JP2019195945A - Laminate and method for producing the same - Google Patents

Abstract

To provide a film and a laminate which have low warpage and can be welded by laser processing with high definition.SOLUTION: A laminate has a base material A1 having absorbance at a wavelength of 355 nm of 0.40 or more, a resin layer α2 which contains a resin A and has a thickness of 0.5-5 μm, and a base material B3 having absorbance at a wavelength of 355 nm of 0.05-0.30 in this order, and has absorbance at a wavelength of 355 nm of more than 0.40.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate and a method for producing the same.

  Conventionally, in joining parts due to the complexity of product shape, joining with an adhesive, mechanical joining with a bolt or the like has been performed. However, adhesives have problems with their adhesive strength, and mechanical joining with bolts and the like has problems of cost, labor for fastening, and mass increase. In hot plate welding, the problem of stringing, vibration welding, and ultrasonic welding required treatment of burrs generated near the joint. On the other hand, laser welding of a resin molded body is a method of irradiating a laser beam to an overlapped resin molded body, transmitting the irradiated one, and absorbing, melting and fusing the other, and heating is local. Therefore, it is less affected by heat, can be joined in a non-contact manner, it is easy to join complex shapes, no adhesive is required, three-dimensional joining is possible, non-contact processing, no burr generation This is a construction method that can be mentioned as an advantage. Therefore, it rapidly spreads in a wide range of fields where high quality materials are required, such as the automobile industry and the electric / electronic industry, and the demand for materials obtained by laser welding is increasing.

  However, in order to use such a laser welding technique, for example, a resin molded body that transmits laser light is necessary, and in order to ensure the laser light transmittance, there are restrictions on characteristics such as the type and thickness of the resin molded body. Take it. On the other hand, it is necessary to use a resin having a thermoplastic property that easily absorbs laser light, that is, can efficiently convert light energy into heat energy and can be welded by the heat, for the resin molded body that absorbs laser light. (Patent Document 1). Further, in the processing of the resin molded body, there are some cases where the adhesive strength is insufficient due to the fact that warpage tends to occur. When warping occurs in the resin molded body, a method of applying a pressing force so as to correct the warping during welding is also employed, but depending on the shape of the resin molded body, it is often difficult to apply the pressing force efficiently. Since the residual stress remains in the resin molded body from which the pressing force is removed after welding, there is a problem that it is difficult to obtain high adhesive strength (Patent Document 2).

Japanese Patent Laid-Open No. 2006-153215 Japanese Patent No. 3510817

  In view of the background of such a conventional technique, the present invention is to provide a laminated body that can be bonded with high precision by low warpage and laser processing, and a method for manufacturing the same.

The present invention employs the following means in order to solve such problems.
(1) Substrate A having an absorbance at a wavelength of 355 nm higher than 0.40, a resin layer α having a thickness of 0.5 μm to 5 μm including the resin A, and a substrate B having an absorbance at a wavelength of 355 nm of 0.05 to 0.30. A laminate having this order.
(2) The laminate according to (1), which includes a resin layer β including the resin B between the resin layer α and the base material B, and the resin B has a glass transition temperature lower than that of the resin A.
(3) The laminate according to (2), wherein the water contact angle on the surface of the resin layer β is less than 15 degrees.
(4) The resin B is a thermoplastic resin, and the resin B is a polyester resin, a (meth) acrylic resin, a polyolefin resin, an ethylene-vinyl acetate copolymer resin, a polyamide resin, a chloroprene resin, an aramid resin, and an acrylic urethane resin. The laminate according to (2) or (3), which is at least one resin selected from the group consisting of:
(5) A substrate A having an absorbance at a wavelength of 355 nm higher than 0.40, a resin layer α containing the resin A, and a substrate B having an absorbance at a wavelength of 355 nm of 0.05 to 0.30 in this order, and a wavelength of 250 nm The manufacturing method of the laminated body which irradiates a ~ 380nm and 0.01W-50W laser from the said base-material B side.
(6) The laminate according to (5), which has a resin layer β containing a resin B between the resin layer α and the base material B, and the resin B has a glass transition temperature lower than that of the resin A. Production method.

  According to the present invention, it is possible to provide a laminate that can be bonded with high warp and high-definition by laser processing, and a method for manufacturing the same.

It is sectional drawing of the laminated structure 1 (The laminated body which has the base material A, the resin layer (alpha), and the base material B in this order). It is sectional drawing of the laminated structure 2 (The laminated body which has the base material A, the resin layer (alpha), the resin layer (beta), and the base material B in this order). It is the figure which showed the example of the laser irradiation pattern in this invention. It is sectional drawing of the liquid expansion | deployment sheet | seat which has the laminated body of this invention as a partial structure.

  Hereinafter, the present invention will be described in detail together with preferred embodiments, but the scope of the present invention is not limited to these embodiments.

  The laminate of the present invention has a substrate A having an absorbance higher than 0.40 at a wavelength of 355 nm, a resin layer α having a thickness of 0.5 μm to 5 μm including the resin A, and an absorbance at a wavelength of 355 nm of 0.05 to 0.30. It is the laminated body which has the base material B in this order. This structure is referred to as a laminated structure 1, and FIG. Further, the laminate of the present invention has a resin layer β containing the resin B between the resin layer α and the base material B included in the laminated structure 1, and the resin B has a glass transition temperature lower than that of the resin A. A laminated body may be sufficient. This structure is referred to as a stacked structure 2, and a cross-sectional view thereof is shown in FIG.

  In the laminated body of the present invention, it is preferable that the base material B in the laminated structure 1 and the portion constituted by the base material B and the resin layer β in the laminated structure 2 each have laser light transmittance (hereinafter referred to as a laminated film). What is constituted by the base material B and the resin layer β in the configuration 2 may be referred to as a liquid developing member). On the other hand, it is preferable that the part constituted by the resin layer α and the substrate A in both the laminated structures 1 and 2 has a laser light absorption property (hereinafter, constituted by the resin layer α and the substrate A in the laminated structures 1 and 2). (This part is sometimes called an ultraviolet absorbing member). Having laser beam transparency means that the absorbance is low. Specifically, the absorbance is preferably 0.05 to 0.30. Moreover, having laser light absorptivity means that the absorbance is high, and specifically, the absorbance is preferably higher than 0.40.

Each of the base material B and the base material A is preferably a resin film. The resin film refers to a resin film having an average thickness of 500 μm or less. When the average thickness exceeds 500 μm, a resin molded product is obtained, and both are distinguished by the average thickness. The method for forming the resin film may be unstretched, uniaxially stretched, or biaxially stretched. Since the resin film is more flexible than the resin molded body, the contact property between the bonding surfaces is good at the time of laser welding, the heat conduction efficiency can be increased, and the welding layer (in the present invention, the resin layer α or the resin layer). Even when the thickness of β) is designed to be thin, the intended adhesion strength can be achieved. Further, when the surface of the base material B or the base material A has waviness, a pressing force may be applied to correct the warpage in order to satisfactorily ground the joint surface in the joining operation. In the conventional technique, warping may occur after joining due to the residual stress, but in the present invention, the average thickness of the base material B and the base material A is set to 500 μm or less so that the base material A and the base material B Since the pressing force is dispersed by flexibility, it is possible to perform bonding without causing warpage.
Further, by using a resin film having a thickness smaller than that of the resin molded body, it is possible to form a thin film laminate that cannot be formed by the resin molded body.

