TW202120333A - Layered composite object and bonded object - Google Patents

Layered composite object and bonded object Download PDF

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TW202120333A
TW202120333A TW109135097A TW109135097A TW202120333A TW 202120333 A TW202120333 A TW 202120333A TW 109135097 A TW109135097 A TW 109135097A TW 109135097 A TW109135097 A TW 109135097A TW 202120333 A TW202120333 A TW 202120333A
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group
layer
resin
treatment
compounds
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TW109135097A
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大谷和男
沼尾臣二
高橋信行
新林良太
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日商昭和電工股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/04—Dielectric heating, e.g. high-frequency welding, i.e. radio frequency welding of plastic materials having dielectric properties, e.g. PVC
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/06—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/08—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Epoxy Resins (AREA)

Abstract

A layered composite object which comprises a layer comprising at least one material selected from the group consisting of fiber-reinforced plastics, glasses, and ceramics and one or more resinous coating layers superposed on the material layer, wherein at least one of the resinous coating layers is a modified-polyolefin layer formed from a resin composition including a modified polyolefin, the modified-polyolefin layer being at least one layer selected from among a layer including reaction product 1, which is a product of reaction among a maleic-anhydride-modified polyolefin, a bifunctional epoxy resin, and a bifunctional phenol compound, a layer including reaction product 2, which is a product of reaction between a maleic-anhydride-modified polyolefin and a thermoplastic epoxy resin, and a layer including a mixture of a polyolefin with a thermoplastic epoxy resin.

Description

複合積層體及接合體Composite laminated body and joint body

本案發明關於一種能夠將選自纖維強化塑膠、玻璃及陶瓷所成群中至少1種材料與聚烯烴以高強度接合之複合積層體及其製造方法、使前述材料與聚烯烴接合而成之接合體及其製造方法。The present invention relates to a composite laminate capable of high-strength bonding of at least one material selected from the group of fiber reinforced plastics, glass, and ceramics with polyolefin, and a method of manufacturing the same, and a bonding formed by bonding the aforementioned materials and polyolefins Body and its manufacturing method.

電子裝置產業或汽車產業中，技術之進化進一步地在進行，對素材之需求較多樣化且高度化。為了將製品之性能提高至界限，且同時地實現複數機能，將相異種材料(以下稱作異種材)配置在適材適處之多重材料構造變得必要且不可或缺。多重材料構造是接合異種材而成，作為其接合手段，有探討溶融溶接或接著等各種接合技術。 關於多重材料構造，例如在智慧型手機中，全面玻璃化正在進展，有尋求將玻璃與透明性較佳之聚碳酸酯等之樹脂以***成形等來接合之技術。In the electronic device industry or the automobile industry, the evolution of technology is progressing further, and the demand for materials is more diversified and advanced. In order to improve the performance of products to the limit and realize multiple functions at the same time, a multi-material structure in which dissimilar materials (hereinafter referred to as dissimilar materials) are arranged in suitable materials becomes necessary and indispensable. The multi-material structure is formed by joining dissimilar materials. As a joining method, various joining technologies such as melt welding or bonding have been explored. Regarding the multi-material structure, for example, in smartphones, full-scale vitrification is progressing, and there is a search for technology to join glass and resin such as polycarbonate, which is more transparent, by insert molding.

作為玻璃與樹脂之接合方法，有揭示對顆粒狀之工程塑膠賦予對玻璃之接著力提升劑之後，以使其與玻璃接觸之狀態加熱溶融，藉此來將前述工程塑膠溶融接著於前述玻璃之技術(專利文獻1)。在汽車中，有尋求一種將FRP(纖維強化塑膠)與樹脂接合之場面，並將FRP與樹脂強固地接合之技術。動力機器中，將陶瓷作為***材，有多數使用以樹脂鑄模之絕緣容器等之絕緣體，有尋求一種將陶瓷與樹脂強固地接合之技術。As a bonding method of glass and resin, it is disclosed that after adding an adhesive enhancer to the glass to the granular engineering plastic, it is heated and melted in a state in which it is in contact with the glass, thereby melting and bonding the engineering plastic to the glass. Technology (Patent Document 1). In automobiles, there is a need to join FRP (Fiber Reinforced Plastic) and resin, and the technology to firmly join FRP and resin. In power equipment, ceramics are used as insert materials, and most of them use insulators such as insulated containers molded with resin, and there is a search for a technology to strongly bond ceramics and resin.

以往，若將異種材彼此直接接合，則因為材料間之熱收縮相異，在界面上會集中應力，有成為裂痕或剝離之原因之問題。 關於此問題，有揭示一種在絕緣容器之樹脂鑄模構造中，於陶瓷與樹脂之間塗布矽烷偶合劑，並藉由進行界面處理，來防止樹脂鑄模構造之內部界面上裂痕的產生之技術(非專利文獻1)。In the past, if dissimilar materials are directly joined to each other, because the thermal shrinkage between the materials is different, stress will be concentrated on the interface, which may cause cracks or peeling. Regarding this problem, there is disclosed a technology (non-condensed) that in the resin mold structure of the insulated container, a silane coupling agent is applied between the ceramic and the resin, and the interface treatment is performed to prevent the occurrence of cracks on the internal interface of the resin mold structure. Patent Document 1).

