JP5869428B2 - Transfer material and method for producing polycarbonate resin laminate - Google Patents

Description

  The present invention relates to a manufacturing apparatus, a processing machine, a casing or cover material for electrical equipment, a transport machine for automobiles, ships, airplanes, etc., window materials for various buildings such as houses, decorative panels for interiors / exteriors, carports, The present invention relates to a polycarbonate resin laminate that can be suitably used as a component material for various industrial devices, machinery, and buildings, such as simple roofs such as terraces, resin soundproof walls, and security window materials.

For example, as cover materials for various manufacturing devices such as semiconductor manufacturing devices and flat panel display manufacturing devices, window materials and cover plates for machine tools and transportation machines such as cranes and excavators, or window materials for buildings such as houses and hospitals, Conventionally, a glass material has been mainly used. However, in recent years, a synthetic resin plate has been used in place of a glass material from the viewpoint of weight reduction and economic efficiency such as material cost and processing cost.
Among them, a polycarbonate resin-based laminate having a polycarbonate resin as a main component is a frequently used material because it is excellent in impact resistance, heat resistance, transparency and workability.
However, polycarbonate resin laminates based on polycarbonate resin can be used outdoors exposed to sunlight or wind and rain, or in high-temperature and high-humidity environments such as automobiles (temperature 85 ° C, humidity 85% ), The adhesive layer deteriorates or decomposes due to the permeation of moisture and water vapor, and there is a problem that bubbles, whitening, and peeling are likely to occur in the polycarbonate resin laminate.

  In order to solve such a problem, for example, Patent Document 1 discloses that after the plasma treatment is performed on the surface of the polycarbonate resin plate, vacuum lamination is performed at 150 ° C. for 30 minutes, thereby peeling adhesion to the polycarbonate resin laminate. A method for producing a laminate that enhances strength is disclosed.

JP 2009-137012 A

  As described above, although the peel adhesion strength can be increased by laminating the surface of the polycarbonate resin laminate at a high temperature, the polycarbonate resin layer and other resin layers such as The laminate may be warped by being greatly affected by the difference in coefficient of linear expansion from the ethylene-vinyl acetate copolymer resin layer. This warpage is reduced by lowering the heat laminating temperature, but this causes a problem that the peel adhesion strength to the polycarbonate resin laminate is insufficient.

On the other hand, as another method for increasing the peel adhesion strength to the carbonate resin laminate, selection of an adhesive constituting the adhesive layer and improvement of the method of providing the adhesive layer are conceivable.
When a solvent-type adhesive layer is provided on the polycarbonate resin layer, the polycarbonate is a resin with poor solvent resistance, so if the adhesive layer is applied directly to the surface, cracks will occur and the characteristics of the polycarbonate resin laminate Will be lost. Therefore, there is a method in which an adhesive is applied to a transfer substrate made of a film material, dried, thermally transferred to a polycarbonate resin laminate, and the transfer substrate is peeled off to provide an adhesive layer on the polycarbonate resin laminate. It has been adopted.

However, in this method, it is difficult to form a sufficient adhesive film when an adhesive is applied to the surface of the transfer substrate, and slipping is poor when the transfer substrate is wound after the adhesive is dried. Even if it is difficult to wind in a roll shape, even if it is wound in a roll shape, the adhesive on the surface of the transfer substrate and the back surface of the transfer substrate are blocked, making it difficult to peel off. In addition, after the transfer substrate is thermally transferred to a polycarbonate resin laminate, the transfer adhesive layer and the transfer substrate remain adhered to each other, making it difficult to peel off the transfer substrate. There is.
In this method, unless the transfer substrate and the adhesive to be applied are properly selected, the peel adhesion strength to the polycarbonate resin laminate cannot be increased, and the yield of the laminate cannot be improved.

  In view of the above-mentioned problems of the prior art, the present invention provides a polycarbonate resin system by transferring a transfer substrate coated with an adhesive to a polycarbonate resin layer when forming a laminate comprising a polycarbonate resin as a main component. An adhesive layer having a sufficiently high peel adhesive strength to the laminate is provided on the surface of the polycarbonate resin layer, and thus, the resin layer such as ethylene-vinyl acetate copolymer resin is laminated on the adhesive layer. It is an object of the present invention to suppress warping of a laminated plate and maintain a predetermined peel adhesive strength even when placed in a high temperature and high humidity environment.

  The present inventor has intensively studied to solve the above problems, and in the process of producing a polycarbonate resin laminate, the adhesive layer of the transfer material is transferred to the surface of the plate material mainly composed of polycarbonate resin to provide the adhesive layer. By optimizing the transfer substrate selection and transfer method, the coating properties of the adhesive by controlling the wettability of the transfer substrate and the peelability of the transfer substrate from the adhesive layer when transferred are improved. In addition, the roll roughness and the blocking property are improved satisfactorily by controlling the surface roughness of the transfer base material as appropriate, and the adhesive layer formed by peeling the transfer base material has ethylene. -It has been found that by laminating other resin layers such as vinyl acetate copolymer resin layers, it is possible to increase the peel adhesion strength with other resin layers while suppressing warping of the laminate, and based on this knowledge invention It has been led to conceive.

