JP2021049710A - Hard coat resin substrate with elastic body for joining, hard coat substrate joined body, and method for manufacturing hard coat substrate joined body - Google Patents

Abstract

To provide a hard coat resin substrate that can be joined with a molded article base body made of various materials, with a preferable joint strength.SOLUTION: A hard coat resin substrate 1 with an elastic body for joining includes a hard coat layer 112 comprising a curable resin deposited on a part of at least one surface of a resin substrate 111, and an elastic body 12 for joining comprising a thermoplastic resin formed on a part of the surface of the hard coat layer 112.SELECTED DRAWING: Figure 4

Description

The present invention relates to a hard coat resin base material with an elastic body for joining, a hard coat base material joint body, and a method for manufacturing a hard coat base material joint body. In the present specification, the "hard coat base material bonded body" refers to various "hard coat resin base materials" having a hard coat layer on a part of the surface of the resin base material, and various "molded product base materials". It shall refer to all the laminated bodies that are joined to. As a specific example of this "hard coat base material joint body", the "hard coat resin base material with an elastic body for joining" is a window glass with a hard coat layer, and the "molded product base material" is a carbon fiber reinforced resin (CFRP). ) Etc., and the former is joined to the latter, and the joint structure of the automobile window glass can be mentioned as an example.

For example, in a molded product made of a functional resin such as carbon fiber reinforced resin (CFRP), metal, or various other materials, in order to improve the scratch resistance, a hard coat layer is provided on a part of the surface of the molded product. It is widely practiced to provide. Such a hard coat layer is usually formed by coating with a curable resin, transferring with a film with a hard coat layer, or attaching a film with a hard coat layer. Further, as the above-mentioned film with a hard coat layer, a thermal transfer film in which a hard coat layer and an adhesive layer are laminated and integrated on a base film is widely used (see Patent Document 1).

Here, in order to reduce the weight of vehicles whose main purpose is to save energy, there are an increasing number of cases where lighter resin organic glass is used instead of inorganic glass as windows for vehicles such as automobiles (). See Patent Document 2). However, organic glass often does not have sufficient scratch resistance, and when it is used as a window for a vehicle, it is usually essential to provide the above-mentioned hard coat layer on a part of the surface thereof. ..

However, as described in Patent Document 2 (see paragraph [0015] of the same document), when a hard coat layer is provided on the surface layer of the window glass, it is adhered when it is bonded to the vehicle body with an adhesive. Sex tends to be inadequate. Further, depending on the material of the resin forming the hard coat layer, there is a possibility that various adhesives generally used in the past cannot be used. Regarding the joining of the "hard coat resin base material with elastic body for joining" provided with the hard coat layer and various "molded product base materials", a sufficiently preferable joining method has not yet been established, and a patent has been granted. Various joining methods are being sought, including a design change of the laminated structure of the joining portion as disclosed in Document 2.

Japanese Unexamined Patent Publication No. 2014-208493 Japanese Unexamined Patent Publication No. 2018-134750

The present invention is to obtain a hard-coated base material bonded body in which a hard-coated resin base material with an elastic body for bonding provided with a hard-coated layer and a molded product base material made of various materials are bonded with preferable bonding strength. Make it an issue.

When laminating a hard-coated resin base material with an elastic body for bonding provided with a hard-coating layer on a molded product base material, the present inventors interpose a thermoplastic elastic body between the two, and then perform such a method. By a manufacturing method in which an energy wave such as a laser beam is irradiated to the bonding laminate that can be obtained by welding, and the hard coat resin base material with the bonding elastic body, the elastic body, and the molded product base material are integrated by welding. We have found that the above problems can be solved. Then, the present invention including a hard-coated resin base material with an elastic body for bonding, a hard-coated base material bonded body having a structure suitable for this manufacturing method, and a manufacturing method thereof has been completed. More specifically, the present invention provides the following.

(1) For bonding in which a hard coat layer containing a curable resin is laminated on at least one surface of a resin base material, and a part of the surface of the hard coat layer contains a thermoplastic resin. A hard coat resin base material with an elastic body for joining on which an elastic body is formed.

The hard-coated resin base material with an elastic body for bonding (1) is carried out by a method of joining the hard-coated resin base material to a molded product base material made of various materials by applying energy such as electromagnetic waves or heat. It can be suitably used for producing a hard-coated base material bonded body. As a result, a hard-coated base material bonded body in which a hard-coated resin base material with an elastic body for bonding is bonded to a molded product base material made of various materials with necessary and sufficient bonding strength is manufactured under good productivity. can do.

(2) The method according to (1), wherein the hard coat layer is laminated on both surfaces of the resin base material, and the elastic body for bonding is formed on a part of the surface of the hard coat layer. Hard coat resin base material with elastic body for joining.

According to (2) the hard coat resin base material with an elastic body for joining, even in the double-sided hard coat type hard coat resin base material with an elastic body for joining, where it is particularly difficult to maintain the bonding strength to the molded product base, (1). ), It is possible to obtain a hard-coated base material bonded body in which a hard-coated resin base material is bonded to a molded product base material made of various materials with necessary and sufficient bonding strength.

(3) The hard coat resin base material with an elastic body for bonding according to (1) or (2), wherein the thermoplastic resin forming the elastic body for bonding is an olefin elastomer or a polyester elastomer.