使用於絕緣容器之陶瓷為了防止汙染，在其表面上有實施玻璃質之釉藥(SiO2 -10%Al2 O3 )來使用。因此，前述樹脂鑄模構造中，陶瓷表面之釉藥與樹脂之界面是呈現容易滑脫之狀態。 非專利文獻1中，著眼於上述觀點，藉由在矽烷偶合劑之界面處理，企圖提升樹脂鑄模構造之內部界面之接著強度。 [先前技術文獻] [專利文獻]In order to prevent contamination of ceramics used in insulated containers, a vitreous glaze (SiO 2 -10% Al 2 O 3 ) is applied on the surface. Therefore, in the aforementioned resin mold structure, the interface between the glaze on the ceramic surface and the resin is easy to slip off. In Non-Patent Document 1, focusing on the above point of view, an attempt is made to improve the bonding strength of the internal interface of the resin mold structure by treating the interface of the silane coupling agent. [Prior Technical Documents] [Patent Documents]

[專利文獻1]日本特開2006-297662號公報 [非專利文獻][Patent Document 1] JP 2006-297662 A [Non-Patent Literature]

[非專利文獻1]日本機械學會論文集(A編)77卷774號(2011-2)[Non-Patent Document 1] Proceedings of the Japanese Society of Mechanical Engineers (Edition A) Volume 77, No. 774 (2011-2)

[本發明欲解決之課題][Problems to be solved by the present invention]

然而，以往技術中，在汽車零件或OA機器等之用途中，對玻璃與樹脂有無法實現充分接合強度之課題。 且，專利文獻1之技術中，作為***成形時之玻璃破裂對策，必須將射出壓之上限最大降低至60MPa左右，有無法充分提高射出壓之課題，或有難以應付耐久性提升之需要之課題。且，非專利文獻1之技術中，無法解決由於材料間之熱收縮相異而使應力集中在界面之樹脂端部之問題，進一步的接合強度提升或耐久性提升變得更加困難。However, in the prior art, in applications such as automobile parts and OA equipment, there is a problem that sufficient bonding strength cannot be achieved for glass and resin. In addition, in the technique of Patent Document 1, as a countermeasure against glass breakage during insert molding, the upper limit of the injection pressure must be reduced to about 60 MPa at the maximum. There is a problem that the injection pressure cannot be sufficiently increased, or there is a problem that it is difficult to cope with the need for durability improvement. . In addition, the technique of Non-Patent Document 1 cannot solve the problem of stress concentration on the resin end of the interface due to the difference in thermal shrinkage between materials, and it becomes more difficult to further improve the bonding strength or the durability.

本案發明有鑑於相關技術背景，課題為提供一種將選自纖維強化塑膠、玻璃及陶瓷所成群中至少1種材料與聚烯烴強固地接合之用途所適合之複合積層體及其關聯技術。前述關聯技術意指前述複合積層體之製造方法、使前述材料與聚烯烴接合而成之接合體及其製造方法。 [用於解決課題之手段]In view of the related technical background, the subject of the present invention is to provide a composite laminate and related technologies that are suitable for the purpose of strongly bonding at least one material selected from the group of fiber reinforced plastics, glass, and ceramics with polyolefin. The aforementioned related technology means a method of manufacturing the composite laminate, a joined body formed by joining the material and polyolefin, and a method of manufacturing the joined product. [Means used to solve the problem]

本案發明為了達成前述目的，提供以下手段。 且，本說明書中，接合意指使物與物接合，接著及溶著為其之下位概念。接著意指介隔著如膠帶或接著劑之有機材(熱硬化性樹脂或熱可塑性樹脂等)，將兩個被著材(欲接著者)作為接合狀態，溶著意指被著材之熱可塑性樹脂等之表面因熱而溶融，並藉由接觸加壓與冷卻，以分子擴散所造成之纏繞及結晶化而作為接合狀態。In order to achieve the aforementioned object, the present invention provides the following means. In addition, in this specification, joining means joining an object to an object, and then and dissolving it as a subordinate concept. Next refers to the organic material (thermosetting resin or thermoplastic resin, etc.) such as tape or adhesive, and the two materials to be attached (the one to be connected) are used as a joint state, and the melting means the thermal plasticity of the material to be attached. The surface of the resin is melted by heat, and by contact pressure and cooling, the entanglement and crystallization caused by molecular diffusion are used as the bonding state.