That is, the transfer material of the present invention is a transfer material with an adhesive layer for forming an adhesive layer on a plate material mainly composed of a polycarbonate resin, and the transfer material contains a block isocyanate curing agent on one surface of the transfer substrate. And an adhesive layer formed by applying an olefin-based adhesive, and having a configuration satisfying the following conditions A) and B).
A) The wetting index (based on the wetting tension of JIS K6768) of the surface of the transfer substrate on which the adhesive layer is provided is 31 mN / m or more and less than 40 mN / m. B) The transfer substrate adhesive layer is provided. The wetting index of the surface not provided with the adhesive layer is smaller than the wetting index of the surface provided with the adhesive layer, or the surface roughness of the surface provided with no adhesive layer (the arithmetic average roughness of JIS B 0601) Is 0.8 μm or more larger than the surface roughness (Ra) of the surface on which the adhesive layer is provided.

Further, the polycarbonate resin-based laminate of the present invention is a plate material mainly composed of a polycarbonate resin in which the transfer material having the above-described structure is laminated by polymerizing the adhesive layer on one side surface, and the transfer material of the transfer material It is characterized by having an adhesive layer in which an olefin adhesive containing a blocked isocyanate curing agent is applied to one surface of the plate material by peeling the material.
Furthermore, in the method for producing a polycarbonate resin laminate of the present invention, an adhesive layer is provided by applying an olefin adhesive containing a blocked isocyanate curing agent to one surface of a transfer substrate, and the adhesive layer is dried. A step of winding a transfer substrate to produce a transfer material with an adhesive layer, and extruding a plate material mainly composed of polycarbonate resin into a plate shape by a cooling roll, or after forming into a plate shape, at least one side of this plate material And a step of laminating a transfer base material by superimposing the adhesive layer of the transfer material, and a step of peeling the transfer base material and providing an adhesive layer on one surface of the plate material, To do.

According to the present invention, it is possible to reliably form a solvent-type adhesive layer in a desired thickness on a base material layer made of polycarbonate resin by an appropriate transfer method.
And the board which makes the base material which uses polycarbonate resin provided with the adhesion layer as the main ingredient using the transfer material of the present invention, and laminates other resin layers on this is also a low laminating temperature. , No air bubbles, whitening, peeling, etc. caused by degradation or decomposition of the adhesive layer, can suppress the warping of the laminate, and can be used under harsh conditions outdoors and in the car, high transparency and durability It can be used as a plate material for various fields and applications that require both high performance and low warpage.

It is a schematic cross section which shows an example of the polycarbonate resin-type laminated board of one Embodiment of this invention. It is a schematic cross section which shows an example of the transfer material of one Embodiment of this invention.

  Hereinafter, the present invention will be described in detail based on an embodiment which is an example of the present invention. The present invention is not limited to the embodiments described below.

<Polycarbonate resin laminate>
FIG. 1 shows a polycarbonate resin laminate (hereinafter also referred to as “the present laminate”) 90 according to an embodiment of the present invention. The polycarbonate resin laminate 90 is a polycarbonate resin mainly composed of a polycarbonate resin. An adhesive layer 20 is laminated on at least one side of a base material layer (hereinafter also referred to as “base material layer”) 10 to form a polycarbonate resin-based laminate (hereinafter also referred to as “laminate”) 30. In addition, another resin layer such as an ethylene-vinyl acetate copolymer resin layer (hereinafter also referred to as “EVA layer”) 40 is sequentially laminated.
In preparing the laminate 30, the adhesive layer 20 is formed on the base material layer 10 by thermally transferring the adhesive layer 20 of the transfer material 100 described later to the surface of the base material layer 10. is there.

The polycarbonate resin-based laminate of the present invention only needs to have a laminate 30 in which an adhesive layer 20 is laminated on at least one side of the base material layer 10, and is configured by laminating another resin layer thereon. May be.
That is, for example, the adhesive layer 20 of the laminated plate 30 provided with the EVA layer 40, and as shown in FIG. 1, any one of the moisture proof layer 60, the adhesive layer 70, and the antifouling layer 80 is provided on the EVA layer 40. It also includes a laminate of two or more. Moreover, what comprised the laminated board 30 by providing the ultraviolet-ray absorption layer 50 between the single side | surface or both surfaces of the base material layer 10, or between the base material layer 10 and the contact bonding layer 20 is also contained. The laminated plate 30 may be configured by providing the adhesive layer 20 on both sides of the base material layer 10, and the adhesive layer 20 may be provided with a configuration in which other resin layers such as the EVA layer 40 are sequentially laminated. .

First, each layer of this laminated board 90 and its laminated structure are demonstrated.
<Polycarbonate resin base material layer 10>
The base material layer 10 should just be a layer which has polycarbonate resin as a main ingredient. That is, 50% by mass or more, particularly 80% by mass or more, particularly 90% by mass or more (including 100% by mass) of the resin component constituting the polycarbonate resin-based substrate layer 10 may be a polycarbonate resin. May be included.

  Here, the polycarbonate resin is a linear polymer containing a carbonate ester bond in the main chain. For example, various dihydroxy diaryl compounds and phosgene are reacted by the phosgene method, or carbonic acid such as dihydroxy diaryl compounds and diphenyl carbonate. The polymer etc. which can be obtained by making it react with ester by the transesterification method can be mentioned. Specifically, a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) can be mentioned. However, the present invention is not limited to this.

  The molecular weight of the polycarbonate resin is not particularly limited. Those having a viscosity average molecular weight of about 15,000 to 30,000 that can be formed into a sheet by ordinary extrusion are preferred.

  The thickness of the base material layer 10 is 0.5 mm to 15 mm, preferably 1.5 mm to 8 mm, and more preferably 1.7 mm to 5 mm. If the said thickness is 0.5 mm or more, a handleability can be maintained favorable and a yield does not fall. On the other hand, if the thickness is 15 mm or less, it is preferable because the cost is not particularly high.