[Substrate A]
The material of the substrate A used in the present invention is not particularly limited, but it is preferable to use an organic polymer as a material from the viewpoint of ease of handling. Examples of the organic polymer that can be suitably used in the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, ABS resin, polycarbonate, polystyrene, and polyvinyl. Examples thereof include various polymers such as alcohol, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, and polyacetal. Among these, it is preferable to contain polyethylene terephthalate. The organic polymer may be either a homopolymer or a copolymer, and any one kind of organic polymer or a blend of plural kinds of organic polymers can be used.

  The organic polymer that can be suitably used for the substrate A in the present invention is an organic polymer whose basic skeleton is linear as listed above (herein, linear is branched). The organic polymer having the basic skeleton is abbreviated as a linear organic polymer). Even if a cross-linking agent having two or more functional groups in the molecule is added and reacted or irradiated with radiation, the number-average molecular weight is 5,000 to 20,000 even if partial cross-linking is formed. If so, it is defined as a linear organic polymer.

  The form of the substrate A may be a single layer film or a film having two or more layers, for example, a film formed by a coextrusion method. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used. The surface of the substrate A on the side where the resin layer α is formed is subjected to pretreatment such as corona treatment, ion bombardment treatment, solvent treatment, or surface roughening treatment in order to improve the adhesion with the resin layer α. It does not matter. In addition, a coating layer of an organic substance, an inorganic substance, or a mixture thereof may be applied to the opposite surface of the substrate A on the side on which the resin layer α is formed for the purpose of improving the slipping property at the time of winding the film. Absent.

  The thickness of the substrate A used in the present invention is preferably 500 μm or less from the viewpoint of ensuring flexibility. Moreover, 5 micrometers or more are more preferable from a viewpoint of ensuring the intensity | strength with respect to a tension | pulling or an impact. Furthermore, the lower limit is more preferably 10 μm or more, and the upper limit is more preferably 200 μm or less, from the standpoint of film processing and handling.

  The color of the substrate A used in the present invention is not particularly limited, but the substrate A has a high absorbance at a wavelength of 355 nm in order to maintain high ultraviolet absorption performance even when the absorbance of the resin layer α at a wavelength of 355 nm is low. Is required. Therefore, the absorbance of the substrate A used in the present invention at a wavelength of 355 nm is higher than 0.40.

[Resin A]
The resin A contained in the resin layer α used in the present invention may be one type or plural types. Examples of the resin A include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, Polybutyl succinate, polyester resin such as polyethylene-2,6-naphthalate, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluorinated ethylene resin, trifluorinated ethylene chloride resin, Fluoropolymers such as tetrafluoroethylene-6propylene copolymer / vinylidene fluoride resin, acrylic resin, methacrylic resin, polyacetal resin, polyg Cholic acid resins, polylactic acid resins, or the like can be used. Among these, a polyester resin is particularly preferable from the viewpoint of strength, heat resistance, transparency, and ultraviolet (hereinafter sometimes referred to as UV) permeability.

  The polyester resin in the present invention refers to a polycondensate of a dicarboxylic acid component and a diol component. Each of the dicarboxylic acid component and the diol component may be a single component or a plurality of types of components. Here, the polyester resin in which both the dicarboxylic acid component and the diol component are single components is referred to as a homopolyester resin, and the polyester resin in which any one of the dicarboxylic acid component and the diol component is a plurality of components is referred to as a copolyester resin.

  Examples of the homopolyester resin in the present invention include the above-mentioned polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, as well as poly-1,4-cyclohexanedimethylene terephthalate, polyethylene diphenylate, and the like. Can be mentioned.

  The copolyester resin in the present invention is preferably a copolyester resin comprising at least three or more components selected from the following dicarboxylic acid components and diol components. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4 Examples include '-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexane dicarboxylic acid, and ester derivatives thereof. Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis (4 ′ -Β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol and the like.

[Resin layer α]
The resin layer α including the resin A is preferably provided by being laminated on the base material B or the base material A in the case of the laminated structure 1 and on the base material A in the case of the laminated structure 2. The method is not particularly limited, and methods such as a gravure coating method, a reverse coating method, a kiss coating method, a die coating method, and a bar coating method can be used. The coating solution concentration, coating film drying conditions, or coating film cooling conditions are not particularly limited, but the coating film drying conditions adversely affect various properties such as heat shrinkage of the base material B or base material A. It is desirable to carry out within a range that does not reach.

  The thickness of the resin layer α is preferably 5 μm or less from the viewpoint of suppressing the amount of the ultraviolet absorber described below, increasing the concentration per unit volume, and ensuring flexibility, and ensures in-plane uniformity of the resin layer α. In view of the above, 0.5 μm or more is preferable. That is, the thickness of the resin layer α is preferably 0.5 to 5 μm, more preferably 0.5 to 3 μm, and still more preferably 1 to 3 μm. It is preferable that the resin layer α generates heat by absorbing laser light and develops adhesiveness. Thus, in order to absorb a laser beam, it is preferable that the light absorbency of wavelength 355nm is higher than 0.40. If the absorbance is lower than 0.40, a sufficient calorific value cannot be obtained and the adhesiveness may be insufficient.

  The ultraviolet absorbing member obtained by laminating the resin layer α on the substrate A preferably has an absorbance at a wavelength of 355 nm higher than 0.40 in order to absorb laser light described later. In order to bring the absorbance of the ultraviolet absorbing member into a preferable range, a method of containing the ultraviolet absorber described below in the resin layer α may be used. The resin layer α joins the base material A and the base material B or a liquid spreading member which is a member including the base material A and the base material B. Compared with the case where the conventional resin molded bodies are directly laser-welded, in the present invention, since the resin layer α can relieve the stress caused by the bonding through the resin layer α, the occurrence of warpage can be suppressed. In order to sufficiently obtain the effect of stress relaxation by the resin layer α, the thickness of the resin layer α is preferably 0.5 μm or more.

[Ultraviolet absorber]
Although the ultraviolet absorber contained in the resin layer α of the present invention has the ability to absorb light in the vicinity of the boundary between the ultraviolet region and the visible light region (around 380 to 400 nm) and the visible light short wavelength region (400 to 430 nm). From the viewpoint of improving the absorptance of laser light having a wavelength of 355 nm, which will be described later, it is preferable to specialize in the ability to absorb ultraviolet rays in a wavelength region of 380 nm or less. It is possible to cut light rays in the vicinity of the boundary between the ultraviolet region and the visible light region (around 380 to 400 nm) and the visible light short wavelength region (400 to 430 nm) only by containing the ultraviolet absorber. More preferably, it is contained at a high concentration.

  The ultraviolet absorber contained in the resin layer α used in the present invention may be a single type or a combination of a plurality of types. There are no particular restrictions on the structural skeleton of the UV absorber, but benzotriazole, benzophenone, benzoate, benzoxazinone, salicylic acid, benzoxazine, triazine, azomethine, indole, and dihydroxybenzophenone are readily available. From the viewpoint of sex. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet absorbers having the same skeleton structure may be used, or ultraviolet absorbers having different skeleton structures may be combined. Specific examples are illustrated below, but (*) is added to the end of the compound name for those having a maximum wavelength in the wavelength region of 320 to 380 nm. The ultraviolet absorbent used in the present invention is preferably an ultraviolet absorbent having a maximum absorption wavelength between wavelengths of 320 to 380 nm. When the maximum wavelength is smaller than 320 nm, it may be difficult to sufficiently cut the ultraviolet region on the long wavelength side depending on the addition concentration.