[1] 一種複合積層體，其係具有： 含有選自纖維強化塑膠、玻璃及陶瓷所成群中至少1種之材料層，與 積層於前述材料層上之1層或複數層之樹脂塗布層之複合積層體， 且，前述樹脂塗布層中至少1層係由包含改質聚烯烴之樹脂組成物所形成之改質聚烯烴層，前述改質聚烯烴層係選自包含馬來酸酐改質聚烯烴與2官能環氧樹脂與2官能酚化合物之反應物1之層、包含馬來酸酐改質聚烯烴與熱可塑性環氧樹脂之反應物2之層及包含聚烯烴與熱可塑性環氧樹脂之混合物之層中至少1種。 [2] 如[1]之複合積層體，其中，前述反應物1係在包含馬來酸酐改質聚烯烴之溶液中，使2官能環氧樹脂與2官能酚化合物複加成反應而成。 [3] 如[1]之複合積層體，其中，前述反應物2係使2官能環氧樹脂與2官能酚化合物之複加成反應所生成之熱可塑性環氧樹脂，與馬來酸酐改質聚烯烴反應而成。 [4] 如[1]之複合積層體，其中，前述混合物為聚丙烯與熱可塑性環氧樹脂之混合物。 [5] 如[1]~[4]中任一者之複合積層體，其中，前述樹脂塗布層係含有包含前述改質聚烯烴層與前述改質聚烯烴層以外之層之複數層，且前述改質聚烯烴層以外之層之至少1層係選自由包含熱可塑性環氧樹脂之樹脂組成物所形成之熱可塑性環氧樹脂層及由包含熱硬化性樹脂之樹脂組成物所形成之熱硬化性樹脂層中至少1種。 [6] 如[5]之複合積層體，其中，前述熱硬化性樹脂係選自胺甲酸乙酯樹脂、環氧樹脂、乙烯酯樹脂及不飽和聚酯樹脂所成群中至少1種。 [7] 如[1]~[6]中任一項之複合積層體，其中，於前述材料層與前述樹脂塗布層之間具有鄰接於前述材料層與前述樹脂塗布層而積層之含官能基之層， 且前述含官能基之層包含選自下述(1)~(7)所成群中至少1個官能基， (1)來自矽烷偶合劑，且選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基 (2)使來自矽烷偶合劑之胺基與選自環氧化合物及硫醇化合物中至少1種反應而成之官能基 (3)使來自矽烷偶合劑之氫硫基與選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種反應而成之官能基 (4)使來自矽烷偶合劑之(甲基)丙烯醯基與硫醇化合物反應而成之官能基 (5)使來自矽烷偶合劑之環氧基與選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種反應而成之官能基 (6)來自異氰酸酯化合物之異氰酸基 (7)來自硫醇化合物之氫硫基。 [8] 如[1]~[7]中任一項之複合積層體，其中，前述材料層係在其表面施予選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種前處理而成。[1] A composite laminate having: Contains at least one material layer selected from the group of fiber reinforced plastics, glass and ceramics, and A composite laminate of one or more resin coating layers laminated on the aforementioned material layer, In addition, at least one of the resin coating layers is a modified polyolefin layer formed of a resin composition containing modified polyolefin, and the modified polyolefin layer is selected from the group consisting of maleic anhydride modified polyolefin and bifunctional The layer of reactant 1 of epoxy resin and bifunctional phenol compound, the layer of reactant 2 containing maleic anhydride-modified polyolefin and thermoplastic epoxy resin, and the layer of mixture of polyolefin and thermoplastic epoxy resin At least one. [2] The composite laminate according to [1], wherein the aforementioned reactant 1 is formed by a multi-addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound in a solution containing maleic anhydride modified polyolefin. [3] The composite laminate according to [1], wherein the aforementioned reactant 2 is a thermoplastic epoxy resin produced by the multi-addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound, and is modified with maleic anhydride Polyolefin reaction. [4] The composite laminate according to [1], wherein the aforementioned mixture is a mixture of polypropylene and thermoplastic epoxy resin. [5] The composite laminate according to any one of [1] to [4], wherein the resin coating layer contains a plurality of layers including the modified polyolefin layer and layers other than the modified polyolefin layer, and At least one of the layers other than the modified polyolefin layer is selected from a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a thermal plastic epoxy layer formed of a resin composition containing a thermosetting resin At least one of the curable resin layers. [6] The composite laminate according to [5], wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. [7] The composite laminate according to any one of [1] to [6], wherein a functional group-containing group is laminated adjacent to the material layer and the resin coating layer between the material layer and the resin coating layer The layer, And the aforementioned functional group-containing layer contains at least one functional group selected from the group consisting of (1) to (7) below, (1) It is derived from a silane coupling agent and is selected from at least one functional group from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2) A functional group formed by reacting an amine group derived from a silane coupling agent with at least one selected from epoxy compounds and thiol compounds (3) The sulfhydryl group derived from the silane coupling agent is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and A functional group formed by the reaction of at least one of a group of amine-based compounds (4) Functional group formed by reacting (meth)acrylic acid group derived from silane coupling agent with thiol compound (5) A functional group formed by reacting an epoxy group derived from a silane coupling agent with at least one compound selected from the group consisting of an amine group and a (meth)acrylic acid group, an amine compound, and a thiol compound (6) Isocyanate group from isocyanate compound (7) Hydrosulfide groups derived from thiol compounds. [8] The composite laminate according to any one of [1] to [7], wherein the aforementioned material layer is applied to its surface selected from degreasing treatment, UV ozone treatment, air jet treatment, polishing treatment, plasma treatment, and electric At least one kind of pre-treatment in the group of corona discharge treatment.