<Adhesive layer 20>
The adhesive layer 20 is a layer for suitably bonding the base material layer 10 and the EVA layer 40, and is formed by thermally transferring the adhesive layer 20 of the transfer material 100 described later to the base material layer 10. In order to adjust the peel adhesion strength of the base material layer 10 and the EVA layer 40 to a desired range, selection of the material of the adhesive layer 20 is important.

  Examples of the main agent constituting the adhesive layer 20 include a polyolefin resin, an acrylic resin, a polyurethane resin, a silicone resin, and a polyvinyl acetal resin. These may be used alone or in combination of two or more.

Among these, it is preferable to form from the olefin adhesive composition which has an olefin adhesive as a main ingredient.
The olefin-based adhesive constituting the main component of the olefin-based adhesive composition preferably has a glass transition point (Tg) of −50 to 50 ° C., particularly −30 ° C. to 40 ° C., and particularly −10 ° C. to 30 ° C. Those having a temperature of 0 ° C. or lower are preferred.
In the olefin-based adhesive composition, the content of the olefin-based adhesive may be 50% by mass or more, particularly 70% by mass or more and 100% by mass or less, and particularly 80% by mass or more and 100% by mass or less. It is preferable to mix.

The olefin adhesive composition preferably contains a blocked isocyanate curing agent in addition to the olefin adhesive.
At this time, when the blocked isocyanate curing agent is not blended, for example, when an ordinary isocyanate curing agent is blended instead of the blocked isocyanate curing agent, the adhesive composition seems to be cured when the polycarbonate is dried. Since it does not harden during vacuum lamination, it becomes difficult to obtain a desired peel adhesion strength.
In the olefin-based adhesive composition, the block isocyanate-based curing agent is 1 part by mass to 10 parts by mass, particularly 2 parts by mass or more and 7 parts by mass or less, particularly 3 among them, with respect to 100 parts by mass of the olefin adhesive. It is preferable to blend so as to be at least 5 parts by mass.

The olefin-based adhesive composition preferably contains an epoxy-based curing agent in addition to the olefin-based adhesive and the block isocyanate-based curing agent.
By blending an epoxy curing agent, the curing reaction is effectively accelerated, and the peel adhesion strength can be further increased by vacuum lamination.
In the olefin adhesive composition, the epoxy curing agent is 1 part by mass to 10 parts by mass, particularly 2 parts by mass or more and 7 parts by mass or less, particularly 3 parts by mass, with respect to 100 parts by mass of the olefin adhesive. It is preferable to blend so as to be at least 5 parts by mass.

  In addition to the above components, for example, various modifiers such as a melamine compound and an oxazoline group-containing resin, a curing agent, a crosslinking agent, an additive, and the like may be blended in the adhesive layer 20. These may be used alone or in combination of two or more.

  The thickness of the adhesive layer 20 is not particularly limited, but in the case of an adhesive, it is preferably 1 μm to 30 μm, more preferably 3 μm to 15 μm. If the thickness is 1 μm or more, the peel strength can be maintained, and if the thickness is 30 μm or less, the adhesive force can be maintained while suppressing the cost.

<Ethylene-vinyl acetate copolymer resin layer 40>
The EVA layer 40 laminated on the base material layer 10 through the adhesive layer 20 is flexible and hard to be hardened even at low temperatures, has a high tear strength, is difficult to crack, has good heat sealability, and has excellent transparency. The higher the vinyl acetate content, the better the heat sealability at a low temperature. Therefore, the EVA layer 40 can be suitably used as an adhesive layer and a filling layer.
The thickness of the EVA layer 40 is not particularly limited. For example, 50 μm to 1500 μm, preferably 100 μm to 1000 μm, and more preferably 150 μm to 800 μm. If the thickness is 50 μm or more, there is no problem in durability and strength from the viewpoint of workability, and if the thickness is 1500 μm or less, the productivity and adhesion are not lowered. This is preferable.

<Ultraviolet absorbing layer 50>
The ultraviolet absorption layer 50 can be formed as a layer having a thickness of 10 μm to 100 μm containing, for example, a polycarbonate resin as a main component and containing 1 to 10% by mass of the ultraviolet absorber.
The ultraviolet absorbing material is not particularly limited as long as it has ultraviolet absorbing performance, and examples thereof include benzotriazole, benzophenone, and triazine. However, it is not limited to these. In addition, what is marketed can be used as polycarbonate resin containing a ultraviolet absorber, for example, Panlite L5250ZS by Teijin Chemicals Ltd. can be used.

<Dampproof layer 60>
Examples of the main component of the moisture-proof layer 60 include polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polycyclohexanedimethylene terephthalate acid and glycol-modified copolyester having high barrier properties (moisture resistance). (PCTA). These may be used alone or in combination of two or more.

  The thickness of the moisture-proof layer 60 is not particularly limited. It is preferably 1 μm to 250 μm, preferably 20 μm to 100 μm, and more preferably 30 μm to 70 μm. If the said thickness is 1 micrometer or more, favorable handleability can be maintained and a yield will not fall. On the other hand, when the thickness is 250 μm or less, the cost is not increased.

  In order to further improve the gas barrier property, a vapor deposition film of an inorganic compound such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, zinc oxide, indium oxide, silica, alumina, titanium oxide or a mixture thereof is formed on at least one of the moisture-proof layer 60 You may provide the vapor deposition layer which consists of 5 nm-300 nm in thickness.

<Adhesive layer 70>
Examples of the main component of the adhesive layer 70 include an ethylene-methacrylic acid copolymer resin (EMAA), an ethylene-acrylic acid copolymer resin (EAA), an ethylene-vinyl acetate copolymer resin (EVA), an acrylic resin, and an ionomer. These may be used alone or in combination of two or more.