According to (3) the hard coat resin base material with an elastic body for bonding, the above-mentioned effects of the hard coat resin base material with an elastic body for bonding according to (1) or (2) can be obtained at a more preferable level. It can be enjoyed with higher accuracy.
(4) The method according to any one of (1) to (3), wherein the bonding elastic body is formed only on an outer frame portion along the outer periphery of the hard coat resin base material with the bonding elastic body. Hard coat resin base material with elastic body for joining.

According to the hard coat resin base material with an elastic body for joining in (4), the opening frame portion where the area of the joint portion on the molded product base side is smaller than the surface area of the hard coat resin base material with an elastic body for joining. In the case of joining to, the hard coat resin base material with elastic body for joining can enjoy the above-mentioned effects of the hard coat resin base material with elastic body for joining any of (1) to (3). It is possible to form a window glass or the like with a hard coat layer by bonding the molded product substrate to the surface with necessary and sufficient bonding strength.

(5) A hard-coated base material joint in which the hard-coated resin base material with an elastic body for bonding according to any one of (1) to (4) is bonded to a molded product substrate via the elastic body for bonding. ..

The hard-coated base material bonded body of (5) is a molded product base material obtained by applying energy such as electromagnetic waves or heat to the hard-coated resin base material with an elastic body for bonding according to any one of (1) to (4). It can be obtained by the method of joining to. This hard coat base material joint body enjoys each of the above-mentioned effects of the hard coat resin base material with an elastic body for joining (1) to (4), and the hard coat resin with an elastic body for joining to the molded product base material. It can be assumed that the base materials are bonded with necessary and sufficient bonding strength.

(6) The hard coat base material joint body in which the hard coat resin base material with an elastic body for joining according to (4) is joined to a molded product base material via the elastic body for joining, and the above. A hard-coated base material joint in which a molded product base has an opening frame, and the hard-coated resin base material with an elastic body for joining is fitted in the opening frame.

The hard-coated base material bonded body of (6) is obtained by the method of joining the hard-coated resin base material with an elastic body for bonding (4) to a molded product base material by applying energy such as electromagnetic waves or heat. Can be done. This hard-coated base material bonded body enjoys each of the above-mentioned effects of the hard-coated resin base material with an elastic body for bonding in (4), and has a surface area of the hard-coated resin base material with an elastic body for bonding. Even when joining to the opening frame portion where the area of the joint portion on the molded product substrate side is narrow, the hard coat resin substrate with elastic body for bonding is bonded to the surface of the molded product substrate with necessary and sufficient bonding strength. be able to.

(7) The hard coat group according to (5) or (6), wherein the main material of the molded product base material is a resin material or a metal material different from the hard coat resin base material with an elastic body for bonding. Material joint.

According to the hard coat base material bonded body of (7), it was difficult to obtain the necessary and sufficient bonding strength by the conventional bonding method using an adhesive, based on the hard coat layer and the amount of different materials. It is possible to obtain a hard-coated base material bonded body in which the molded product base material is bonded to the molded product base material with good bonding strength.

(8) The molded product base is a vehicle base, and the hard coat resin base material with an elastic body for joining is a vehicle window glass, emblem, pillar, front molding, roof, bonnet, door, door trim, seat, or The hard-coated substrate joint according to any one of (4) to (7), which is a front panel or a part of these parts.

According to the hard-coated base material joint of (8), similarly to the hard-coated base material joint of (7), even in the joining of a vehicle joint formed by joining various vehicle parts to the vehicle base. , (4) to (7) can be enjoyed by each of the above-mentioned effects of the hard-coated base material joint body, and the joint strength of various parts to the vehicle base material can be improved.

(9) A method for producing a hard-coated base material bonded body in which a hard-coated resin base material is bonded to a molded product base material, wherein the hard-coated resin base material is one of at least one surface of the resin base material. A hard coat layer containing a curable resin is laminated on the portion, and a joining elastic body containing a thermoplastic resin is formed on a part of the surface of the hard coat layer. A coated resin base material, in which the hard-coated resin base material with an elastic body for bonding is laminated on a part of the surface of the molded product base material with the elastic body for bonding directed toward the surface of the molded product base material. By irradiating the bonding laminate with an energy wave in the laminating step of obtaining the bonding laminate, the hard-coated resin base material with the bonding elastic body is passed through the bonding elastic body to the molded product substrate. A method for producing a hard-coated base material bonded body, which comprises an energy wave irradiation step of bonding to a part of the surface of the hard-coated base material.

In the method for producing a hard-coated base material bonded body according to (9), energy such as electromagnetic waves or heat is applied to the joint portion between the hard coat layer containing a curable resin and the elastic body containing a thermoplastic resin. did. As a result, fine irregularities are formed on a part of the surface of the hard coat layer, and the bonding strength between the hard coat layer and the elastic resistance can be improved by the anchor effect of the fine irregularities. As a result, according to the method for producing a hard-coated base material bonded body (9), a hard-coated resin base material with an elastic body for joining provided with a hard-coated layer and a molded product base material made of various materials are necessary and sufficient. It is possible to obtain a hard coat base material bonded body that is bonded with a high bonding strength.

(10) The method for producing a hard-coated base material bonded body according to (9), wherein the energy wave is laser light.