  Although it does not specifically limit as a benzotriazole type ultraviolet absorber, For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (*), 2- (2'-hydroxy-3 ', 5'-). Di-tert-butylphenyl) benzotriazole (*), 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole (*), 2- (2′-hydroxy- 3′-tert-butyl-5′-methylphenyl) benzotriazole (*), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole (*), 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) -5-chlorobenzotriazole (*), 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″) , 6 "- (Trahydrophthalimidomethyl) -5′-methylphenyl) -benzotriazole (*), 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (*), 2,2′-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol (*), 2- (2′-hydroxy-3 ′ , 5′-ditertiarypentylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tertiary octylphenyl) benzotriazole, 2,2′-methylenebis (4-tertiaryoctyl-6-benzotriazolyl) E) Phenol (*), etc. The benzophenone-based ultraviolet absorber is not particularly limited, but, for example, 2,4-dihydroxybenzophenone. 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone (*), 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 2,2 ′, 4,4′-tetrahydroxy-benzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), and the like.

  Although it does not specifically limit as a benzoate type ultraviolet absorber, For example, resorcinol monobenzoate, 2, 4- di tert-butyl phenyl-3, 5- di tert-butyl 4-hydroxy benzoate, 2, 4- di tert- Amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,6-ditert-butylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5- Examples thereof include di-tert-butyl-4-hydroxybenzoate and octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

  Although it does not specifically limit as a triazine type ultraviolet absorber, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-) Methylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-methoxyphenyl) -s-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -s-triazine, 2,4-diphenyl-6 -(2-hydroxy-4-propoxyphenyl) -s-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -s Triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-hexyloxy) -3-methylphenyl) -s-triazine (*), 2,4,6-tris (2-hydroxy-4-octoxyphenyl) -s-triazine, 2- (4-isooctyloxycarbonylethoxyphenyl)- Examples include 4,6-diphenyl-s-triazine and 2- (4,6-diphenyl-s-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol.

  Although it does not specifically limit as a benzoxazinone type ultraviolet absorber, 2,2'-p-phenylenebis (4H-3,1-benzoxazin-4-one) (*), 2,2'-p-phenylene Bis (6-methyl-4H-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-chloro-4H-3,1-benzoxazin-4-one) (*) 2,2′-p-phenylenebis (6-methoxy-4H-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-hydroxy-4H-3,1-benzo) Oxazin-4-one), 2,2 ′-(naphthalene-2,6-diyl) bis (4H-3,1-benzoxazin-4-one) (*), 2,2 ′-(naphthalene-1, 4-Diyl) bis (4H-3,1-benzoxa Down-4-one) (※), 2,2 '- (thiophene-2,5-diyl) bis (4H-3,1-benzoxazin-4-one) (※) and the like.

  The ultraviolet absorber used in the present invention is preferably an ultraviolet absorber having at least one skeleton structure of triazine, azomethine, indole, or dihydroxybenzophenone. These skeleton structures are excellent in the ability to absorb ultraviolet rays in a wavelength region of 380 nm or less as compared with other generally used ultraviolet absorbers. Further, since the melting point is relatively low, surface precipitation as a solid component of the ultraviolet absorber itself is suppressed, and it can be preferably used from the viewpoint of keeping the ultraviolet absorption effect constant.

  The concentration of the ultraviolet absorber contained in the resin layer α is not particularly limited, but the content of the ultraviolet absorber in the resin layer α is not limited to the entire resin layer α in order not to impair the characteristics of the resin A contained in the resin layer α. When it is 100% by mass, it is preferably 25% by mass or less, more preferably 15% by mass or less. Further, although depending on the thickness of the resin layer α, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in order to satisfy the target ultraviolet absorption rate.

[Base material B]
Although the base material B used for this invention is not specifically limited, From a viewpoint of the ease of handling, it is preferable that it is a resin film which uses organic polymer as a raw material. Examples of the organic polymer that can be suitably used in the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, ABS resin, polycarbonate, polystyrene, and polyvinyl. Examples thereof include various polymers such as alcohol, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, and polyacetal. Among these, it is preferable to contain polyethylene terephthalate. The organic polymer may be either a homopolymer or a copolymer, and any one kind of organic polymer or a blend of plural kinds of organic polymers can be used.

  In the laser irradiation step to be described later, the base material B becomes a surface on which the laser is incident. For this reason, it is required that the ultraviolet ray permeability is high. In particular, in the case of producing a laminate by irradiation with 355 nm laser light, the spectral transmittance of the laser light at 355 nm is preferably 55% or more, preferably 65% or more in accordance with ISO13468-1: 1997. Is more preferable, and 70% or more is more preferable.

  As a form of the base material B, a single layer film or a film having two or more layers, for example, a film formed by a coextrusion method may be used. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used.

  The surface of the base material B on the side where the resin layer α is formed is subjected to pretreatment such as corona treatment, ion bombardment treatment, solvent treatment, or surface roughening treatment in order to improve adhesion to the resin layer α. It does not matter. In addition, a coating layer of an organic material, an inorganic material, or a mixture thereof may be provided on the surface opposite to the side on which the resin layer α is formed for the purpose of improving the slipping property at the time of winding the film.

  Although the thickness of the base material B used for this invention is not specifically limited, From a viewpoint of ensuring a softness | flexibility, 500 micrometers or less are preferable and 5 micrometers or more are preferable from a viewpoint of ensuring the intensity | strength with respect to a tension | tensile_strength or an impact. Furthermore, the lower limit is more preferably 10 μm or more, and the upper limit is more preferably 200 μm or less, from the viewpoint of ease of film processing and handling.

  Since the base material B plays a role as a laser light transmitting material, it is preferable that the absorbance with respect to a desired laser wavelength is low. In particular, the liquid developing member using the laminate of the present invention preferably has low absorbance (high transmittance) with respect to 355 nm ultraviolet laser light described later, and the absorbance is 0.05 to 0.30. If the absorbance is greater than 0.30, the transmitted laser beam is weakened, the amount of heat generated by the ultraviolet absorber contained in the resin layer α is reduced, and sufficient adhesiveness due to the resin layer α or resin layer β described later cannot be obtained. There is a case. In general, as long as an organic polymer is used as a material, the absorbance is 0.05 or more, so the lower limit is 0.05.

[Resin B]
Between the resin layer α and the base material B included in the present invention, a resin layer β containing the resin B may be provided. In the case of the laminated structure 1 that does not have the resin layer β, in the laser irradiation process described later, the ultraviolet light transmitted from the base material B side is absorbed by the ultraviolet absorber included in the resin layer α and generates heat, and is included in the resin layer α. The resin A is subjected to a process of welding the base material B and the base material A. On the other hand, in the case of the laminated structure 2 having the resin layer β, the ultraviolet light transmitted from the substrate B side is absorbed by the ultraviolet absorber contained in the resin layer α and generates heat, and the heat is contained in the adjacent resin layer β. The resin B having a glass transition temperature lower than that of A is heated to undergo a process of welding the base material B and the resin layer α. By providing the resin layer β, the number of layers in the laminate increases by one, so that the processing configuration becomes complicated. However, by providing the resin layer β, the ultraviolet absorption function is provided in the resin layer α, and the adhesive development function is provided in the resin layer β. It is possible to separate the functions. The resin layer α is advantageous in that it is thicker from the viewpoint of exhibiting adhesiveness, whereas the resin layer α is thinner from the viewpoint of propagating heat generated by ultraviolet absorption to the adjacent layer (base material B or base material A). This is advantageous, and it may be difficult to achieve both properties, but this problem is solved by separating the functions by providing the resin layer β.