  Although the thickness of the contact bonding layer 70 is not specifically limited, It is preferable that they are 50 micrometers-1500 micrometers, Preferably they are 100 micrometers-1000 micrometers, Furthermore, they are 150 micrometers-800 micrometers. If the thickness is 50 μm or more, durability and strength can be maintained from the viewpoint of workability, and if the thickness is 1500 μm or less, the productivity and the adhesion may be lowered. Nor.

<Anti-fouling layer 80>
The main component of the antifouling layer 80 may include an acrylic resin, a fluorine resin, a silicone resin, or a mixture thereof excellent in weather resistance, stain resistance, and solvent resistance.

  The thickness of the antifouling layer 80 is not particularly limited, but is preferably 1 μm to 200 μm, preferably 15 μm to 150 μm, more preferably 30 μm or more, or 100 μm or less. If the said thickness is 1 micrometer or more, favorable handleability can be maintained and a yield will not fall. On the other hand, when the thickness is 100 μm or less, the cost is not increased.

<Other ingredients>
The laminated plate 90 has various heat stabilizers, antioxidants (such as phosphorus-based and phenol-based antioxidants), ultraviolet absorbers (such as benzotriazole and triazine), light, and the like within a range that does not impair the effects of the present invention. Stabilizers, near infrared absorbers (sulfur, sulfur compounds, copper compounds and other near infrared absorbers), colorants, fluorescent brighteners, lubricants, mold release agents, antiblocking agents (silica, crosslinked polystyrene beads) Etc.), processing aids, fillers, antibacterial agents, fungicides, softeners, antistatic agents, spreading agents (epoxy soybean oil, liquid paraffin, etc.), flame retardants, anti-drip agents, flame retardant aids, etc. An additive may be contained.

<thickness>
The thickness of the laminate 90 or the laminate 30 may be designed according to the application, and is not particularly limited. However, in general, the warp tends to decrease as the thickness increases, but even if the thickness is 1.5 mm to 2.5 mm, it is preferable that the warp specified below falls within 2 mm / 200 mm. .

<Physical properties>
When the EVA layer 40 is thermally laminated on the adhesive layer 20 provided on the base material layer 10, the warp of the main laminate 90 or the laminate 30 after heat lamination is 2 mm / 200 mm. It is contained below and is preferably 1.5 mm / 200 mm or less, more preferably 1 mm / 200 mm or less.

  Further, when the EVA layer 40 is thermally laminated on the adhesive layer 20 provided on the base material layer 10, the laminate 90 or the laminate 30 has a peel adhesion strength of 40 N / 25 mm between the adhesive layer 20 and the EVA layer 40. It is preferable that it is the above (JIS K6854 conformity, peeling speed 100 mm / min, peeling angle 180 °, measurement width 25 mm), particularly 50 N / 25 mm or more, and particularly preferably 60 N / 25 mm or more.

  Furthermore, when the EVA layer 40 is thermally laminated on the adhesive layer 20 provided on the base material layer 10, the present laminated plate 90 or the laminated plate 30 has the adhesive layer 20 in an environment of a temperature of 85 ° C. and a humidity of 85%. And the EVA layer 40 preferably have a peel adhesive strength of 20 N / 25 mm or more (conforms to JIS K6854, peel rate 100 mm / min, peel angle 180 °, measurement width 25 mm), particularly 25 N / It is more preferably 25 mm or more, and particularly preferably 30 N / 25 mm or more.

  When the EVA layer 40 is thermally laminated to the polycarbonate resin laminate (laminate 30) having the base material layer 10 as a main component, if the lamination is performed at a high temperature, the peel adhesive strength can be increased, but the linear expansion is performed. While being affected greatly by the difference in coefficients, warping occurs in the laminated plate after thermal lamination, while if the lamination temperature is lowered, warping can be reduced, but sufficient peel adhesion strength cannot be obtained. There is. On the other hand, the laminate 90 or the laminate 30 is sufficiently peeled and adhered to the EVA layer 40 by laminating the adhesive layer 20 on the base material layer 10 as described above. It succeeded in suppressing the warp while obtaining strength, and further, even when exposed to an environment such as high temperature and high humidity for a long time, it was possible to suppress peeling and prevent deterioration in transparency. .

Next, the transfer material 100 for providing the adhesive layer 20 on the surface of the base material layer 10 will be described.
FIG. 2 shows a transfer material 100 according to an embodiment of the present invention. The transfer material 100 has the adhesive layer 20 on one surface of a transfer base material 110 (hereinafter also referred to as “base material”) 110 made of a film material. It has a configuration in which a transfer adhesive layer 20 is provided by applying a constituent adhesive.

<Transfer substrate 110>
The transfer substrate 110 is an adhesive layer provided on the surface of the transfer substrate 110 on the surface of the substrate layer 10, which is a plate material mainly composed of a polycarbonate resin formed by extrusion molding. 20 is thermally transferred to form a bonding layer 20 on the base material layer 10.

  Examples of main performance required for the transfer substrate 110 include: A film wetted with an adhesive is formed on the surface of the substrate 110 to such an extent that the adhesive is not repelled when the adhesive is applied to the substrate 110 (wetability); The base material 110 is not attacked by the solvent contained in the adhesive (chemical resistance), and the base material 110 does not thermally expand or contract in a drying process of about 80 ° C. for volatilizing the solvent after the adhesive is applied. Can be conveyed (heat resistance), can be wound after the drying step (winding property), and after winding, the adhesive layer 20 provided on the surface and the back surface of the substrate 110 are blocked. (Blocking property), after the adhesive layer 20 is thermally transferred to the surface of a plate material (base material layer 10) mainly composed of a polycarbonate resin, the adhesive layer 20 and the base material 110 transferred to the plate material Is peelable (peelability), etc. And the like.