As the method for producing the hard coat base material joint body of (10), in the production method described in (9), energy is applied to the joint portion between the hard coat layer and the elastic body by irradiation with laser light. As a result, it is possible to efficiently and accurately apply the amount of energy locally required to the joint portion while minimizing the unfavorable influence on the portion other than the joint portion. As a result, according to the method for producing the hard-coated base material bonded body of (10), the quality stability and productivity of the entire hard-coated base material bonded body can be improved while enjoying the above-mentioned effects of the manufacturing method of (9). It can be improved to a more preferable level.

(11) The hard coat group according to (9) or (10), wherein the main material of the molded product base material is a resin material or a metal material different from the hard coat resin base material with an elastic body for bonding. A method for manufacturing a material joint.

According to the method for producing a hard-coated base material bonded body according to (11), it is difficult to obtain the necessary and sufficient bonding strength by the conventional bonding method using an adhesive. It is possible to obtain a hard-coated base material bonded body in which a molded product base material made of a material amount is bonded with good bonding strength.

(12) The method for producing a hard-coated base material bonded body according to any one of (9) to (11), wherein the thermoplastic resin forming the elastic body for bonding is an olefin-based elastomer or a polyester-based elastomer.

According to the method for producing a hard-coated base material bonded body according to (12), the above-mentioned effects of the method for producing a hard-coated base material bonded body according to any one of (9) to (11) can be more preferably obtained at a more preferable level. It can be enjoyed with high accuracy.

(13) Any of (9) to (12), wherein the molded product substrate has an opening frame, and in the laminating step, the hard coat resin substrate with an elastic body for joining is fitted into the opening frame. A method for producing a hard-coated substrate bonded body according to the above.

According to the method for producing a hard-coated base material joint body according to (13), the area of the joint portion on the molded product base side is narrower than the surface area of the hard-coated resin base material with an elastic body for joining. In the joining of the above, the molded product base material of the hard coat resin base material with an elastic body for joining can be enjoyed by enjoying the above-mentioned effects of the method for producing the hard coat base material joint body according to any one of (9) to (12). Bonding to the surface can be performed with necessary and sufficient bonding strength.

(14) The molded product base is a vehicle base, and the hard coat resin base material with an elastic body for joining is a vehicle window glass, emblem, pillar, front molding, roof, bonnet, door, door trim, seat, or The method for manufacturing a hard-coated base material joint according to any one of (9) to (13), which is a part of the front panel or parts thereof.

According to the method for manufacturing a hard coat base material joint body of (14), similarly to the manufacturing method of (13), in the joining of a vehicle joint body formed by joining various vehicle parts to the vehicle base material, the joint body is also used. By enjoying the above-mentioned effects of the hard coat manufacturing method according to any one of (9) to (13), it is possible to improve the bonding strength of various parts to the vehicle substrate.

According to the present invention, a hard coat base material bonded body in which a hard coat resin base material with an elastic body for bonding provided with a hard coat layer and a molded product base material made of various materials are bonded with preferable bonding strength is obtained. be able to.

In order to explain an embodiment of the method for producing a hard-coated base material bonded body of the present invention, the hard-coated base material bonded body is decomposed into a molded product base material and a hard-coated resin base material with an elastic body for bonding. It is an exploded perspective view shown by. It is a drawing which shows typically the embodiment of the energy wave irradiation process performed in the manufacturing method of the hard coat base material bonded body of this invention. FIG. 2 is a cross-sectional view of the hard-coated base material bonded body shown in FIG. 2, which is a drawing schematically showing a layer structure of a portion irradiated with an energy wave such as a laser beam when the manufacturing method of the present invention is carried out. It is sectional drawing which shows typically the layer structure of the hard coat resin base material with elastic body for bonding which comprises the hard coat base material joint body of this invention. It is a top view which shows typically the structure of the hard coat resin base material with an elastic body for bonding which comprises the hard coat base material joint body of this invention. It is an enlarged photograph by a laser microscope of the surface of the fine unevenness formed in the hard coat layer of the hard coat resin base material with an elastic body for bonding. (Note that the rectangular frame in the figure indicates the region that was joined to the molded product substrate via the elastic body.)

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The present invention can be carried out with appropriate modifications within the scope of the object.

<Hard coat resin base material with elastic body for joining>
As shown in FIG. 3, the hard-coated resin base material 1 with an elastic body for bonding of the present invention is integrated with the molded product base material 2 to form the hard-coated base material bonded body 10 of the present invention. It is a material.

As shown in FIG. 4, the hard-coated resin base material 1 with an elastic body for bonding contains a curable resin on at least one surface of a resin base material 111 that constitutes a main portion as a skeleton portion thereof. In the hard coat resin base material 11 provided with the hard coat layers 112 and 113, a bonding elastic body 12 containing various thermoplastic resins is further formed on the hard coat layers 112 and 113. Is the minimum basic configuration.

Further, the hard coat resin base material 11 constituting the hard coat resin base material 1 with an elastic body for bonding has a structure in which hard coat layers 112 and 113 are provided on both sides of the resin base material 111 as shown in FIG. It may be. In this case, the elastic body 12 for joining is formed on one of the hard coat layers 112 and 113. Each of these hard coat layers 112 and 113 functions as a surface protective layer of the resin base material 111 in the hard coat resin base material 1 with an elastic body for bonding and the hard coat base material joint body 10 using the same.