  When the resin layer β is provided, the glass transition temperature of the resin B used for the resin layer β is preferably lower than that of the resin A as described above. Since the glass transition temperature of the resin B used for the resin layer β is lower than that of the resin A, the effect of further improving the adhesive strength by the resin layer β can be expected.

  The resin B used for the resin layer β of the present invention is selected from the group consisting of polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin, and acrylic urethane resin. At least one resin is preferred. Moreover, it is preferable that it is a thermoplastic resin which is softened by heat and exhibits adhesiveness, that is, a hot-melt property. As described above, a thermoplastic resin having a hot melt property that can be preferably used as the resin B may be referred to as a hot melt adhesive hereinafter.

  The thickness of the resin layer β containing the resin B is preferably 3 to 50 μm, more preferably 5 to 40 μm. If the thickness is less than 3 μm, there may be a case where the in-plane uniform thickness cannot be secured due to insufficient processing accuracy. Moreover, a pinhole may generate | occur | produce and desired adhesive strength may not be acquired. On the other hand, when the thickness becomes thicker than 50 μm, there is an increased concern that the manufacturing cost increases due to the excessive use of the resin B, or the resin layer β protrudes from the end portion in the laminate transport process or the slit process, and the process is contaminated. There is.

  As the resin B, it is preferable to use a polyester resin or a (meth) acrylic resin among the above groups from the viewpoints of adhesive strength with the base material B and the resin layer α, heat resistance, and the like. Furthermore, it is particularly preferable to use a polyester resin or (meth) acrylic resin having a melting point of 40 ° C. or higher and 150 ° C. or lower as a hot melt adhesive. If the melting point is less than 40 ° C., the adhesive B may flow to a portion where the resin B does not want to be bonded due to the flow of the resin B at the time of thermal bonding, and if the melting point is higher than 150 ° C. If a high temperature is not applied at this time, it may not be possible to bond, and work efficiency may be reduced, or the base material B and the resin layer α, which are adherends, may be damaged by heat. is there. Further, the resin B preferably has an aromatic skeleton because the cohesive strength of the resin is improved and the adhesive strength of the resin layer β is improved. Further, only one kind of the above-described resins may be used as the resin B, or a plurality of resins may be used.

  The hot melt adhesive that can be used as the resin B is exemplified, but the resin B that can be used in the present invention is not limited to this. For example, “Aron Melt” (registered trademark) PES-120L, PES-140H, PES-111EE, PES310S30, PES375S40, PPET1008, PPET1025, PPET2102, PPET1303S (above, manufactured by Toagosei Co., Ltd.), Y-167, H-930- S, H-180S (manufactured by Tanaka Chemical Co., Ltd.), “Nichigo Polyester” (registered trademark) SP-154, SP-165, SP-170, SP-176, SP-180, SP-182, SP- 185 (above, manufactured by Nippon Synthetic Chemical Co., Ltd.), “Byron” (registered trademark) 200, 240, 300, 550, BX1001 (above, manufactured by Toyobo Co., Ltd.), “Polysol” (registered trademark) SE-1720, SE- 4210E, SE-6210, SE-6210L (hereinafter , It can be suitably used by Showa Denko Co., Ltd.) and the like.

[Surfactant]
A surfactant may be used together with the resin B for the resin layer β in the present invention. The surfactant plays a role of imparting hydrophilicity to the resin B. As shown in FIG. 4, in the case of adopting a configuration in which a liquid flow path is provided, hydrophilicity works beneficially as a function of improving the developability (suction performance) of the liquid. The surfactant to be used is not limited, but among the surfactants, it is preferable to contain a nonionic surfactant having a polyalkylene glycol skeleton (hereinafter referred to as nonionic surfactant having a polyalkylene glycol skeleton). The agent is sometimes simply referred to as a surfactant). The nonionic surfactant having a polyalkylene glycol skeleton used in the present invention has a polyalkylene glycol skeleton as a hydrophilic substituent and a skeleton described later as a hydrophobic substituent.

  Here, as the nonionic surfactant having a polyalkylene glycol skeleton, for example, polyoxyethylene-alkyl sulfate-sodium salt such as polyoxyethylene lauryl-sulfate sodium salt, polyoxyethylene-lauryl ether, Polyoxyethylene-alkyl ethers such as polyoxyethylene-cetyl ether, polyoxyethylene-oleyl ether, polyoxyethylene-stearyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene-isodecyl ether, polyoxyethylene- Monolaurate, polyoxyethylene-monostearate, polyoxyethylene-alkyl esters such as polyoxyethylene-monooleate, polyoxyethylene sorbitan-monolaurate Polyoxyethylene sorbitan-monostearate, polyoxyethylene sorbitan-monooleate, sorbitan ester / ethylene oxide addition type such as polyoxyethylene sorbitan-monooleate, monoglyceride / ethylene oxide addition type such as polyoxyethylene-coconut fatty acid glyceryl, polyoxyethylene -Triglyceride / ethylene oxide addition type such as hydrogenated castor oil, polyoxyethylene-laurylamine, polyoxyethylene-alkyl (coconut) amine, polyoxyethylene-stearylamine, polyoxyethylene-oleylamine, polyoxyethylene-tallow alkylamine, Alkyl polyether amine type polyoxyethylene monomethyl ether such as polyoxyethylene alkyl-propylene diamine, poly Surfactants such as oxyethylene-dimethyl ether, polyoxyethylene-glyceryl ether, polyoxyethylene α, ω-bis-3-aminopropyl-ether, polyethylene glycol-polypropylene glycol-polyethylene glycol (block copolymer) and the like can be mentioned. The nonionic surfactant having a polyalkylene glycol skeleton that can be used in the present invention is not limited to this.

  Of the nonionic surfactants having a polyalkylene glycol skeleton, compounds having an alkyl substituent as a hydrophobic substituent are more preferred. As specific examples commercially available, “Pionin” (registered trademark) D-1004, D-1007, D-1706-N, D-1715-N, D-1105, D-1110, D-1103-D, D -1105-D, D-1103-S, D-1105-S, D-1107-S, D-1109-S, D-1004, D-1004, D-1004, "New Calgen" (registered trademark) D -1203, D-1205, D-1208, "Pionine" (registered trademark) D-1305-Z, D-1323-Z, D-1803, D-1402, D-1420, D-1504, D-1508, D-1518, D-1106 DIR, D-1110DIR, D-1107SP3, D1301-P, D-1305-P (manufactured by Takemoto Yushi Co., Ltd.), “Emulgen” (registered trademark) 1 2KG, 103, 104P, 105, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 24430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, “Emulgen” (registered trademark) 2020G-HA, 2025G (above, manufactured by Kao Corporation), and the like. When the hydrophobic substituent is an alkyl group, it is easy to produce and obtain a surfactant having a different number of carbon atoms in the alkyl group, so that there is an advantage that the HLB value described later can be arbitrarily changed.

  Among the compounds represented by the nonionic surfactant having a polyalkylene glycol skeleton, specific examples commercially available as an allyl phenyl ether type compound having an allyl phenyl group containing an aromatic group as a hydrophobic substituent include: "Pionine" (registered trademark) D-6512, D-6414, DTD-51, D-6315, D-6112, Pionein D-7240, "New Calgen" (registered trademark) C-150, C-173, C-200 C-314, CP-50, CP-80, CP-120, CP-15-200, E-200 (above, Takemoto Yushi Co., Ltd.) and the like. When the hydrophobic substituent is an allylphenyl group, for example, when an aromatic resin B is used in combination, the adhesive strength is improved by the effect of improving the cohesive force by stacking the aromatic ring of the resin B and the surfactant, which is preferable. . Further, when the hydrophobic substituent is an allylphenyl group, it is easy to produce and obtain a surfactant in which the repeating number of allylphenyl groups is arbitrarily adjusted. Therefore, there is an advantage that the HLB value described later can be arbitrarily changed. is there.