In particular, in order to transfer the adhesive layer 20 having a sufficient thickness to the surface of the base material layer 10, an adhesive film is formed with an appropriate thickness when the adhesive is applied to the surface of the transfer base material 110. Therefore, the wetting index (based on the wetting tension of JIS K6768) of the surface on which the adhesive is applied of the transfer substrate 110 is 31 mN / m or more and less than 40 mN / m. preferable.
When the wetting index is 31 mN / m or more, it is possible to apply the adhesive uniformly to the coated surface without being peeled off when the adhesive is applied to the base material. On the other hand, from 40 mN / m If it is large, the adhesiveness between the adhesive and the substrate becomes too strong, and it becomes difficult to transfer the adhesive layer when transferring to the polycarbonate resin.

  Examples of materials that can be generally used as the transfer substrate 110 include polyethylene terephthalate film, polypropylene film, nylon film, polystyrene film, vinyl chloride film, and polyethylene film. The most preferable is a polypropylene film.

For example, polyethylene terephthalate film can satisfy wettability, chemical resistance, heat resistance, and windability, but has a tendency to adhere to the adhesive used in the present invention, so it adheres after thermal transfer. There is a problem that the layer and the base material adhere and cannot be peeled off.
On the other hand, if it is a polypropylene film, the above problems will be solved and it can be used conveniently. As long as it is a film containing polypropylene, a single-layer film or a laminated film of two or more layers obtained by laminating films of other materials can be suitably used. The film used as the transfer substrate 110 is preferably formed by being biaxially stretched so that the peeling operation is easy.

Regardless of the material of the film used as the transfer substrate 110, the thickness and application conditions of the adhesive layer 20 provided by applying an adhesive on the surface thereof, the substrate 110 after drying the applied adhesive, and the like. Depending on the winding conditions, the adhesive layer 20 and the back surface of the substrate 110 may be blocked after winding.
In that case, it is possible to prevent blocking by using the interleaf paper 120 described later and winding the base material 110 in a state where it is overlapped on the adhesive layer 20, or matting on the back surface of the base material 110. Blocking can also be prevented by performing processing and reducing the contact area between the adhesive layer 20 and the back surface of the substrate 110.

As a preferable aspect of the mat processing, in order to prevent blocking, the wetting index of the surface (back surface) of the transfer base 110 on which the adhesive is not applied is the surface (surface) of the side on which the adhesive is applied. This is less than the wetting index.
If the wetting index on the back surface side of the transfer substrate 110 is smaller than the wetting index on the front surface side where the adhesive is applied, the affinity on the back surface side of the adhesive will be lower than the affinity on the front surface side, thus blocking. The transfer substrate 110 can be used as a roll.
Alternatively, the surface roughness of the surface on which the adhesive is not applied (according to the arithmetic average roughness Ra of JIS B 0601) is 0.8 μm or more than the surface roughness (Ra) of the surface on which the adhesive is applied. It can be enlarging.
If the surface roughness is smaller than 0.8 μm, the anti-blocking effect may not be sufficient, and the adhesive layer 20 and the matted surface may be blocked. The material 110 can be wound up well.

<Interleaf 120>
When mat processing is difficult for the transfer substrate 110, the performance required for the substrate 110 may be ensured by using the interleaf paper 120.

The slip sheet 120 is a film that is sandwiched when winding is performed after an adhesive is applied to the base material 110 and dried. By using the slip sheet 120, the back surface of the base material 110 and the adhesive layer 20 are blocked. Can be prevented.
For example, when a polypropylene film is used as the transfer substrate 110, the matte surface of the adhesive paper 120 is in contact with the adhesive layer 20 by using a matted polypropylene film as the interleaf paper 120, thereby preventing blocking. It becomes possible.

<Production method>
A method for manufacturing the laminate 90 will be described below.

  In this laminate 90, an adhesive is applied to the transfer substrate 110 and dried to provide an adhesive layer 20 on the surface of the transfer substrate 110, and the transfer base 110 is wound up to produce a transfer material 110 with an adhesive layer. And after extruding the base material layer 10 which is a plate material mainly composed of a polycarbonate resin and making it into a plate shape by a cooling roll, or after making it into a plate shape, on the surface of at least one side of the base material layer 10, A process of obtaining a laminated plate 30 in which the adhesive layer 20 is provided on the surface of the base material layer 10 by peeling off only the transfer base material 110 and then laminating the adhesive layer 20 of the transfer material 100 and heat laminating; And the process of thermally laminating the EVA layer 40 on the adhesive layer 20 of the laminate 30.

Specifically, first, a transfer material 100 in which an adhesive layer 20 is laminated on a transfer substrate 110 that is a film is prepared.
The transfer material 100 can be manufactured by applying an adhesive on one side of the transfer substrate 110 and drying it to fix the adhesive layer 20 which is an adhesive film.
In addition, as a film of the transfer base material 110, what is marketed, for example, the "biaxially stretched OPP film" etc. by a phthalam chemical company can be used.

  Examples of the method for applying the adhesive include a gravure coating method, a reverse coating method, a roll coating method, a blade coating method, a knife coating method, a rod coating method, a spray coating method, a flow coating method, a die coating method, a comma coating method, Any method such as a dipping method, an offset method, and a bar coating method can be adopted, and a normal drying step or, if necessary, a thermal curing step may be used.