When the hard-coated resin base material 1 with an elastic body for bonding has any of the above-mentioned layer configurations, when it is bonded to the molded product base material 2 to form the hard-coated base material bonded body 10, it is bonded. The hard-coated resin base material 1 with an elastic body for bonding is bonded to the molded product base 2 with the elastic body 12 for bonding facing the surface of the molded product base 2.

The hard coat layers 112 and 113 are usually provided with an adhesive layer (usually, an adhesive layer for maintaining the necessary adhesion between the resin base material 111 and the hard coat layers 112 and 113 on the side serving as an interface with the resin base material 111. (Not shown) is further provided. This adhesive layer is preferably a two-layer adhesive layer in which a primer layer and a heat seal layer are arranged in order from the side of the hard coat layers 112 and 113 (see Patent Document 1).

The elastic body 12 for joining is formed on a part of the surface of the hard coat layers 112 and 113. The portion forming the elastic body 12 for bonding is not limited to a specific portion, but when the hard-coated resin substrate 1 with the elastic body for bonding is bonded to the molded product substrate 2 as the hard-coated substrate bonding body 10. A portion to be a joint surface between the hard-coated resin base material 11 and the molded product base material 2 may be assumed and appropriately formed in the portion required for that purpose.

For example, as shown in FIG. 5, a hard-coated resin base material 1 with an elastic body for joining, wherein the elastic body 12 for joining is formed only on an outer frame portion along the outer periphery of the hard-coated resin base material 11. It can be mentioned as an example of a preferred embodiment of the invention. In this case, as shown in FIGS. 1 and 2, for example, a hard coat resin group is formed by joining the bonding elastic body 12 formed only on the outer frame portion to the outer edge of the opening frame of the molded product base 2. The material 11 can form a window glass for a vehicle with a hard coat, which is formed by being fitted to an opening frame of a molded product base which is a part of a vehicle or the like.

The overall shape of the hard coat resin base material 1 with an elastic body for bonding is typically flat, but is not limited to this, and can be appropriately selected depending on the intended use. For example, the present invention can also be applied when various resin members molded into a shape including a curved surface are used as a hard coat resin base material with an elastic body for joining.

(Resin base material)
As the resin base material 111 constituting the hard coat resin base material 1 with an elastic body for bonding, a resin base material containing various resins as a main material can be appropriately selected depending on the intended use. However, organic glass can be particularly preferably used as the resin base material 111 constituting the hard coat resin base material 1 with an elastic body for bonding. The "organic glass" in the present invention is defined as "organic glass" in JIS R3211: 2015, and is composed of a material and a layer structure similar thereto, and can similarly exhibit the effects peculiar to the present invention. Let's say things. As a typical specific example of "organic glass", a hard synthetic resin mainly made of a polycarbonate resin can be mentioned.

From the viewpoint of transparency required when the hard-coated resin base material 1 with an elastic body for bonding is assumed to be used as a window glass for a vehicle, the resin base material 111 includes a polycarbonate resin, an acrylic resin, or a polyester. A resin base material using a resin or the like as a main material can be preferably used. Further, among these, since it is excellent in impact resistance, a resin base material mainly made of polycarbonate resin is particularly preferably used as the resin base material 111 constituting the hard coat resin base material 1 with an elastic body for bonding according to the present invention. be able to.

(Hard coat layer)
The hard coat layers 112 and 113 are layers made of a resin composition containing a curable resin (hereinafter, also referred to as “curable resin composition”). The hard coat layers 112 and 113 maintain good scratch resistance on the surface of each base material and the joint body in the hard coat resin base material 1 with an elastic body for bonding and the hard coat base material joint body 10.

As the curable resin used as the main material of the curable resin composition forming the hard coat layers 112 and 113, a thermosetting resin or an ionizing radiation curable resin can be appropriately selected and used.

When a thermosetting resin is used as the base resin of the curable resin composition for forming the hard coat layers 112 and 113, polyester resin, epoxy resin, polyurethane resin, aminoalkyd resin, melamine resin, guanamine resin, urea resin, etc. A thermosetting resin such as a thermosetting acrylic resin can be used.

When an ionizing thermosetting resin is used as the base resin of the curable resin composition for forming the hard coat layers 112 and 113, a polymerizable oligomer or prepolymer conventionally used as a resin having ionizing radiation curability It can be appropriately selected from the above and used. Examples of such polymerizable oligomers and prepolymers include oligomers and prepolymers having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based and polyether-based urethane (meth). ) Oligomers, caprolactone-based urethane (meth) acrylates, polyester (meth) acrylate-based oligomers, polyether (meth) acrylate-based oligomers, prepolymers, and the like can be preferably used.

When an ionizing radiation curable resin is used as the curable resin for forming the hard coat layers 112 and 113, the ionizing radiation irradiating these resins may polymerize or crosslink the molecules of an electromagnetic wave or a charged particle beam. Those having an energy quantum, for example, ultraviolet rays (UV) or electron beams (EB) can be selected. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays can also be selected.

Further, the curable resin composition can contain a silicone compound from the viewpoint of improving weather resistance and hard coatability and obtaining excellent transparency. The silicone compound includes a reactive silicone compound having a reactive functional group such as an amino group, an epoxy group, a mercapto group, a carboxy group, a hydroxy group, a (meth) acryloyl group and an allyl group, or a reactive functional group thereof. Any non-reactive silicone compound that does not can be used.