[9] 一種複合積層體之製造方法，其係如[1]~[8]中任一項之複合積層體之製造方法，且前述複合積層體係在前述材料層與前述樹脂塗布層之間，具有鄰接於前述材料層與前述樹脂塗布層而積層之含官能基之層，前述含官能基之層係將前述材料層之表面使用選自下述(1’)~(7’)所成群中至少1種來處理而成， (1’) 具有選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基之矽烷偶合劑 (2’) 選自環氧化合物及硫醇化合物中至少1種與具有胺基之矽烷偶合劑之組合 (3’) 具有選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種與具有氫硫基之矽烷偶合劑之組合 (4’) 硫醇化合物與具有(甲基)丙烯醯基之矽烷偶合劑之組合 (5’) 選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種與具有環氧基之矽烷偶合劑之組合 (6’) 異氰酸酯化合物 (7’) 硫醇化合物。 [10] 如[9]之複合積層體之製造方法，其中，前述處理係選自下述(2”)~(5”)中至少1種， (2”) 以具有胺基之矽烷偶合劑處理後，加成選自環氧化合物及硫醇化合物中至少1種之處理 (3”) 以具有氫硫基之矽烷偶合劑處理後，加成選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種之處理 (4”) 以具有(甲基)丙烯醯基之矽烷偶合劑處理後，加成硫醇化合物之處理 (5”) 以具有環氧基之矽烷偶合劑處理後，加成具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種之處理。 [11] 如[9]或[10]之複合積層體之製造方法，其中，在形成前述樹脂塗布層前，形成含官能基之層時，在形成含官能基之層之前，於前述材料層施予選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種前處理。[9] A method for manufacturing a composite laminate, which is the method for manufacturing a composite laminate according to any one of [1] to [8], and the composite laminate system is between the material layer and the resin coating layer, It has a functional group-containing layer that is laminated adjacent to the material layer and the resin coating layer, and the functional group-containing layer is a group selected from the following (1') to (7') using the surface of the material layer At least one of them is processed, (1') Silane coupling agent having at least one functional group selected from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2’) A combination of at least one selected from epoxy compounds and thiol compounds and a silane coupling agent with an amine group (3') Among the group of compounds having an epoxy compound, an amine compound, an isocyanate compound, a compound having a (meth)acryloyl group and an epoxy group, and a compound having a (meth)acryloyl group and an amino group At least one combination with silane coupling agent with hydrogen sulfide group (4') Combination of mercaptan compound and silane coupling agent with (meth)acrylic acid group (5') A combination of at least one selected from the group of compounds having amine groups and (meth)acrylic acid groups, amine compounds, and thiol compounds, and a silane coupling agent having epoxy groups (6’) Isocyanate compound (7') Thiol compound. [10] The method of manufacturing a composite laminate according to [9], wherein the aforementioned treatment is selected from at least one of the following (2”) to (5”), (2") After treatment with silane coupling agent with amine group, at least one selected from epoxy compound and thiol compound is added. (3") After treatment with a silane coupling agent having a hydrogen sulfide group, the addition is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (methyl) ) Treatment of at least one of the groups of acryl and amine compounds (4") After treatment with (meth)acrylic silane coupling agent, the treatment of adding thiol compound (5") After treatment with a silane coupling agent having an epoxy group, at least one of the group of compounds having an amine group and a (meth)acrylic acid group, an amine compound, and a thiol compound is added. [11] The method for manufacturing a composite laminate as in [9] or [10], wherein, before forming the resin coating layer, when forming the functional group-containing layer, before forming the functional group-containing layer, apply the material layer At least one pretreatment selected from the group consisting of degreasing treatment, UV ozone treatment, jet treatment, grinding treatment, plasma treatment and corona discharge treatment.

[12] 一種接合體，其係如[1]~[8]中任一項之複合積層體之樹脂塗布層側之面與聚烯烴經接合一體化。 [13] 一種接合體之製造方法，其係如[12]之接合體之製造方法，且以選自超音波溶著法、振動溶著法、電磁誘導法、高周波法、雷射法及熱壓法所成群中至少1種方法，於前述複合積層體之樹脂塗布層側之面溶著前述聚烯烴。 [14] 一種接合體之製造方法，其係如[12]之接合體之製造方法，且以射出成形法於前述複合積層體之樹脂塗布層側之面溶著前述聚烯烴。 [發明效果][12] A joined body in which the surface of the resin coating layer side of the composite laminate body according to any one of [1] to [8] is joined and integrated with polyolefin. [13] A method of manufacturing a bonded body, which is the method of manufacturing a bonded body as in [12], and is selected from the group consisting of ultrasonic fusion method, vibration fusion method, electromagnetic induction method, high frequency method, laser method, and thermal At least one method among the group of pressing methods is to dissolve the polyolefin on the surface of the composite laminate on the resin coating layer side. [14] A method for manufacturing a bonded body, which is the method for manufacturing a bonded body as in [12], and the polyolefin is melted on the resin coating layer side of the composite laminate by an injection molding method. [Effects of the invention]

藉由本案發明，能夠提供一種將選自纖維強化塑膠、玻璃及陶瓷所成群中至少1種材料與聚烯烴強固地接合之用途所適合之複合積層體及其關聯技術。According to the invention of the present application, it is possible to provide a composite laminate and related technology suitable for the purpose of strongly joining at least one material selected from the group consisting of fiber reinforced plastics, glass, and ceramics with polyolefin.