On the other hand, apart from the transfer material with an adhesive layer 100, a base material layer 10 which is a plate material mainly composed of a polycarbonate resin is formed.
The formation method of the base material layer 10 is not specifically limited, For example, it can form by melt-extruding polycarbonate resin from T die using an extruder.

And after extruding polycarbonate resin and shape | molding in a sheet form with a cooling roll, the adhesive layer 20 side of above-mentioned transfer material 100 is in contact with the base material layer 10 in the state whose temperature of this sheet | seat is 100 to 170 degreeC. Thus, they can be laminated and thermally laminated. The transfer material 100 may be heat-laminated in a state where the sheet is reheated with a heater and the temperature is raised to 130 ° C to 160 ° C.
Moreover, when extruding polycarbonate resin and making it into a sheet form with a cooling roll, the adhesive layer 20 side of the above-mentioned transfer material 100 can be laminated | stacked so that the base material layer 10 may be touched, and these can be heat-bonded. . Furthermore, after the base material layer 10 sheet is once cooled and manufactured, the transfer material 100 may be adhered and laminated by heating it again.
Thereafter, only the transfer base material 110 is peeled from the laminated transfer material 100, whereby the laminated board 30 having the adhesive layer 20 fixed on the surface of the base material layer 10 is formed.

Next, the laminate 30 is preliminarily dried with a hot air circulation dryer or a vacuum dryer under the conditions of a drying temperature of 100 ° C. to 130 ° C. and a drying time of 0.5 to 5 hours.
Then, preferably within 1 hour after drying, the EVA layer 40, the moisture-proof layer 60, the adhesive layer 70, and the antifouling layer 80 are laminated on the adhesive layer 20 side of the laminate 30 and integrated by thermo-compression by vacuum suction or the like. A polycarbonate resin is obtained by thermocompression-molding each of the above-mentioned layers as an integral molded body under the conditions of a lamination temperature of 120 ° C. to 135 ° C. and a lamination time of 20 minutes to 60 minutes using a normal molding method such as a lamination method. The system laminate 90 can be manufactured. In addition, the said manufacturing method is only an example.

<Application>
Since the laminate 90 can be excellent in transparency, adhesive strength, heat resistance, moisture resistance, durability, and low warpage, for example, a manufacturing apparatus, a processing machine, a casing or a cover material of an electric device, etc. For automobiles, ships, aircraft and other transport equipment or houses, various building windows, interior / exterior decorative panels, car roofs, terraces and other simple roofs, plastic soundproof walls, security window materials, displays It can be suitably used as a constituent material for various industrial devices such as face plates, machinery, and buildings.

<Explanation of words>
In this specification, the expression “X to Y” (X and Y are arbitrary numbers) means “X or more and Y or less” unless otherwise specified, and “preferably larger than X” or “ The meaning of “preferably smaller than Y” is also included.
In addition, the expression “more than X” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number) means “greater than X” or “preferably less than Y”. Including meaning.

  Embodiments and effects of the present invention will be specifically described by way of examples and comparative examples of the present invention. In addition, this invention is not limited at all by these examples.

Examples 1 and 2 and Comparative Examples 1 to 6 below are embodiments of a transfer material, and Examples 3 and 4 are embodiments of a polycarbonate resin laminate.
The evaluation results for the transfer materials of Examples 1 and 2 and Comparative Examples 1 to 6 are shown in Table 1 below, and these evaluation results are measured and evaluated by the following test methods.

[Coating properties]
The appearance after the adhesive was applied to the transfer substrate 110 and dried was confirmed, and whether or not the adhesive was a film was visually evaluated.
○: The adhesive layer is a film.
X: The adhesive layer is repelled and does not become a film and is not sufficiently fixed.

[Windability after drying]
After the adhesive is applied to the transfer substrate 110 and dried, the transfer material 100 is wound up by a take-up machine to form a roll. At that time, it was confirmed whether or not it could be wound into a roll.
When the slip sheet 120 is used, the slip sheet 120 is unwound from the unwinder at a position before the transfer material 100 is wound by the take-up machine, and the slip sheet 120 is placed on the surface of the adhesive layer 20 of the transfer material 100. The transfer material 100 is wound up with the interleaf paper 120 sandwiched therebetween.
○: Winding is possible.
×: It is difficult to wind up.

[Blocking properties]
After the transfer material 100 is wound up, the transfer material 100 is stored in a roll shape in an environment of a temperature of 40 ° C. for 5 days. Thereafter, the transfer material 100 wound in a roll shape was fed out and it was confirmed whether or not the transfer material 100 could be fed out.
○: Feeding is possible.
X: The adhesive layer fixed as a film on the substrate surface peels off.

[Transferability]
After the adhesive layer 20 of the transfer material 100 was thermally transferred to the base material layer 10 that is a polycarbonate plate and sufficiently cooled, it was confirmed whether or not the transfer base material 110 could be peeled from the adhesive layer 20.
○: The substrate can be peeled from the adhesive layer.
X: The substrate cannot be peeled from the adhesive layer.

〔Comprehensive evaluation〕
The pass / fail of the above evaluation results was evaluated as a whole.
If all of the evaluation items are “◯” in the evaluation result, the overall evaluation is “◯”. If there was one or more “x”, the overall evaluation was “x” and the result was rejected.