Further, the curable resin composition forming the hard coat layers 112 and 113 preferably further contains a scratch resistant filler and a weather resistant agent in order to further improve the hard coat property and the weather resistance. Scratch-resistant fillers that can be contained in the hard coat layers 112 and 113 include inorganic and organic fillers. Inorganic substances include inorganic particles such as alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Can be mentioned. Among these inorganic scratch-resistant fillers, silica particles are one of the preferable ones. This is because the silica particles improve the hard coat property and do not impair the transparency of the hard coat layer. As the silica particles, conventionally known silica particles can be appropriately selected and used, and colloidal silica particles and the like can also be preferably mentioned. Colloidal silica particles have little effect on transparency even when the amount added is increased.

Further, the curable resin composition used for forming the hard coat layers 112 and 113 preferably contains a weather resistance improving agent in order to obtain excellent weather resistance. Examples of the weather resistant agent include an ultraviolet absorber, a light stabilizer, and the like. The ultraviolet absorber absorbs harmful ultraviolet rays and improves the long-term weather resistance and stability of the hard coat base material bonded body. Further, although the light stabilizer itself hardly absorbs ultraviolet rays, stabilization can be obtained by efficiently capturing harmful free radicals generated by ultraviolet rays. Examples of the ultraviolet absorber include inorganic ones such as titanium dioxide, cerium oxide and zinc oxide, and benzotriazole-based and triazine-based organic ultraviolet absorbers, and among them, triazine-based ultraviolet absorbers are preferable. Further, as the light stabilizer, for example, a hindered amine-based light stabilizer (HALS) is preferably mentioned.

Further, the curable resin composition forming the hard coat layers 112 and 113 can contain various additives as long as the performance is not impaired. The various additives include, for example, polymerization inhibitors, cross-linking agents, antistatic agents, adhesive improvers, antioxidants, leveling agents, thixophilic imparting agents, coupling agents, plasticizers, defoaming agents, fillers, etc. It is a solvent or the like.

(Elastic body for joining)
The elastic body 12 for bonding can be formed by using a resin film obtained by forming various thermoplastic resins into a film. The resin film has elasticity that can be welded to the hard coat layer 112 of the hard coat resin base material 1 with an elastic body for bonding and the molded product base material 2 and can form an elastic resin layer at the joint portion between the two. If it is a material, from the optimum resin material as appropriate according to the material of the hard coat resin base material 1 with an elastic body for joining and the molded product base material 2, and the method of performing energy irradiation for integrating these. Can be selected.

In the joint portion between the hard coat layer 112 of the hard coat resin base material 1 with an elastic body for joining and the molded product base 2, the thermoplastic resin used as the main material of the elastic body 12 for joining to be arranged between the two is polyethylene. Resins, polypropylene resins, polybutene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymer resins, etc., or various olefin-based elastomers or polyester-based elastomers based on any of them. Appropriately select from styrene-based elastomer, vinyl chloride-based elastomer, chlorinated polyethylene-based elastomer, chlorosulphonized ethylene-based elastomer, polyurethane-based elastomer, polyamide-based elastomer, silicone rubber-based elastomer, acrylic rubber-based elastomer, fluororubber-based elastomer, etc. Can be done. Among these, an olefin-based elastomer or a resin film made of a polyester-based elastomer can be particularly preferably used as the elastic body 13.

(Manufacturing method of hard coat resin base material with elastic body for bonding)
The hard coat resin base material 1 with an elastic body for bonding is first produced by transferring a transfer hard coat film laminate as disclosed in Patent Document 1 onto a resin base material 111 via an adhesive layer. After obtaining the hard coat resin base material 11, it can be manufactured by forming a bonding elastic body 12 on an arbitrary portion on the hard coat layer 112 of the hard coat resin base material 11.

In the above-mentioned hard coat film laminate for transfer, a hard coat resin base material 1 with an elastic body for bonding and a base film which is a support base material for supporting the hard coat resin base material 1 with an elastic body for bonding are laminated. It is a resin film. The hard coat resin base material 1 with an elastic body for bonding constituting the hard coat film laminate for transfer is transferred to a part of the surface of the resin base material 111 made of organic glass or the like to form the hard coat layers 112 and 113. Will be done.

Further, the above-mentioned forming of the elastic body 12 for joining is described even when, for example, a frame-shaped layer is formed on the outer edge portion of the hard coat resin base material with a predetermined width in a plan view as shown in FIG. A hard coat film laminate for transfer can be preferably used. In this case, first, the elastic body for joining is trimmed and arranged in a matching shape, or is arranged in a strip shape in a frame shape. Next, it is sandwiched and fixed by a high melting point material such as metal (specifically, aluminum or SUS) from the upper part, and then a laser beam is irradiated from the hard coat resin base material side to form a part on the hard coat layer. A hard coat resin base material with an elastic body for bonding can be obtained by adhering an elastic body for bonding. Since the energy required for bonding differs between the hard-coated resin base material and the metal (aluminum, SUS, etc.), a low-energy condition is used so that the elastic body for bonding adheres only to the hard-coated resin base material.

<Hard coat base material joint>
As shown in FIG. 3, the hard-coated base material bonded body 10 of the present invention is for bonding in which the hard-coated resin base material 11 constituting the hard-coated resin base material 1 with an elastic body for bonding contains a thermoplastic resin. It is a bonded body having a structure in which it is bonded to the molded product substrate 2 with an elastic body 12 interposed therebetween. The technical scope of the hard-coated substrate joint of the present invention includes all vehicles, structures, and other structures having substantially the same layer structure, including a portion having such a structure.