關於本發明之實施型態之複合積層體及其關聯技術進行詳述。 且，本說明書中，「(甲基)丙烯醯基」之用語意指丙烯醯基及/或甲基丙烯醯基。同樣地，「(甲基)丙烯酸」意指丙烯酸及/或甲基丙烯酸，且「(甲基)丙烯酸酯」意指丙烯酸酯及/或甲基丙烯酸酯。A detailed description of the composite laminate and related technologies of the embodiment of the present invention will be given. In addition, in this specification, the term "(meth)acryloyl" means an acrylic group and/or a methacryloyl group. Similarly, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth)acrylate" means acrylic acid ester and/or methacrylic acid ester.

[複合積層體] 如圖1所示，本實施型態之複合積層體1係具有：含有選自纖維強化塑膠(FRP)、玻璃及陶瓷所成群中至少1種之材料層2，與積層於前述材料層上之1層或複數層之樹脂塗布層3之複合積層體。前述樹脂塗布層3中至少1層係由包含改質聚烯烴之樹脂組成物所形成之改質聚烯烴層31。[Composite laminated body] As shown in Figure 1, the composite laminate 1 of this embodiment has: a material layer 2 containing at least one selected from the group consisting of fiber reinforced plastics (FRP), glass and ceramics, and laminated on the aforementioned material layer One layer or multiple layers of resin coating layer 3 composite laminate. At least one of the aforementioned resin coating layers 3 is a modified polyolefin layer 31 formed of a resin composition containing modified polyolefin.

＜材料層2＞ 材料層2之形態並無特別限定，但亦可為塊狀或薄膜狀。 構成材料層2之纖維強化塑膠(FRP)、玻璃、陶瓷並無特別限定。 作為纖維強化塑膠(FRP)，有舉出對胺甲酸乙酯樹脂、環氧樹脂、乙烯酯樹脂、不飽和聚酯、聚醯胺樹脂、酚樹脂等之熱硬化性樹脂複合各種纖維，並使強度提升之玻璃纖維強化塑膠(GFRP)、碳纖維強化塑膠(CFRP)、硼纖維強化塑膠(BFRP)、醯胺纖維強化塑膠(AFRP)等。亦有舉出由玻璃纖維或碳纖維SMC(片狀模壓複合材料；sheet moulding compound)而成之成形體等。 作為玻璃，有舉出蘇打石灰玻璃、鉛玻璃、硼矽酸玻璃、石英玻璃等。 作為陶瓷，有舉出氧化鋁、氧化鋯、鈦酸鋇等之氧化物系陶瓷、氫氧磷灰石等之氫氧化物系陶瓷、碳化矽等之碳化物系陶瓷、氮化矽等之氮化物系陶瓷等。＜Material layer 2＞ The form of the material layer 2 is not particularly limited, but it may also be in the form of a block or a film. The fiber reinforced plastic (FRP), glass, and ceramic constituting the material layer 2 are not particularly limited. As fiber reinforced plastics (FRP), there are thermosetting resins such as p-urethane resin, epoxy resin, vinyl ester resin, unsaturated polyester, polyamide resin, phenol resin, etc. Strengthened glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), amide fiber reinforced plastic (AFRP), etc. There are also formed bodies made of glass fiber or carbon fiber SMC (sheet moulding compound). Examples of glass include soda lime glass, lead glass, borosilicate glass, quartz glass, and the like. Examples of ceramics include oxide-based ceramics such as alumina, zirconia, and barium titanate, hydroxide-based ceramics such as hydroxide apatite, carbide-based ceramics such as silicon carbide, and nitrogen such as silicon nitride. Compound ceramics, etc.

材料層2中，玻璃之厚度以強度之觀點來看，較佳為0.3mm以上，再較佳為0.5mm以上。且，玻璃之厚度之上限並無特別限制，但較佳為30mm以下，再較佳為10mm以下。 且，材料層2中，FRP及陶瓷之厚度以強度之觀點，各自較佳為1.0mm以上，再較佳為2.0mm以上。且，FRP及陶瓷之厚度之上限並無特別限制，但較佳為20mm以下，再較佳為15mm以下。In the material layer 2, the thickness of the glass is preferably 0.3 mm or more, and more preferably 0.5 mm or more from the viewpoint of strength. Furthermore, the upper limit of the thickness of the glass is not particularly limited, but it is preferably 30 mm or less, and more preferably 10 mm or less. In addition, in the material layer 2, the thickness of FRP and ceramic is each preferably 1.0 mm or more, and more preferably 2.0 mm or more from the standpoint of strength. Moreover, the upper limit of the thickness of FRP and ceramics is not particularly limited, but it is preferably 20 mm or less, and more preferably 15 mm or less.