Example 1
A biaxially stretched propylene film (thickness: 40 μ, manufactured by Phutamura Chemical Co., Ltd.) was used as the transfer substrate 110, and the adhesive composition was applied to one side surface by a gravure coating method and dried. The transfer material 100 on which the adhesive layer 20 was laminated was produced.
A biaxially stretched propylene film with a single-sided mat (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) is used as the slip sheet 120, and the slip sheet 120 is in contact with the adhesive layer 20 of the transfer material 100. The transfer material 100 was wound up in a roll shape with a gap in between.
Note that. The adhesive composition comprises a polyolefin-based adhesive (Tg: 20 ° C.), a block isocyanate-based curing agent (NCO content 10%, NCO block dissociation temperature = 130 ° C.), and an epoxy-based curing agent (trimethylolpropane triglycidyl ether). Are mixed at a mass ratio of 100: 3: 3.

Next, a polycarbonate resin (“NOVALEX 7027U”; manufactured by Mitsubishi Engineering Plastics Co., Ltd.) is put into the hopper of the extruder, melted at a temperature of 280 ° C., extruded through a gear pump using a sheeting die, A polycarbonate resin base material layer 10 is formed by passing it through a polishing apparatus to form a sheet, and at the same time, the adhesive layer 20 side of the prepared transfer material 100 is laminated on the polycarbonate resin base material layer 10 and thermally laminated. Then, a polycarbonate resin laminate having a total thickness of 2.0 mm was prepared by laminating the transfer material 100 with an adhesive layer and a polycarbonate plate.
After sufficiently cooling the laminate, only the transfer substrate 110 was peeled off to obtain a polycarbonate resin laminate 30 in which the adhesive layer 20 and the polycarbonate plate were laminated.
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Example 2)
A single-sided matte polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the transfer substrate 110, and the transfer material 100 was produced by laminating the adhesive layer 20 on the non-matt surface in the same manner as in Example 1.
The transfer material 100 was wound up in a roll shape with no interleaf.
Then, in the same manner as in Example 1, a laminated plate formed by laminating the transfer material with an adhesive layer 100 and the polycarbonate plate was prepared, and after sufficiently cooling, only the transfer base material 110 was peeled off, and the polycarbonate resin laminated plate 30 was obtained. Got.
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the surface roughness and wettability of the transfer substrate 110 used.

(Comparative Example 1)
Implemented except that a biaxially stretched polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the transfer substrate 110, and a biaxially stretched polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the interleaf paper 120. In the same manner as in Example 1, a transfer material 100 with an adhesive layer 20 was produced.
When this transfer material 100 was verified, it was possible to wind it up in a roll shape, but when the transferred transfer material 100 was unwound, the adhesive layer 20 adhered to the interleaf 120 and the transfer substrate 110 It peeled off from the surface and could not be paid out (blocking property: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Comparative Example 2)
Implemented except that biaxially stretched PET film (thickness: 25 μ, manufactured by Mitsubishi Plastics Co., Ltd.) was used as the transfer substrate 110, and a single-sided matte polypropylene film (thickness: 40μ, manufactured by Futamura Chemical Co., Ltd.) was used as the interleaf paper 120. In the same manner as in Example 1, a transfer material 100 with an adhesive layer 20 was produced.
When the transfer material 100 was verified, it was possible to wind it in a roll shape and to feed it out from the wound state.
Furthermore, in the same manner as in Example 1, a laminated plate formed by laminating the transfer material 100 with an adhesive layer and a polycarbonate plate was prepared, and after sufficiently cooling it, only the transfer substrate 110 was peeled off. The layer 20 and the transfer substrate 110 were in a state of being in strong contact, and only the transfer substrate 110 could not be peeled off (transferability: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Comparative Example 3)
A transfer material 100 with an adhesive layer 20 was produced in the same manner as in Example 1 except that a release PET film (thickness: 38 μ, manufactured by Mitsubishi Plastics, Inc.) was used as the transfer substrate 110.
When this transfer material 100 was verified, when the adhesive was applied to the surface of the transfer substrate 110, the adhesive was repelled and could not be formed as a film (coatability: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the surface roughness and wettability of the transfer substrate 110 used.

(Comparative Example 4)
Example except that a biaxially stretched polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the transfer substrate 110 and a release PET film (thickness: 38 μ, manufactured by Mitsubishi Plastics, Inc.) was used as the interleaf paper 120. In the same manner as in Example 1, a transfer material 100 with an adhesive layer 20 was produced.
When this transfer material 100 was verified, when the transfer material 100 was wound up, the adhesive layer 20 provided on the transfer substrate 110 and the release PET film as the interleaf paper 120 had poor adhesion and slipped. The film could not be wound into a roll (winding property: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Comparative Example 5)
A biaxially stretched polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the transfer substrate 110, and a biaxially stretched PET film (thickness: 25μ, manufactured by Mitsubishi Plastics, Inc.) was used as the interleaf 120. In the same manner as in Example 1, a transfer material 100 with an adhesive layer 20 was produced.
When this transfer material 100 was verified, when the transfer material 100 wound up in a roll shape was fed out, the adhesive layer 20 adhered to the interleaf paper 120 and peeled off from the surface of the transfer substrate 110 and fed out. It was not possible (blocking property: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Comparative Example 6)
Implemented except that a single-sided matte polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the transfer substrate 110 and a biaxially stretched polypropylene film (thickness: 40 μ, manufactured by Futamura Chemical Co., Ltd.) was used as the interleaf paper 120. In the same manner as in Example 1, a transfer material 100 with an adhesive layer 20 was produced.
When this transfer material 100 was verified, when the transfer material 100 wound up in a roll shape was fed out, the adhesive layer 20 adhered to the interleaf paper 120 and peeled off from the surface of the transfer substrate 110 and fed out. It was not possible (blocking property: x).
The evaluation results of the produced transfer material 100 are shown in Table 1. Table 2 shows the roughness and wettability of the surfaces of the transfer substrate 110 and the slip sheet 120 used.