[Molded product base]
The type of the member used as the molded product base 2 constituting the hard coat base material joint 10 is not particularly limited. Hard coat properties such as scratch resistance are required. For example, windows of various vehicles such as automobiles, other interior and exterior parts, solar cell covers or solar cell substrates, building structures of general residences and public facilities. Exterior materials, interior materials, members of home appliances, etc. can be widely used as molded product substrates.

However, the present invention is particularly superior to the conventional method when the molded product base 2 is made of a resin material or a metal material different from that of the hard coat resin base material 1 with an elastic body for bonding. Expresses in. From such a viewpoint, the material of the molded product base 2 is more preferably a resin material or a metal material different from that of the hard coat resin base material 1 with an elastic body for bonding. The resin material different from the hard-coated resin base material 1 with an elastic body for bonding means a resin material different from the main resin materials forming the resin base material 111 and the hard coat layers 112 and 113. However, in particular, a material different from the main resin material forming the hard coat layers 112 and 113, which hinders the improvement of the bonding strength, is a more important requirement for the manifestation of the above-mentioned superiority.

Specific examples of the resin constituting the molded product substrate 2 include functional resins such as the carbon fiber reinforced resin (CFRP) described above, polyolefins such as polypropylene commonly used as molded products, and acrylonitrile-butadiene-. A styrene copolymer or the like can be mentioned as a typical example. Specific examples of the metal constituting the molded product substrate 2 include aluminum, stainless steel, iron, magnesium, titanium and the like. The shape of the molded product base 2 can be appropriately selected according to the intended use of the molded product, and is not limited to the plate shape. Further, it is more preferable that the molded product base 2 has an opening frame for fitting the hard coat resin base material 1 with an elastic body for joining. Even in such an embodiment in which the joint surface is relatively narrow, the present invention can sufficiently improve the joint strength between the hard-coated resin base material 1 with an elastic body for joining and the molded product base material 2. Is.

[Vehicle joint]
The hard coat base material joint 10 is preferably used as a vehicle joint, specifically, a vehicle window glass, emblem, pillar, front molding, roof, bonnet, door (particularly back door or side). Exterior parts such as doors, interior parts such as door trims, seats, and front panels, or hard-coated resin base materials 1 with elastic bodies for joining that form part of these parts are used for vehicles as molded parts bases 2. It can be carried out as a bonded body bonded to a substrate. According to these embodiments, it is possible to provide a joint body in which various parts are firmly bonded to a vehicle substrate for vehicle use.

Further, as an example of a particularly preferable embodiment of the hard coat base material joint body 10, a vehicle window glass joint in which a vehicle window glass is made of organic glass and the same is bonded to the vehicle base material can be mentioned. it can. In this case, the organic glass constituting the window glass for the vehicle corresponds to the hard coat resin base material 1 with an elastic body for joining which constitutes the hard coat base material joint body 10, and similarly, carbon fiber reinforced resin, aluminum, etc. The vehicle substrate made of various metals of the above corresponds to the molded product substrate 2. In this case, the contour of the hard coat resin base material 1 with an elastic body for joining used as a window glass for a vehicle is aligned with the outer edge of the opening (window frame or the like) of the molded product base 2 which is the base for the vehicle. The hard-coated base material joint body 10 of the present invention can be applied to a window glass joint body for a vehicle by fitting it into a window glass joint body of the present invention.

The hard-coated base material joint 10 can be widely applied as a window glass for a vehicle to a back window, a front window, a side window of an automobile, a skylight for a sunroof, and a window of a vehicle other than an automobile. And, it can be widely applied to the bonding of other members with a hard coat layer to a substrate.

[Manufacturing method of hard coat base material joint]
The hard-coated base material bonded body of the present invention can be manufactured by a manufacturing method in which a laminating step and an energy wave irradiation step described in detail below are sequentially performed.

(Laminating process)
In the laminating step, for example, as schematically shown in FIG. 1, the hard coat resin base material 1 with an elastic body for joining is placed on the molded product base 2 with the elastic body 12 for joining directed toward the surface of the molded product base 2. This is the process of laminating. The laminate thus obtained is used as a bonding laminate constituting the hard coat base material bonding body 10, and is integrated by subjecting it to an energy wave irradiation step, which is the next step.

Instead of the hard-coated resin base material 1 with the elastic body for joining, a hard-coated resin base material having no elastic body 12 for joining is used, and after undergoing a step of arranging the elastic body for joining on the molded product base side, After that, it is also possible to obtain the above-mentioned bonding laminate by laminating the hard coat resin base material. However, in terms of productivity, it is significantly significant to use the hard coat resin base material 1 with an elastic body for joining because the number of external setup steps can be reduced and the accuracy of the elastic body placement position can be easily improved. ..

(Energy wave irradiation process)
In the energy wave irradiation step, for example, in the manner schematically shown in FIGS. 2 and 3, the joining elastic body 12 is molded by irradiating the above-mentioned joining laminate obtained in the lamination step with an energy wave. This is a step of joining the hard coat resin base material 1 with an elastic body for joining and the molded product base 2 via the elastic body 12 for joining by welding to the surface of the product base 2. In the embodiment shown in FIG. 3, the laser beam L is irradiated from the hard coat resin base material 1 side with an elastic body for bonding, but it is irradiated from the molded product base 2 side depending on the type of the molded product base 2. It may be.