於材料層2積層樹脂塗布層3之前，以表面之汙染物之去除及/或固定效果為目的，對材料層2之表面實施前處理較佳。藉由前處理，如圖1所示，能夠在材料層2之表面形成微細之凹凸21，使其粗面化。藉此，能夠使材料層2之表面與樹脂塗布層3之接著性提升。Before the material layer 2 is laminated with the resin coating layer 3, it is better to perform pretreatment on the surface of the material layer 2 for the purpose of removing and/or fixing the contaminants on the surface. Through the pretreatment, as shown in FIG. 1, it is possible to form fine concavities and convexities 21 on the surface of the material layer 2 to roughen it. Thereby, the adhesion between the surface of the material layer 2 and the resin coating layer 3 can be improved.

作為前處理，有舉例如脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理、電暈放電處理、雷射處理、蝕刻處理、火焰處理等。 作為前處理，為洗淨材料層2之表面之前處理或對表面設有凹凸之前處理較佳，具體來說，為選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種較佳。 前處理亦可僅實施有1種，或2種以上。作為此等之前處理之具體方法，能夠使用公知方法。 通常認為，在FRP之表面有存在來自樹脂或補強材之羥基，且在玻璃或陶瓷表面原本就有存在羥基，但能夠藉由前述前處理，生成新的羥基，並增加材料層2之表面之羥基。Examples of the pretreatment include degreasing treatment, UV ozone treatment, jet treatment, polishing treatment, plasma treatment, corona discharge treatment, laser treatment, etching treatment, flame treatment, and the like. As the pre-treatment, it is preferable to clean the surface of the material layer 2 or to provide unevenness on the surface. Specifically, it is selected from the group consisting of degreasing treatment, UV ozone treatment, air jet treatment, polishing treatment, plasma treatment, and electric treatment. At least one of the group of corona discharge treatments is preferable. The pretreatment may be implemented by only one type, or two or more types. As a specific method of these previous treatments, a publicly known method can be used. It is generally believed that there are hydroxyl groups derived from resins or reinforcing materials on the surface of FRP, and hydroxyl groups originally exist on the surface of glass or ceramics. However, new hydroxyl groups can be generated through the aforementioned pretreatment, and the surface of the material layer 2 can be increased. Hydroxy.

前述脫脂處理意指將材料層表面之油脂等汙垢，以丙酮、甲苯等之有機溶劑等溶解並去除之方法。The aforementioned degreasing treatment refers to a method of dissolving and removing dirt such as grease on the surface of the material layer with organic solvents such as acetone and toluene.

前述UV臭氧處理意指以由低壓水銀燈發出之短波長之紫外線所具有之能量與藉此產生之臭氧(O3 )力，來洗淨或改質表面之方法。為玻璃時，進行表面之有機系雜質之去除之表面洗淨法之一。一般來說，使用低壓水銀燈之洗淨表面改質裝置被稱作「UV臭氧清淨機」、「UV洗淨裝置」、「紫外線表面改質裝置」等。The aforementioned UV ozone treatment refers to the method of cleaning or modifying the surface with the energy of the short-wavelength ultraviolet light emitted by the low-pressure mercury lamp and the ozone (O 3) power generated thereby. When it is glass, it is one of the surface cleaning methods to remove organic impurities on the surface. Generally speaking, cleaning surface modification devices using low-pressure mercury lamps are called "UV ozone cleaners", "UV cleaning devices", "ultraviolet surface modification devices" and so on.

作為前述噴氣處理，有舉例如濕式噴氣處理、注射式噴氣處理、噴砂處理等。其中，濕式噴氣處理由於相較於乾式噴氣處理能夠得到較緻密之面，故較佳。As the aforementioned air jet treatment, there are, for example, wet air jet treatment, injection air jet treatment, sandblasting treatment, and the like. Among them, the wet air jet treatment is preferable because it can obtain a denser surface compared to the dry air jet treatment.

作為前述研磨處理，有舉例如使用研磨布之拋光研磨，或使用研磨紙(砂紙)之滾輪研磨、電解研磨等。As the aforementioned polishing treatment, there are, for example, buffing and polishing using abrasive cloth, or roller polishing and electrolytic polishing using abrasive paper (sandpaper).

前述電漿處理意指以高壓電源與桿棒製作電漿束，碰撞素材表面使分子激發之官能狀態，且有舉出能夠對素材表面賦予羥基或極性基之大氣壓電漿處理方法等。The aforementioned plasma treatment refers to a functional state in which a high-voltage power supply and a rod are used to make a plasma beam and collide with the surface of the material to excite molecules, and there are atmospheric piezoelectric plasma treatment methods that can impart hydroxyl groups or polar groups to the surface of the material.

前述電暈放電處理意指有舉出施予在高分子薄膜之表面改質之方法，由電極放出之電子會切斷高分子表面層之高分子主鏈或側鏈，將其所產生之自由基作為起點，使表面產生羥基或極性基之方法。The aforementioned corona discharge treatment refers to a method of modifying the surface of a polymer film. The electrons emitted from the electrode will cut the polymer main chain or side chain of the polymer surface layer, and the free A method for generating hydroxyl groups or polar groups on the surface as a starting point.

前述雷射處理意指藉由雷射照射僅將表面層急速加熱且冷卻，並以改善表面之特性之技術使表面之粗面化有效化之方法。能夠使用公知之雷射處理技術。The aforementioned laser treatment refers to a method of rapidly heating and cooling only the surface layer by laser irradiation, and effectively increasing the surface roughness with a technique for improving the characteristics of the surface. A well-known laser processing technology can be used.