(Example 3)
After the laminate 30 produced in Example 1 was pre-dried with a vacuum dryer at a drying temperature of 130 ° C. and a drying time of 30 minutes, the EVA layer 40 (thickness: 250 μm, “Solar EVA”) was formed on the adhesive layer 20 side. Manufactured by Mitsui Chemicals Fabro Co., Ltd., polyethylene naphthalate film (thickness: 50 μm, “Teonex”; manufactured by Teijin Kasei Co., Ltd.) as the moisture-proof layer 60, and EVA sheet (thickness: 250 μm, “Solar EVA” as the adhesive layer 70; ; Mitsui Chemicals Fabro Co., Ltd.), polyethylene tetrafluoroethylene (thickness: 50 μm, “Neofluon”; manufactured by Daikin Industries Co., Ltd.) as the antifouling layer 80 is laminated in this order, and 135 using a vacuum thermocompression laminator. Lamination was carried out at 30 ° C. for 30 minutes to produce a polycarbonate resin laminate 90.

Example 4
Using the laminate 30 produced in Example 2, a polycarbonate resin laminate 90 was produced in the same manner as Example 3.

  The polycarbonate resin laminate 90 produced in each of Examples 3 and 4 was evaluated for appearance evaluation, peel adhesion strength, and warpage. Both had no appearance abnormality, high peel adhesion strength, and warpage. It was confirmed that it was extremely small.

The measurement method for each evaluation item is as follows.
That is, the external appearance evaluation was a visual evaluation of the external appearance of the laminate 90 after being stored for 1000 hours in an initial environment, at a temperature of 85 ° C., and in a humidity of 85%, and no abnormal appearance was confirmed.
The peel adhesion strength is a method based on JIS K6854, measured at 25 mm width, peel speed of 100 mm / min, peel angle of 180 °, and after storage for 1000 hours in an environment of 85 ° C. and 85% humidity. The peel adhesion strength between the adhesive layer 20 and the EVA layer 40 was measured, and both had an initial strength of 40 N / 25 mm or more (including material destruction and inability to peel), and after storage for 1000 hours It was confirmed that a strength of 20 N / 25 mm or more was obtained.
In addition, the warpage was measured by measuring the gap between the most warped point and the surface of the desk with a steel rule in a room with a temperature of 23 ° C. and leaving a 200 mm square laminate on a horizontal desk. The gap was 2 mm or less.

  From the above results, it was found that the solvent type adhesive layer 20 can be formed on the base material layer 10 made of polycarbonate resin by an appropriate transfer method according to the present invention.

10 polycarbonate resin base layer (base layer), 20 adhesive layer, 30 polycarbonate resin laminate (laminate), 40 ethylene-vinyl acetate copolymer resin layer (EVA layer), 50 UV absorbing layer, 60 moisture barrier , 70 Adhesive layer, 80 Antifouling layer, 90 Polycarbonate resin laminate (this laminate), 100 Transfer material, 110 Transfer substrate, 120 Interleaf

Claims (6)

A transfer material with an adhesive layer for forming an adhesive layer on a plate material mainly composed of polycarbonate resin,
The transfer material (100) includes an adhesive layer (20) formed by applying an olefin-based adhesive containing a blocked isocyanate curing agent on one surface of a transfer substrate (110), and the following A) and B): A transfer material with an adhesive layer, characterized by having a configuration that satisfies the conditions.
A) The wetting index (according to the wetting tension of JIS K6768) of the surface of the transfer substrate (110) on which the adhesive layer (20) is provided is 31 mN / m or more and less than 40 mN / m B) Transfer group The wetting index of the surface of the material (110) where the adhesive layer (20) is not provided is smaller than the wetting index of the surface where the adhesive layer (20) is provided, or the adhesive layer (20) is provided. The surface roughness (based on arithmetic average roughness Ra of JIS B 0601) of the surface not provided is 0.8 μm or more larger than the surface roughness (Ra) of the surface provided with the adhesive layer (20). about   The transfer material with an adhesive layer according to claim 1, wherein the transfer substrate (110) is a biaxially stretched single-layer film containing polypropylene or a laminated film of two or more layers. The transfer material with an adhesive layer according to claim 1, wherein an epoxy-based curing agent is contained in the olefin-based adhesive containing a blocked isocyanate-based curing agent. An olefin-based adhesive containing a blocked isocyanate curing agent is applied to one surface of the transfer substrate (110) to provide an adhesive layer (20), and after the adhesive layer (20) is dried, the transfer substrate (110 ) To produce a transfer material (100) with an adhesive layer, and when a plate material (10) mainly composed of polycarbonate resin is extruded and formed into a plate shape by a cooling roll, or after this plate material ( 10) at least one side of the transfer material (100), the transfer base material (110) is laminated and the transfer base material (110) is laminated, and the transfer base material (110) is peeled off to form the plate material (10). And 10) a step of providing an adhesive layer (20) on one surface. A method for producing a polycarbonate resin-based laminate, comprising: The method for producing a polycarbonate resin laminate according to claim 4, wherein an epoxy curing agent is contained in the olefin adhesive containing the blocked isocyanate curing agent. The polycarbonate resin laminate according to claim 4 or 5, further comprising a step of laminating an ethylene-vinyl acetate copolymer resin layer (40) on an adhesive layer (20) provided on the plate material (10). Production method.

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