The energy wave used in this energy wave irradiation step can apply various energies such as light, heat, and electric energy that can be bonded to the bonding surface of the bonding laminate in a controllable and appropriate amount. If so, it is not limited to a specific energy wave. However, as shown in FIG. 2, a method of locally irradiating the joint portion with the laser light L by the laser light irradiation device 20 is particularly preferable as the embodiment of the present invention.

In the hard-coated base material bonded body manufactured by the production method of the present invention, fine irregularities (not shown in FIGS. 1 to 5) are formed on substantially the entire surface of the joint portion between the hard coat layer 112 and the elastic body 12 for bonding. , See FIG. 6) is formed. It is preferable that the fine irregularities are present only on the surface of the hard coat layer 112 on which the elastic body 12 for bonding is formed in the hard coat base material joint body 10. The fine irregularities in such an embodiment can be intentionally formed by the above-mentioned manufacturing method.

Due to the presence of the above-mentioned fine irregularities in the joint portion with the elastic body 12 for bonding which is a part of the surface of the hard coat layer 112, the fine irregularities which are a part of the hard coat layer 112 made of the curable resin composition. The convex portion of the above bites into the inside of the elastic body 12 for joining made of a thermoplastic resin, and an anchor effect that cannot be exhibited in the absence of such fine irregularities 121 is exhibited. As a result, the bonding strength at this interface can be significantly improved as compared with the so-called dry lamination with a conventional adhesive.

In order to more reliably enjoy the above-mentioned anchoring effect that contributes to the improvement of the bonding strength on the bonding surface including the surface of the hard coat layer 112, the fine unevenness has a surface roughness Ra of 0.1 μm or more and 500 μm or less. It is preferable to have. The presence of irregularities of an appropriate size significantly improves the joint strength. The surface roughness Ra of the fine unevenness 121 is more preferably 0.5 μm or more and 100 μm or less, and further preferably 1 μm or more and 20 μm or less. The "surface roughness Ra" in the present specification refers to a part of the surface of the hard coat layer 112 exposed by peeling off the molded product base 2 and the elastic body 12 for joining, and is defined as New View 5000 (manufactured by Zygo). The surface shape in the range of 1000 μm × 1000 μm was imaged with an objective lens: 10 times, a zoom lens: 1 times, and a Scan Lens: 15 μm, and calculated from an image obtained in accordance with JIS B 0601: 2001. It is a value obtained by calculating the deviation of the average from the center line of the roughness curve.

Further, the average pitch between the convex portions of the fine irregularities is preferably 1 μm or more and 1000 μm or less, more preferably 10 μm or more and 500 μm or less, and further preferably 25 μm or more and 200 μm or less. Regarding the "average pitch between the convex portions" in the present specification, a part of the surface of the hard coat layer 112 exposed by peeling off the molded product base 2 and the elastic body 12 for bonding is observed with a laser microscope. The value obtained by this is used.

In the energy wave irradiation step performed at the time of carrying out the above manufacturing method, the hard coat layer is formed by appropriately adjusting the intensity of the energy to be irradiated (the product of the irradiation amount and the irradiation time) according to the material amount resin of the hard coat layer. The surface roughness Ra of the above-mentioned fine irregularities formed in the above, the density of the convex portions, and the like can be controlled within the above-mentioned desired preferable range.

<Joint strength test>
In the hard-coated base material bonded body of the present invention, in order to confirm whether or not the hard-coated layer made of a curable resin can have sufficient bonding strength with respect to the facing surface in the laminated body, under different irradiation conditions. "Tensile shear adhesion strength test (based on JIS K6850)" was performed on two samples (Examples 1 and 2) obtained by irradiating with laser light. As the test conditions, the measurement temperature was 23 ° C. and the tensile speed was 10 mm / min. The results are as shown in Table 1.

[Preparation of sample]
(Hard coat resin base material with elastic body for joining)
"Organic glass with a hard coat layer" in which a hard coat layer formed by curing an acrylate-based oligomer is provided on both sides of an organic glass made of polycarbonate (100 mm x 50 mm, thickness 4 mm) is used as a hard coat resin base material. There was. A polyester resin-based thermoplastic elastomer (“Hytrel HTD-741H” (manufactured by Toray DuPont)) is formed on a part of one of the hard coat layers of the hard coat resin base material to a thickness of 200 μm. The obtained resin film (10 mm × 25 mm) is placed, sandwiched between aluminum from above, fixed with a jig, and then irradiated with laser light from the hard coat resin base material side to form a part of the hard coat layer with elasticity for bonding. A body was formed, and a hard coat resin base material material with an elastic body for bonding was obtained. The laser irradiation condition was set to 0.2 kW-0.3 kW so as to adhere only to the hard coat resin base material.
(Lamination and laser irradiation)
Lamination obtained by laminating the above-mentioned "hard-coated resin base material with elastic body for bonding" and the above-mentioned hard-coated resin base material on which the elastic body for bonding is not formed with the elastic body for bonding facing. The bodies were integrated by melt bonding by irradiation with laser light. In each of the examples, the same laminate was used, and only the irradiation conditions of the laser beam were changed for each example. The irradiation conditions of the laser light for each example were such that the irradiation time was 1 second and the irradiation amount was as shown in Table 1.