  Among the compounds represented by the nonionic surfactant having a polyalkylene glycol skeleton, as specific examples commercially available as sorbitan fatty acid derivatives, “Leodol” (registered trademark) TW-L120, TW-L106, TW— P120, TW-S120V, TW-S106V, TW-S-320V, TW-O120V, TW-O106V, TW-O320V, TW-IS399C, "Leodol Super" (registered trademark) TW-L120 (above, Kao Corporation Product), “Pionine” (registered trademark) D-941, D-945, D-945T (manufactured by Takemoto Yushi Co., Ltd.), and the like.

  The number average molecular weight (Mn) of the nonionic surfactant having a polyalkylene glycol skeleton is preferably 500 to 20,000, more preferably 2,000 to 20,000, and particularly preferably 5,000 to 18. , 000. That is, when the number average molecular weight is 500 or more, the surfactant component adheres to the surface or cross section of the transport roll or slit blade in the transport process, printing process, slit process, etc., when the laminate is rolled. Can be satisfactorily prevented, and as a result, the frequency of cleaning in each process is significantly reduced, which is preferable. Such a number average molecular weight of 20,000 or less is preferable because the surfactant can be easily dispersed uniformly in the resin layer β.

  Further, the melting point or freezing point of the surfactant is not particularly limited, but is preferably 30 ° C. or lower. More preferably, it is 25 degrees C or less, More preferably, it is 20 degrees C or less. When the melting point or freezing point is higher than 30 ° C., the surfactant is likely to bleed out from the resin layer β, and the adhesive strength of the resin layer β may vary, leading to a decrease in adhesive strength. Moreover, when the melting point or the freezing point is 30 ° C. or lower, it is preferable from the viewpoint of workability because the heating and dissolving operation of the surfactant is not required when preparing a coating liquid in which the resin layer β and the surfactant are mixed.

  In the resin layer β in the present invention, the amount of the surfactant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 12 parts by mass, and still more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the resin B. 10 parts by mass. When the amount of the surfactant is less than 0.1 parts by mass, the hydrophilicity of the surface of the resin layer β cannot be sufficiently obtained, and the introduction property of the liquid sample may not be sufficiently exhibited. Moreover, the effect which prevents that the main component contained in the resin layer (beta) adheres by a laminated body conveyance process, a slit process, etc. may not fully be exhibited. If the amount of the surfactant is larger than 20 parts by mass, the compounding ratio of the resin B to the surfactant in the resin layer β is lowered, so that the strength of the resin layer β is lowered and stable film formation becomes difficult. In some cases, the storage stability of the paint in which the layer β and the surfactant are mixed is reduced. In addition, it is difficult to obtain sufficient compatibility with the resin layer β, the surfactant that bleeds out on the surface of the resin layer β increases, the adhesiveness of the resin layer β is impaired, and the desired adhesive strength may not be obtained. is there. When the surfactant bleeds out, the surfactant component may adhere in the laminate transporting process, the slitting process, etc., and contamination of the processing process may occur. The amount of 0.1 to 20 parts by mass is preferable because a resin layer β that solves the above disadvantages can be obtained.

  The water contact angle on the surface of the resin layer β in the present invention is preferably less than 15 degrees. It is preferable that the contact angle with respect to water is less than 15 degrees because a high-speed and stable introduction of a liquid sample can be sufficiently realized.

  The surfactant used in the present invention is preferably a surfactant having an HLB value of 8-15. It is preferable to use a surfactant having an HLB value of 8 to 15 because hydrophilicity can be imparted to the resin layer β while maintaining compatibility with the resin layer β.

The HLB (HyDophile-Lipophile Balance) value is a hydrophilic / lipophilic balance, and is a value calculated by the Griffin method (all revised edition, introduction to surfactant p128) obtained from the following formula (1).
HLB value of surfactant = (number average molecular weight of hydrophilic group portion / number average molecular weight of surfactant) × 20 Formula (1).

  When the HLB value of the surfactant is greater than 15, it is difficult to obtain sufficient compatibility between the surfactant and the main component of the resin B, and the amount of the surfactant that bleeds out on the surface of the resin layer β increases and the resin layer β is bonded. In some cases, the desired adhesive strength cannot be obtained. On the other hand, when the HLB value of the surfactant is smaller than 8, the hydrophilicity of the resin layer β may not be sufficiently obtained. It is preferable that the surfactant has an HLB value of 8 to 15 because both compatibility with the resin B and hydrophilicity of the resin layer β can be achieved.

[Liquid spreading member]
The liquid spreading member refers to a configuration in which the resin layer β is laminated on the base material B, and is a partial configuration of the laminated configuration 2 shown in FIG. At the time of welding by laser light, the liquid spreading member plays a role as a laser light transmitting material, and therefore, it is required that the absorbance with respect to a desired laser wavelength is low. In particular, the liquid spreading member preferably has low absorbance (high transmittance) with respect to 355 nm ultraviolet laser light described later, and preferably has an absorbance of 0.05 to 0.30. If the absorbance is greater than 0.30, the transmitted laser light is weakened, the amount of heat generated by the ultraviolet absorber contained in the resin layer α is reduced, and sufficient adhesiveness may not be obtained.

[Laser irradiation conditions]
The type of laser light in the laser irradiation process for forming the laminate of the present invention is arbitrary, and a YAG (yttrium, aluminum, garnet crystal) laser having a wavelength of 1,064 nm, wavelengths of 808 nm, 820 nm, 840 nm, 880 nm, and 940 nm. Each LD (laser diode) laser, a green (second harmonic) laser with a wavelength of 532 nm, an ultraviolet (third harmonic) laser with a wavelength of 355 nm, or the like can be used. Among these, it is more preferable to use an ultraviolet laser from the viewpoint of irradiating the laser from the side of the substrate B having transparency in the ultraviolet region in order to pursue processing quality and fineness in forming the liquid flow path. It is more preferable to use an ultraviolet laser because ultraviolet absorbers are widely available.

  As a method for laser welding, preferred is superposition welding. Overlap welding is a technique in which the surfaces having the largest surface areas of the laser light transmitting material and the laser light absorbing material are overlapped with each other, and then welding is performed with laser light. In the present invention, the laser light transmitting material corresponds to the base material B or the liquid spreading member, and the laser light absorbing material corresponds to an ultraviolet absorbing member.

[Manufacturing method of laminate]
As an example of the method for producing the laminate of the present invention, the substrate A, the resin layer α, and the substrate B are provided in this order, and a laser having a wavelength of 250 nm to 380 nm and 0.01 W to 50 W is irradiated from the substrate B side. The manufacturing method of the laminated body to perform is mentioned. More preferably, there are, for example, the following two methods for manufacturing the laminate shown by the laminate configuration 1. In the first manufacturing method, an ultraviolet absorbing member is obtained by providing a resin layer α containing a resin A and an ultraviolet absorber on a substrate A. The resin layer α surface of the obtained ultraviolet absorbing member and the separately prepared base material B are arranged so as to be in contact with the entire surface without a gap, and laser light with wavelengths of 250 nm to 380 nm and 0.01 W to 50 W is irradiated from the base material B side. It is a procedure to do. In the second manufacturing method, the resin layer α containing the resin A and the ultraviolet absorber is provided on the base material B side. Then, it arrange | positions so that the base material A separately prepared with the resin layer (alpha) surface may contact | connect the whole surface without a gap, and is a procedure which irradiates the laser beam of wavelength 250nm -380nm and 0.01W-50W from the base material B side.

