prepare a resin composition which is an uncured resin layer forming composition. The outline of the composition of the composition is shown in Table 1 below.
The “ratio of inorganic particles” in Table 1 is the ratio (parts by mass) of (surface modification) inorganic particles to 100 parts by mass in total of dendrimer type polyfunctional (meth) acrylate and reactive (meth) acrylate. The same applies to Tables 2 to 4.

(2) Formation of uncured resin layer On a plastic substrate (Cosmo Shine 100A4300 (manufactured by Toyobo Co., Ltd.), material: PET, thickness: 100 μm), an uncured resin layer forming composition is applied with a bar coater. To form a coating film. Then, it was dried at a temperature of 80 ° C. for 1 minute, and an uncured resin layer having a thickness of 9 μm was formed to produce a resin film.

(Evaluation of uncured resin layer (resin film))
(A) Evaluation of stickiness (tack-free property) Whether or not the resin component is attached to the fingertip by placing it on a table so that the uncured resin layer is on the top and flat, touching the surface with a fingertip cleaned with ethyl alcohol Judgment based on criteria. The results are shown in Table 5 below.
○: Not at all.
(Triangle | delta): Although stickiness is slightly felt, there is no problem practically.
X: The sample easily adheres to the finger.

(B) Evaluation of blocking resistance The resin film in which the uncured resin layer is formed and the plastic substrate (the plastic substrate described above) before the uncured resin is formed are each cut into a size of 10 cm ^2. Then, the plastic base material was stacked on the uncured resin layer, and the upper and lower sides were sandwiched between stainless plates, and then a 20 kg weight was placed thereon and left for 5 days. Thereafter, the degree of peeling of the uncured resin layer formed on the resin film and the plastic substrate was determined based on the following criteria. The results are shown in Table 5 below.
○: Can be easily peeled off.
Δ: The uncured resin layer partially remained on the plastic substrate, but there is no problem in practical use.
X: An uncured resin layer remains on the entire surface of the plastic substrate.

(C) Evaluation of stretchability In accordance with the method specified in ASTM-D882 (revised in 1997), the stretch ratio was measured when a resin film cracked under the following conditions using an Instron type tensile tester. The results are shown in Table 5 below. In addition, it is satisfactory if it is 20% or more at 160 ° C., but it is preferably 30% or more.

Measuring device: Orientec Co., Ltd. film strength automatic elongation measuring device Tensilon RTC-1250A
Sample size: width 15 mm x sample length (longitudinal direction) 70 mm
Tensile speed: 200 mm / min Measurement environment: temperature 23 ° C., humidity 65% RH
Stretching temperature: 160 ° C

(3) Formation of cured resin layer On a plastic substrate (Technoloy 125S001G (manufactured by Sumitomo Chemical Co., Ltd.), material: acrylic resin, thickness: 125 μm), an uncured resin layer forming composition is applied with a bar coater. Thus, a coating film was formed. Then, it was dried at a temperature of 80 ° C. for 1 minute, and an uncured resin layer having a thickness of 9 μm was formed to produce a resin film. Thereafter, ultraviolet rays were irradiated using a UV lamp (light hammer, H bulb, manufactured by Heraeus Co., Ltd.) to form a cured resin layer. The integrated light quantity was about 780 mJ / cm ² .

(Evaluation of cured resin layer (cured film))
The following evaluation was performed about the resin film which provided the cured resin layer.
(D) Measurement of surface hardness Cured resin layer in accordance with JISK5600-5-4 using a manual pencil scratch tester for coating film (manufactured by Imoto Seisakusho) and a pencil for scratch hardness test (manufactured by Mitsubishi Pencil Co., Ltd.) The surface pencil hardness was evaluated. The results are shown in Table 5 below. In addition, there is no problem if the surface hardness is F or more, but it is practically preferable that the surface hardness is H or more.