<Evaluation of fine irregularities on the surface of the hard coat layer>
For a part of the surface of the hard coat layer of each example after peeling the elastic body for bonding in the above bonding strength test, using New View 5000 (manufactured by Zygo), the objective lens: 10 times, zoom lens: 1. The surface shape in the range of 1000 μm × 1000 μm is imaged at fold, Scan Lens: 15 μm, and the average deviation from the center line of the roughness curve calculated from the image obtained in accordance with JIS B 0601: 2001 is calculated. Therefore, the surface roughness Ra was obtained. The results are as shown in Table 1.

Further, using a laser microscope (manufactured by KEYENCE Corporation, magnification 10 times), the region of the surface of the hard coat layer of Example 1 that was bonded to the organic glass via the elastic body and the region that was not bonded were used. The boundary part was observed and imaged. FIG. 6 shows the obtained observation image.

From Table 1, it can be seen that the bonding strength with the molded product substrate made of various materials can be significantly improved by using the hard-coated resin substrate with an elastic body for bonding of the present invention.

The hard coat resin base material with an elastic body for joining of the present invention, which has such excellent characteristics in terms of joining strength, has an elastic body for joining in which the elastic body for joining is integrally formed on the base material side in advance. By using the hard-coated resin base material, it is not necessary to arrange and form a layer for ensuring sufficient bonding strength when the hard-coated resin base material is bonded to the molded product base material. It can greatly contribute to the improvement of productivity related to the production of the bonded body.

1 Hard coat resin base material with elastic body for bonding 11 Hard coat resin base material 12 Elastic body for bonding 111 Resin base material 112, 113 Hard coat layer 2 Molded product base 10 Hard coat base material joint body 20 Laser light irradiation equipment L Laser light

Claims (14)

A hard coat layer containing a curable resin is laminated on at least one surface of a resin base material, and a bonding elastic body containing a thermoplastic resin is formed on a part of the surface of the hard coat layer. A hard coat resin base material with an elastic body for joining is formed. The hard coat layer is laminated on both sides of the resin base material.
The bonding elastic body is formed on a part of the surface of any of the hard coat layers.
The hard coat resin base material with an elastic body for joining according to claim 1. The hard coat resin base material with an elastic body for bonding according to claim 1 or 2, wherein the thermoplastic resin forming the elastic body for bonding is an olefin elastomer or a polyester elastomer. The bonding elastic body is formed only on the outer frame portion along the outer periphery of the hard coat resin base material with the bonding elastic body.
The hard coat resin base material with an elastic body for joining according to any one of claims 1 to 3. A hard-coated base material bonded body in which the hard-coated resin base material with an elastic body for bonding according to any one of claims 1 to 4 is bonded to a molded product substrate via the elastic body for bonding. A hard-coated base material bonded body in which the hard-coated resin base material with an elastic body for bonding according to claim 4 is bonded to a molded product substrate via the elastic body for bonding.
The molded product substrate has an opening frame and
A hard coat base material joint body in which the hard coat resin base material with an elastic body for joining is fitted in the opening frame. The hard-coated base material bonded body according to claim 5 or 6, wherein the main material of the molded product base material is a resin material or a metal material different from the hard-coated resin base material with an elastic body for bonding. The molded product base is a vehicle base, and the hard coat resin base material with an elastic body for joining is a vehicle window glass, emblem, pillar, front molding, roof, bonnet, door, door trim, seat, or front panel. Alternatively, the hard-coated base material joint according to any one of claims 4 to 7, which is a part of these parts. A method for producing a hard-coated base material bonded body, in which a hard-coated resin base material is bonded to a molded product base material.
In the hard coat resin base material, a hard coat layer containing a curable resin is laminated on a part of at least one surface of the resin base material, and a thermoplastic resin is applied to a part of the surface of the hard coat layer. A hard-coated resin base material with a bonding elastic body on which a bonding elastic body is formed.
Lamination to obtain a bonding laminate by laminating the hard-coated resin substrate with a bonding elastic body on a part of the surface of the molded product substrate with the bonding elastic body directed toward the surface of the molded product substrate. Process and
By irradiating the bonding laminate with an energy wave, the energy wave irradiation for joining the hard coat resin base material with an elastic body for bonding to a part of the surface of the molded product substrate via the elastic body for bonding. Including the process,
A method for manufacturing a hard-coated base material joint. The method for producing a hard-coated base material bonded body according to claim 9, wherein the energy wave is laser light. The production of the hard coat base material bonded body according to claim 9 or 10, wherein the main material of the molded product base material is a resin material or a metal material different from the hard coat resin base material with an elastic body for bonding. Method. The method for producing a hard-coated base material bonded body according to any one of claims 9 to 11, wherein the thermoplastic resin forming the elastic body for bonding is an olefin-based elastomer or a polyester-based elastomer. The molded product substrate has an opening frame and
The method for producing a hard-coated base material bonded body according to any one of claims 9 to 12, wherein in the laminating step, the hard-coated resin base material with an elastic body for bonding is fitted into the opening frame. The molded product base is a vehicle base, and the hard coat resin base material with an elastic body for joining is a vehicle window glass, emblem, pillar, front molding, roof, bonnet, door, door trim, seat, or front panel. Alternatively, the method for producing a hard-coated base material joint according to any one of claims 9 to 13, which is a part of these parts.

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