  Next, the manufacturing method of the laminated body shown by the laminated structure 2 is shown. As an example, a substrate A having an absorbance at a wavelength of 355 nm higher than 0.40, a resin layer α containing an ultraviolet absorber, and a substrate B having an absorbance at a wavelength of 355 nm of 0.05 to 0.30 in this order, Examples include a method for producing a laminate in which a laser of 250 nm to 380 nm and 0.01 W to 50 W is irradiated from the side of the base material B, and a resin containing a thermoplastic resin B between the resin layer α and the base material B Examples thereof include a method for producing a laminate having the layer β and the resin B having a glass transition temperature lower than that of the resin A. As a more preferred method for producing a laminate, a method for producing a laminate in which the resin layer β contains a surfactant can be mentioned. More specifically, an ultraviolet absorbing member is provided by providing the resin layer α containing the resin A and the ultraviolet absorber on the substrate A, and a liquid is provided by providing the resin layer β containing the resin B on the substrate B. Each deployment member is obtained. The resin layer α surface of the obtained ultraviolet absorbing member and the resin β surface of the liquid spreading member are arranged so as to be in contact with the entire surface without a gap, and laser light having a wavelength of 250 nm to 380 nm and 0.01 W to 50 W from the substrate B side. It is the procedure which irradiates. Further, as described above, when the laminate shown by the laminate configuration 2 is manufactured, the resin layer β may include a surfactant.

  Note that, in any of the stacked structures of the stacked structure 1 and the stacked structure 2, when the wavelength of the laser beam to be irradiated is in the range of 250 nm to 380 nm, the laser light energy is efficiently converted into thermal energy by the ultraviolet absorber. Therefore, it is preferable. Further, the lower limit of the output of the laser beam is preferably 0.01 W or more in order to obtain sufficient thermal energy, and the upper limit is from the viewpoint of preventing deformation / degeneration due to the thermal energy of the base material B through which the laser beam first transmits. 50 W or less is preferable. That is, it is preferable that the output of a laser beam is 0.01W-50W.

  In the laser welding process, it is preferable that the surfaces to be welded are sufficiently grounded. In the present invention, it is preferable to promote grounding on the entire welded surface by using a relatively flexible film material instead of a rigid resin molded body. Moreover, in order to promote sufficient grounding as a processing step, it is more preferable to arrange a glass plate as a weight on the base material B. Although there is no restriction | limiting in the kind of glass plate, It is preferable that the transmittance | permeability with respect to the wavelength of the laser beam to be used is 60% or more, and it is more preferable that it is 70% or more. If the transmittance with respect to the wavelength of the laser beam is less than 60%, the energy of the laser beam to be irradiated does not reach the welded portion sufficiently, and a sufficient adhesive force may not be obtained. In addition, the laser output is increased for welding, which places a burden on laser processing and may cause a decrease in energy efficiency. Although there is no restriction | limiting in the magnitude | size, thickness, and weight of a glass plate, it is preferable that handling is easy.

[Method for manufacturing liquid spreading sheet]
What has the laminated body shown by the laminated structure 2 of this invention as a partial structure is described as a liquid expansion | deployment sheet, and this liquid expansion | deployment sheet provides the resin layer (gamma) in the surface on the opposite side to the resin layer (alpha) of an ultraviolet absorber, for example After providing a space to be a liquid flow path in the spacer member obtained in this manner, the liquid developing member is provided on the resin layer α side, and the cover material is provided on the resin layer γ side. The shape of the liquid channel to be provided is arbitrary. The liquid spreading sheet preferably has a liquid spreading property for sucking pure water from the liquid channel end to the other end. The resin layer γ preferably has the same characteristics as the resin B, and the cover material has the same characteristics as the base material B.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, the method for evaluating the characteristics of the test piece is as follows.

[Thickness of resin layer α and resin layer β]
The laminate was sectioned by the FIB method using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.). Then, the cross section of the sample for observation was observed using the transmission electron microscope (H-9000UHRII by Hitachi, Ltd.) as the acceleration voltage of 300 kV, and the thickness of the resin layer (alpha) and the resin layer (beta) with respect to the standard scale was calculated, respectively.

[Base Material B, Base Material A, Absorbance of Laminate]
Each of the base material B, base material A, and laminate was cut into a size of 5 cm in length and 5 cm in width, and the absorbance at a wavelength of 355 nm was measured using a UV-visible near-infrared spectrophotometer UV-3600 Plus (manufactured by Shimadzu Corporation). did. In addition, it fixed in the apparatus so that a light-incidence surface might turn into arbitrary surfaces in the base material B and the base material A, and a base material B surface in a laminated body. Further, when the absorbance was 3 or more in consideration of measurement error, it was set to 3. In addition, the base material B and the base material A can also be obtained by peeling from the laminate, and when the resin layer α and the resin layer β are attached, they are used for evaluation after wiping with an organic solvent. Moreover, when the base material B, the base material A, and the laminated body are less than 5 cm in length and 5 cm in width, a method of reducing the measurement area by masking the measurement window of the ultraviolet visible near infrared spectrophotometer is taken.

[Adhesion strength of laminate]
As shown in FIG. 3, the base material B and the base material A are peeled off according to JIS Z0237: 2009 using a laminate manufactured by irradiating six linear lasers with a width of 2 mm and a length of 7 cm. The adhesive strength was evaluated three times under the conditions of an angle of 90 ° and a peeling speed of 50 mm / min, and the average value was obtained as a result. When the adhesion strength was 1.5 N / cm or more, the test was “good”, and when it was less than 1.5 N / cm, the test was “failed”.

[Lamination of laminate]
As shown in FIG. 3, a laminate produced by irradiating 6 linear lasers with a width of 2 mm and a length of 7 cm is cut into a long side of 7 cm and a short side of 1.4 cm so as to include the laser irradiation part. The substrate B was allowed to stand on a flat glass plate so that the base material B became the upper surface. Measure the warp of 4 vertices in 1mm increments, and if the height from any glass plate is 2mm or more, reject "x", any vertex is less than 2mm in height from the glass plate The case where there was a pass was marked as “O”. In addition, the case where the adhesion strength of the laminate was “x” and the evaluation of the warpage of the laminate could not be performed was “not evaluated”.

[Water contact angle on the surface of the resin layer β]
The contact angle of the resin layer β with respect to water is a liquid formed when DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.) is used and pure water (2.0 μl) is dropped on the surface of the resin layer β according to JIS R3257: 1999. The water contact angle on the surface of the resin layer β after 5 seconds from the dropping was measured 5 times, and the average value was obtained as a result. The case where the contact angle was less than 15 degrees was evaluated as “◯”, and the case where the contact angle was 15 degrees or more was evaluated as “x”.

[Liquid spreadability of liquid spread sheet]
Pure water was brought into contact with the end of the liquid flow path of the liquid spreading sheet. The case where pure water was sucked to the other end of the liquid flow path was evaluated as “◯”, and the case where it remained at the end of the liquid flow path was evaluated as “x”.

[Glass transition temperature of Resin A and Resin B]
The glass transition temperatures of Resin A and Resin B were determined by the following methods.