(E) Evaluation of scratch resistance The surface of the cured resin layer was reciprocated 100 times with a load of 1.5 kg with a Gakushin friction and wear tester (manufactured by Tester Sangyo Co., Ltd.), and the degree of scratching was visually observed on the rubbing trace. Observed and evaluated according to the following criteria. The results are shown in Table 5 below.
○: No scratches are visible.
Δ: Slight scratches are visible, but there is no practical problem.
X: Scratches are visible throughout.

(F) Adhesiveness In accordance with JISK5400, a grid of 100 squares with a width of 1 mm was made, the surface of the cured resin layer was peeled off with tape, the number of residual squares was counted, and evaluated according to the following criteria. The results are shown in Table 5 below.
○: 91 squares or more left, no peeling △: 51 to 90 squares left ×: 50 squares or less

(G) Cracks It was visually confirmed whether or not there was a crack in the appearance of the cured resin layer. The results are shown in Table 5 below.
○: There are no cracks.
Δ: Although there are some cracks, there is no problem in practical use.
X: Many cracks can be confirmed.

(H) Appearance of coating liquid (uncured resin layer forming composition) The appearance of the prepared coating liquid was visually confirmed. The results are shown in Table 5 below.
○: Transparent and no turbidity is seen.
Δ: Slight turbidity is observed.
X: opaque and turbid
If the opacity is poor and the turbidity is severe, the coating film also becomes cloudy in the same manner, and it becomes impractical depending on the application.

(Example 2)
Except that the ratio of the surface-modified inorganic particles was changed to 44.55 parts by mass in terms of solid content, the formation of the uncured resin layer and its evaluation, and the formation and evaluation of the cured resin layer were conducted in the same manner as in Example 1. went. The composition is shown in Table 1 below, and the evaluation results are shown in Table 5 below.

(Example 3)
Except that the ratio of the surface-modified inorganic particles was changed to 22.5 parts by mass in terms of solid content, the formation of the uncured resin layer and its evaluation, and the formation of the cured resin layer and its evaluation were carried out in the same manner as in Example 1. went. The composition is shown in Table 1 below, and the evaluation results are shown in Table 5 below.

Example 4
Except for changing the proportion of the surface-modified inorganic particles to 117.45 parts by mass in terms of solid content, in the same manner as in Example 1, the formation and evaluation of the uncured resin layer and the formation and evaluation of the cured resin layer went. The composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.

(Example 5)
Formation of an uncured resin layer and its evaluation, in the same manner as in Example 1, except that the reactive (meth) acrylate was changed to 50 parts by mass and the ratio of the surface-modified inorganic particles was changed to 141.75 parts by mass in terms of solid content. The cured resin layer was formed and evaluated. The composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.

(Example 6)
Reactive (meth) acrylate 50 parts by weight, except that the proportion of the surface-modified inorganic particles was changed to 75.33 parts by weight in terms of solid content, in the same manner as in Example 1, formation of an uncured resin layer and its evaluation, and The cured resin layer was formed and evaluated. The composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.

(Example 7)
Example 1 except that the reactive (meth) acrylate was changed to Art Resin H-108SC (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., molecular weight: 2800, solid content: 50 mass%, solvent: ethyl acetate). Thus, the formation and evaluation of the uncured resin layer and the evaluation and formation of the cured resin layer were performed. The composition is shown in Table 2 below, and the evaluation results are shown in Table 5 below.

(Comparative Example 1)
Except not adding a dendrimer type polyfunctional (meth) acrylate, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer. The composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.

(Comparative Example 2)
Except not adding reactive (meth) acrylate, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer. The composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.

(Comparative Example 3)
Except that the surface-modified inorganic particles were not added, the uncured resin layer was formed and evaluated in the same manner as in Example 1, and the cured resin layer was formed and evaluated. The composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.

(Comparative Example 4)
Except that the reactive (meth) acrylate was changed to DPHA (dipentaerythritol hexaacrylate, DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), the formation of the uncured resin layer and its evaluation, and The cured resin layer was formed and evaluated. The composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below. DPHA corresponds to an acrylic monomer.