作為前述蝕刻處理，有舉例如鹼性法、磷酸-硫酸法、氟化物法、鉻酸-硫酸法、鹽鐵法等之化學性蝕刻處理，或電解蝕刻法等之電氣化學性蝕刻處理等。Examples of the aforementioned etching treatment include chemical etching treatments such as alkaline method, phosphoric acid-sulfuric acid method, fluoride method, chromic acid-sulfuric acid method, and salt iron method, or electrochemical etching treatment such as electrolytic etching method.

前述火焰處理意指藉由將燃燒氣體與空氣之混合氣體燃燒，使空氣中之氧電漿化，將氧電漿賦予至處理對象物而得到表面之親水化之方法。能夠使用公知之火焰處理技術。The aforementioned flame treatment refers to a method of plasmating oxygen in the air by burning a mixed gas of combustion gas and air, and applying the oxygen plasma to the object to be treated to obtain the hydrophilization of the surface. A well-known flame treatment technology can be used.

＜樹脂塗布層3＞ [改質聚烯烴層31] 樹脂塗布層中至少1層為由包含改質聚烯烴之樹脂組成物所形成之改質聚烯烴層31。＜Resin coating layer 3＞ [Modified Polyolefin Layer 31] At least one of the resin coating layers is a modified polyolefin layer 31 formed of a resin composition containing modified polyolefin.

前述材料層上藉由有積層如此特定之樹脂塗布層，本實施型態之複合積層體能夠發揮與聚烯烴之優異接著性。By laminating such a specific resin coating layer on the aforementioned material layer, the composite laminate of this embodiment can exhibit excellent adhesion to polyolefin.

能夠將前述樹脂塗布層設為由包含前述改質聚烯烴層31與前述改質聚烯烴層以外之層之複數層所構成，且能夠將改質聚烯烴層以外之層設為選自由包含熱可塑性環氧樹脂之樹脂組成物所形成之熱可塑性環氧樹脂層32及包含熱硬化性樹脂之樹脂組成物所形成之熱硬化性樹脂層33中至少1種。The resin coating layer can be made up of a plurality of layers including the modified polyolefin layer 31 and layers other than the modified polyolefin layer, and the layers other than the modified polyolefin layer can be selected from those containing heat At least one of the thermoplastic epoxy resin layer 32 formed by the resin composition of the plastic epoxy resin and the thermosetting resin layer 33 formed by the resin composition containing the thermosetting resin.

樹脂塗布層由複數層而成時，所必須之改質聚烯烴層31以與材料層為相反側之最表面來積層較佳。When the resin coating layer is composed of multiple layers, the necessary modified polyolefin layer 31 is preferably laminated on the outermost surface on the opposite side to the material layer.

前述改質聚烯烴層31係選自：包含在馬來酸酐改質聚烯烴之存在下，使2官能環氧樹脂與2官能酚化合物進行複加成反應之同時，也使其與馬來酸酐改質聚烯烴骨架中之馬來酸酐進行反應所得之反應物1之層、包含使2官能環氧樹脂與2官能酚化合物之複加成反應所生成之熱可塑性環氧樹脂與馬來酸酐改質聚烯烴骨架中之馬來酸酐進行反應所得之反應物2之層，及包含熱可塑性環氧樹脂與聚烯烴之混合物之層所構成群中至少1種較佳。The aforementioned modified polyolefin layer 31 is selected from the group consisting of: in the presence of maleic anhydride modified polyolefin, the bifunctional epoxy resin and the bifunctional phenol compound are subjected to a complex addition reaction, and at the same time, it is also combined with maleic anhydride. The layer of reactant 1 obtained by the reaction of maleic anhydride in the modified polyolefin skeleton, including the thermoplastic epoxy resin produced by the multi-addition reaction of the bifunctional epoxy resin and the bifunctional phenol compound, and the modification of maleic anhydride At least one of the layer of reactant 2 obtained by reacting maleic anhydride in the polyolefin skeleton and the layer containing a mixture of thermoplastic epoxy resin and polyolefin is preferred.

(反應物1) 反應物1能夠藉由在馬來酸酐改質聚烯烴之溶液中，使2官能環氧樹脂與2官能酚化合物於觸媒存在下進行複加成反應所得。此時認為，馬來酸酐改質聚烯烴亦能與於2官能環氧樹脂、2官能酚化合物及反應物2之項中所後述之2官能環氧樹脂與2官能酚化合物所生成之熱可塑性環氧樹脂反應。(Reactant 1) Reactant 1 can be obtained by multi-addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound in a solution of maleic anhydride modified polyolefin in the presence of a catalyst. At this time, it is believed that the maleic anhydride modified polyolefin can also interact with the thermoplasticity formed by the bifunctional epoxy resin and the bifunctional phenol compound described later in the section of the bifunctional epoxy resin, bifunctional phenol compound, and reactant 2. Epoxy reaction.