  Measurement was performed using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation according to JIS K 7121 (1999). Note that nitrogen with a flow rate of 35 mL / min was used as the purge gas. An evaluation sample is prepared by weighing 2 mg of resin A and resin B each having a solid content of 100% by mass into an aluminum sample pan and crimping. The obtained evaluation sample was heated from −50 ° C. to 160 ° C. at a heating rate of 10 ° C./min to obtain a differential scanning calorimetry chart (the vertical axis represents thermal energy and the horizontal axis represents temperature). In the differential scanning calorimetry chart, the point at which the straight line equidistant in the vertical axis direction from the extended straight line of each baseline intersects the curve of the changed portion was defined as the glass transition temperature.

(Example 1)
Prepared a 12% by mass solid content solution diluted with a mixed solvent of toluene / methyl ethyl ketone = 1/1 (mass ratio) for polyester resin S-140 (Takamatsu Yushi Co., Ltd., glass transition temperature 72 ° C.). Then, “Ubinal” (registered trademark) 3050 (manufactured by BASF Japan Ltd.), which is a dihydroxybenzophenone ultraviolet absorber having a light absorbency in the long wavelength UV region (UV-A: up to 400 nm), is used as S-140. The coating liquid was prepared by adding and stirring so that it might become a ratio of 100 mass parts / 10 mass parts by solid content conversion ratio. The prepared coating solution is applied to one side of a white polyethylene terephthalate (PET) film “Lumirror” (registered trademark) type 100E20 (manufactured by Toray Industries, Inc.) with a gravure coater and dried at 100 ° C. for 30 seconds on one side. An ultraviolet absorbing member 1 having a resin layer α1 having a thickness of 0.5 μm was obtained.

  Thereafter, “Lumirror” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.), which is a transparent PET film, is superimposed on the resin layer α1 surface of the ultraviolet absorbing member 1, and the resin layer α1 surface and the 100T60 surface are in contact with each other without any gap. Thus, the weight was covered with a glass plate from above the 100T60 surface. These are installed in the workpiece of a laser processing apparatus UVTS-4500-HKG (manufactured by Takano Co., Ltd.). The resin layer α1 surface and the 100T60 surface were welded by irradiating a total of 6 times at intervals of 2 mm to obtain the laminate 1 of the present invention shown in FIG. A laser irradiation pattern is shown in FIG.

(Example 2)
For polyester-based resin S-140 (manufactured by Takamatsu Yushi Co., Ltd.), a 20% by mass solid content solution diluted with a mixed solvent of toluene / methyl ethyl ketone = 1/1 (mass ratio) is prepared, and a long wavelength is provided there. “Ubinal” (registered trademark) 3050 (manufactured by BASF Japan Ltd.), which is a dihydroxybenzophenone ultraviolet absorber having a light absorbency in the UV region (UV-A: up to 400 nm), is 100 in terms of solid content conversion ratio with a polyester resin. The coating liquid was prepared by adding and stirring so that it might become a ratio of mass part / 10 mass part. The prepared coating solution is applied to one side of a white polyethylene terephthalate (PET) film “Lumirror” (registered trademark) type 100E20 (manufactured by Toray Industries, Inc.) with a gravure coater and dried at 100 ° C. for 30 seconds on one side. An ultraviolet absorbing member 2 having a resin layer α2 having a thickness of 0.5 μm was obtained.

  Thereafter, “Lumirror” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.), which is a transparent PET film, is superimposed on the resin layer α2 surface of the ultraviolet absorbing member 2, and laser processing similar to that in Example 1 is performed. The laminated body 2 of this invention shown in this was obtained.

(Example 3)
According to the method described in Example 1, an ultraviolet absorbing member 1 was obtained.

  Further, as a component constituting the hot melt adhesive, a polyester type adhesive having a melting point of 100 ° C., a glass transition temperature of −10 ° C., and a number average molecular weight of 22,000 is used as a mixed solvent of toluene / methyl ethyl ketone = 1/1 (mass ratio). After adjusting the diluted solid content concentration to 40% by mass, a nonionic surfactant having a polyalkylene glycol skeleton, Pione D-1105-S (manufactured by Takemoto Yushi Co., Ltd.), as a solid content conversion ratio with a polyester-based adhesive Was added and stirred so that the ratio of 100 parts by mass / 4 parts by mass was obtained. This coating solution was applied to the silicone resin coating surface of the silicone resin film with a comma coater, and dried at 120 ° C. for 30 seconds to provide a resin layer β3 having a thickness of 15 μm on one surface. Thereafter, “Lumirror” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.) is pasted on the surface of the resin layer β3 using a heat sealer under conditions of a sealing temperature of 120 ° C., a sealing time of 1.0 second, and a sealing pressure of 0.2 MPa. The silicone resin film was peeled off to obtain the liquid spreading member 3.

  The obtained resin layer α3 surface of the ultraviolet absorbing member 3 and the resin layer β3 surface of the liquid spreading member 3 are overlapped and covered from above the 100T60 surface of the liquid spreading member 3 with a glass plate as a weight so as to be in contact with the entire surface. . Then, the laminated body 3 of this invention shown in FIG. 2 was obtained by irradiating a laser on the conditions and pattern as described in Example 1. FIG.

  Subsequently, the liquid spreading sheet 3 will be described in the following procedure. Coating with a solid content concentration of 40% by weight, obtained by diluting a polyester adhesive having a melting point of 100 ° C., a glass transition temperature of −10 ° C. and a number average molecular weight of 22,000 using a mixed solvent of toluene / methyl ethyl ketone = 1/1 (mass ratio). The liquid was applied to the silicone resin coating surface of the silicone resin film with a comma coater and dried at 120 ° C. for 30 seconds to provide a resin layer γ3 having a thickness of 15 μm on one surface. The surface of the resin layer γ3 and the 100E20 surface of the separately prepared ultraviolet absorbing member 1 are bonded using a heat sealer under conditions of a sealing temperature of 120 ° C., a sealing time of 1.0 second, and a sealing pressure of 0.2 MPa. A groove having a width of 1 mm and a length of 10 mm was punched into a concave shape using a Thomson blade, and then the silicone resin film was peeled to obtain a spacer member 3. The resin layers γ3 and 100E20 of the spacer member 3 are bonded with a heat sealer under the same conditions as above, and the resin layer α1 surface derived from the ultraviolet absorbing member 1 and the resin layer β3 surface of the liquid developing member 3 separately prepared are overlapped, The liquid spreading member 3 was covered from above the 100T60 surface with a glass plate as a weight so as to be in contact with the entire surface. Then, the liquid expansion | deployment sheet 3 was obtained by irradiating a laser on the conditions and pattern as described in Example 1. FIG. The liquid spreading | diffusion sheet | seat 3 was used for evaluation by using the groove | channel provided in the tip.

(Example 4)
In Example 3, the laminate 4 of the present invention shown in FIG. 2 was similarly used except that “Adeka Stub” (registered trademark) LA-F70 was used instead of “Ubinal” (registered trademark) 3050 (manufactured by BASF Japan Ltd.). Obtained.

  In addition, in the procedure for producing the liquid spreading sheet 3 described in Example 3, “Adeka Stub” (registered) is used instead of “Ubinal” (registered trademark) 3050 (manufactured by BASF Japan Ltd.) as the ultraviolet absorber used for the resin layer α1. A liquid spreading sheet 4 was obtained in the same manner except that the trademark was changed to LA-F70.