(Comparative Example 5)
243 parts by mass of surface-modified inorganic particles, simple silica particles that have not been surface-modified (PGM-ST, Nissan Chemical Industries, Ltd., average particle size: 10-15 nm, solid content: 30% by mass, dispersion medium: PGME) Except having used, it carried out similarly to Example 1, and formed and evaluated the uncured resin layer, and formed and evaluated the cured resin layer. The composition is shown in Table 3 below, and the evaluation results are shown in Table 5 below.

(Example 8)
Example 6 except that the reactive (meth) acrylate was changed to PA-341 (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 6,480, solid content: 50 mass%, solvent: methyl ethyl ketone) Similarly, formation and evaluation of an uncured resin layer and formation and evaluation of a cured resin layer were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.

Example 9
Example 6 except that the reactive (meth) acrylate was changed to PA-359 (urethane acrylate, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 8,304, solid content: 50 mass%, solvent: methyl ethyl ketone). Similarly, formation and evaluation of an uncured resin layer and formation and evaluation of a cured resin layer were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.

(Example 10)
Example except that reactive (meth) acrylate was changed to 8BR-600 (urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 91,000, solid content: 39% by mass, solvent: methyl isobutyl ketone) In the same manner as in Example 6, the formation and evaluation of the uncured resin layer and the formation and evaluation of the cured resin layer were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.

(Example 11)
The reactive (meth) acrylate was changed to 8BR-930MB (urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight: 15,000, solid content: 52 mass%, solvent: methyl isobutyl ketone and methyl ethyl ketone) In the same manner as in Example 6, formation of an uncured resin layer and evaluation thereof, and formation of a cured resin layer and evaluation thereof were performed. The composition is shown in Table 4 below, and the evaluation results are shown in Table 6 below.

The uncured resin layers of Examples 1 to 11 according to the present invention all have good tackiness, blocking resistance, and stretchability, and the cured resin layer obtained by curing this also has surface hardness, scratch resistance, Both adhesion and cracking were good.
On the other hand, in Comparative Examples 1 to 5, it was not possible to satisfy all the evaluation items in the uncured resin layer and the cured resin layer. Moreover, in the comparative example 5, the external appearance of the coating liquid became cloudy white, and it was expected that defects were likely to occur in applications where transparency was required.

Claims (10)

A resin composition comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles. An uncured resin layer comprising a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles. The uncured resin layer according to claim 2, wherein the dendrimer type polyfunctional (meth) acrylate has a weight average molecular weight of 1,000 to 100,000. The uncured resin layer according to claim 2 or 3, wherein the surface-modified inorganic particles are surface-modified silica particles. The surface-modified inorganic particles are contained in an amount of 100 to 350 parts by mass with respect to a total of 100 parts by mass of the dendrimer-type polyfunctional (meth) acrylate and the reactive (meth) acrylate. The uncured resin layer described. 6. The uncured resin layer according to claim 2, wherein the reactive (meth) acrylate is a reactive thermoplastic resin. A resin film having an uncured resin layer according to any one of claims 2 to 6 on a plastic substrate. A coating film including a dendrimer-type polyfunctional (meth) acrylate having a dendrimer structure, a reactive (meth) acrylate having a weight average molecular weight of 1,000 to 120,000, and surface-modified inorganic particles is formed on a plastic substrate. A coating film forming step;
An uncured resin layer forming step in which a drying treatment is performed at room temperature to 150 ° C., and the coating film on the plastic substrate is an uncured resin layer;
The manufacturing method of the resin film which contains sequentially. An injection molding step of performing an injection molding process in which the resin film according to claim 7 is installed in an injection mold, and a molding resin is injected into the cavity to integrate the resin film and the molding resin. ,
An active energy curing step in which the resin film after the injection molding process is irradiated with an active energy ray to perform a curing process;
The manufacturing method of the laminated body containing sequentially. A transfer molding step in which the resin film according to claim 7 is heated and softened, and is brought into close contact with a predetermined shape mold, and the shape of the predetermined shape mold is transferred to the surface of the resin film.
An active energy ray curing step of irradiating an active energy ray to the resin film after the transfer molding treatment and performing a curing treatment;
The manufacturing method of the laminated body containing sequentially.