(Example 5)
Instead of Pionein D-1105-S (manufactured by Takemoto Yushi Co., Ltd.), which is a nonionic surfactant having a polyalkylene glycol skeleton in Example 3, “Leodol” (registered) which is a nonionic surfactant having a polyalkylene glycol skeleton (Trademark) TW-L106 (manufactured by Kao Corporation) was added in the same manner except that the coating solution was prepared by adding and stirring so that the solid content conversion ratio with the polyester resin would be 100 parts by mass / 4 parts by mass. Thus, the laminate 5 of the present invention shown in FIG. 2 was obtained.

  Moreover, in the procedure which produces the liquid expansion | deployment sheet | seat 3 as described in Example 3, it replaces with Pionein D-1105-S (made by Takemoto Yushi Co., Ltd.) which is a nonionic surfactant which has a polyalkylene glycol skeleton used for resin layer (beta) 3. The ratio of the solid content conversion ratio of “Reodol” (registered trademark) TW-L106 (manufactured by Kao Corporation), which is a nonionic surfactant having a polyalkylene glycol skeleton, to a polyester resin is 100 parts by weight / 4 parts by weight. A liquid spreading sheet 5 was obtained in the same manner except that the coating solution was prepared by adding and stirring so as to be.

(Example 6)
The laminate 6 of the present invention shown in FIG. 2 was obtained in the same manner as in Example 3 except that the laser irradiation output was 50 W. Moreover, in the procedure for producing the liquid spreading sheet 3 described in Example 3, a liquid spreading sheet 6 was obtained in the same manner except that the laser irradiation output for bonding the resin layer α3 surface and the resin layer β3 surface was 50 W. .

(Example 7)
A laminate 7 of the present invention shown in FIG. 2 was obtained in the same manner as in Example 3 except that the liquid developing member 7 obtained in the following procedure was used instead of using the liquid developing member 3.

  To a 40% by mass solid content concentration diluted with a mixed solvent of toluene / ethyl acetate = 1/1 (mass ratio) with respect to acrylic resin Oliveine BPD1109 (manufactured by Toyo Ink Co., Ltd., glass transition temperature-20 ° C.) After the adjustment, the ratio of the solid content conversion ratio of Pionein D-1105-S (made by Takemoto Yushi Co., Ltd.), which is a nonionic surfactant having a polyalkylene glycol skeleton, to the polyester-based adhesive is 100 parts by mass / 4 parts by mass. The coating solution was obtained by adding and stirring so as to be. This coating solution was applied to the silicone resin coating surface of the silicone resin film with a comma coater and dried at 120 ° C. for 30 seconds to provide a resin layer β7 having a thickness of 15 μm on one surface. Then, “Lumirror” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.) is bonded to the surface of the resin layer β7 using a sealer at room temperature and a sealing pressure of 0.2 MPa, and the silicone resin film is peeled off. A liquid spreading member 7 was obtained.

  Further, in the procedure for producing the liquid spreading sheet 3 described in Example 3, a liquid spreading sheet 7 was obtained in the same manner except that the resin layer β7 was used instead of the resin layer β3.

(Example 8)
In the same manner as in Example 3 except that Pionein D-1105-S (manufactured by Takemoto Yushi Co., Ltd.), which is a nonionic surfactant, is not used for the liquid spreading member 3, the laminate 8 of the present invention shown in FIG. 2 is obtained. It was. Further, in the procedure for producing the liquid spreading sheet 3 described in Example 3, the liquid layer was similarly used except that the resin layer β3 nonionic surfactant Piion D-1105-S (manufactured by Takemoto Yushi Co., Ltd.) was not used. An unfolded sheet 8 was obtained.

(Comparative Example 1)
In Example 1, “Lumirror” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.) is used instead of “Lumorir” (registered trademark) type 100T60 (manufactured by Toray Industries, Inc.). Thus, a laminate 9 shown in FIG. 1 was obtained.

(Comparative Example 2)
In Example 1, instead of using “Lumirror” (registered trademark) type 100E20 (manufactured by Toray Industries, Inc.), a black PET film “Lumirror” (registered trademark) type 100X30 (manufactured by Toray Industries, Inc.) is used, and resin 1 was obtained in the same manner except that the layer α1 was not provided.

(Comparative Example 3)
A laminate 11 shown in FIG. 1 was obtained in the same manner as in Example 1 except that “Ubinal” (registered trademark) 3050 (manufactured by BASF Japan Ltd.) was not used for the ultraviolet absorbing member 1.

(Comparative Example 4)
Instead of using “Lumirror” (registered trademark) type 100E20 (manufactured by Toray Industries, Inc.), which is a white polyethylene terephthalate (PET) film, as the base material A in Example 2, “Lumirror” (registered trademark) type 100T60, which is a transparent PET film, is used. The laminated body 12 shown in FIG. 2 is obtained in the same manner except that (Toray Industries, Inc.) is used and “UVINAL” (registered trademark) 3050 (BASF Japan) is not used for the ultraviolet absorbing member 1. It was. Further, following the procedure for producing the liquid spreading sheet 3 described in Example 3, a liquid spreading sheet 12 was obtained.

  In Comparative Example 1, since black 100X30 was used for the base material B which is a laser light transmitting material, the absorbance at a wavelength of 355 nm is not in the range of 0.05 to 0.30. For this reason, the adhesion strength was unacceptable, and the warpage could not be evaluated. In Comparative Example 2, 100X30 corresponding to the base material A generates heat by absorbing the laser light, and the adhesion strength of the laminate is acceptable. However, since the resin layer α is not included, the residual stress is sufficiently relaxed. Instead, the warpage of the laminate was unacceptable. In Comparative Example 3, the laser beam was not sufficiently absorbed in any of the layers corresponding to the resin layer α and the base material A, so the adhesion strength was rejected, and the warpage could not be evaluated. Since the comparative example 4 did not use an ultraviolet absorber and transparent 100T60 was used for the substrate A and the substrate B, the absorbance of the laminate at a wavelength of 355 nm was less than 0.40. For this reason, the adhesion strength was unacceptable, and the warpage could not be evaluated.

1: Substrate A
2: Resin layer α
3: Substrate B
4: Resin layer β
5: UV absorbing member 6: Liquid developing member 7: Resin layer γ
8: Cover material 9: Spacer member 10: Liquid flow path

Claims (6)

A substrate A having an absorbance at a wavelength of 355 nm higher than 0.40, a resin layer α having a thickness of 0.5 μm to 5 μm including the resin A, and a substrate B having an absorbance at a wavelength of 355 nm of 0.05 to 0.30 in this order. Laminated body. The laminate according to claim 1, which has a resin layer β containing a resin B between the resin layer α and the base material B, and the resin B has a glass transition temperature lower than that of the resin A. The laminate according to claim 2, wherein the water contact angle of the surface of the resin layer β is less than 15 degrees. The resin B is a thermoplastic resin, and the resin B includes a polyester resin, a (meth) acrylic resin, a polyolefin resin, an ethylene-vinyl acetate copolymer resin, a polyamide resin, a chloroprene resin, an aramid resin, and an acrylic urethane resin. The laminate according to claim 2 or 3, which is at least one resin selected from the above. A substrate A having an absorbance at a wavelength of 355 nm higher than 0.40, a resin layer α containing the resin A, and a substrate B having an absorbance at a wavelength of 355 nm of 0.05 to 0.30 in this order, having a wavelength of 250 nm to 380 nm and The manufacturing method of the laminated body which irradiates 0.01W-50W laser from the said base-material B side. The method for producing a laminate according to claim 5, wherein a resin layer β containing a resin B is provided between the resin layer α and the base material B, and the resin B has a glass transition temperature lower than that of the resin A.

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