(馬來酸酐改質聚烯烴) 作為前述馬來酸酐改質聚烯烴，為將馬來酸酐接枝於聚烯烴者，有馬來酸酐改質聚乙烯、馬來酸酐改質聚丙烯等。有化藥Nouryon股份公司製Kayabrid 002PP、002PP-NW、003PP、003PP-NW、三菱Chemical股份公司製Modic系列等。 且，作為以馬來酸酐使其機能化之聚丙烯添加劑，亦可併用BYK公司製SCONA TPPP2112GA、TPPP8112GA、TPPP9212GA。(Maleic anhydride modified polyolefin) As the maleic anhydride-modified polyolefin, there are maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene and the like for grafting maleic anhydride to polyolefin. There are Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW manufactured by Nouryon Co., Ltd., Modic series manufactured by Mitsubishi Chemical Co., Ltd., etc. In addition, as a polypropylene additive functionalized with maleic anhydride, SCONA TPPP2112GA, TPPP8112GA, and TPPP9212GA manufactured by BYK can also be used in combination.

(2官能環氧樹脂) 作為前述2官能環氧樹脂，有舉例如雙酚型環氧樹脂、雙苯基型環氧樹脂。此等中，亦可單獨使用1種，亦可併用2種以上。具體來說有舉出三菱Chemical股份公司製「jER(註冊商標)828」、同「jER(註冊商標)834」、同「jER(註冊商標)1001」、同「jER(註冊商標)1004」、同「jER(註冊商標)1007」、同「jER(註冊商標) YX-4000」等。(2-functional epoxy resin) As said bifunctional epoxy resin, a bisphenol type epoxy resin and a bisphenyl type epoxy resin are mentioned, for example. Among these, one type may be used alone, or two or more types may be used in combination. Specifically, there are "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Co., Ltd., the same as "jER (registered trademark) 834", the same as "jER (registered trademark) 1001", and the same as "jER (registered trademark) 1004", Same as "jER (registered trademark) 1007", same as "jER (registered trademark) YX-4000", etc.

(2官能酚化合物) 作為前述2官能酚化合物，有舉例如雙酚、聯酚等。此等中，亦可單獨使用1種，亦可併用2種以上。 且，作為此等之組合，有舉例如雙酚A型環氧樹脂與雙酚A、雙酚A型環氧樹脂與雙酚F、雙苯基型環氧樹脂與4,4’-聯酚等。且，有舉例如Nagasechemtex股份公司製「WPE190」與「EX-991L」之組合。(2-functional phenol compound) As said bifunctional phenol compound, bisphenol, biphenol, etc. are mentioned, for example. Among these, one type may be used alone, or two or more types may be used in combination. And, as a combination of these, for example, bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, bisphenyl type epoxy resin and 4,4'-biphenol Wait. And, for example, there is a combination of "WPE190" and "EX-991L" manufactured by Nagasechemtex Co., Ltd.

作為用於熱可塑性環氧樹脂之複加成反應之觸媒，適合使用例如三乙基胺、2,4,6-參(二甲基胺基甲基)酚等之3級胺；三苯基膦等之磷系化合物等。As a catalyst for the complex addition reaction of thermoplastic epoxy resins, tertiary amines such as triethylamine, 2,4,6-ginseng (dimethylaminomethyl)phenol, etc. are suitable for use; triphenyl Phosphorus compounds such as phosphines, etc.

(反應物2) 反應物2能夠藉由使2官能環氧樹脂與2官能酚化合物之複加成反應所生成之熱可塑性環氧樹脂與馬來酸酐改質聚烯烴進行反應所得。作為此反應中使用之馬來酸酐改質聚烯烴、2官能環氧樹脂、2官能酚化合物，能夠使用與生成反應物1時相同者。(Reactant 2) The reactant 2 can be obtained by reacting a thermoplastic epoxy resin produced by a multi-addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with maleic anhydride-modified polyolefin. As the maleic anhydride-modified polyolefin, the bifunctional epoxy resin, and the bifunctional phenol compound used in this reaction, the same ones as when the reactant 1 was produced can be used.

(熱可塑性環氧樹脂) 前述反應物2之製造時所使用之熱可塑性環氧樹脂為亦稱作現場聚合型苯氧樹脂、現場硬化型苯氧樹脂、現場硬化型環氧樹脂等之樹脂，且藉由2官能環氧樹脂與2官能酚化合物在觸媒存在下進行複加成反應，來形成熱可塑構造，亦即線形聚合物構造。熱可塑性環氧樹脂與構成架橋構造之3次元網狀之熱硬化性樹脂相異，具有熱可塑性。(Thermoplastic epoxy resin) The thermoplastic epoxy resin used in the manufacture of the aforementioned reactant 2 is a resin also called in-situ polymerizable phenoxy resin, in-situ hardening phenoxy resin, in-situ hardening epoxy resin, etc., and is made of bifunctional epoxy The resin and the bifunctional phenol compound undergo a complex addition reaction in the presence of a catalyst to form a thermoplastic structure, that is, a linear polymer structure. Thermoplastic epoxy resin is different from the thermosetting resin that constitutes the three-dimensional network of the bridge structure, and has thermoplasticity.

製造前述反應物1、反應物2時所使用之2官能環氧樹脂與2官能酚化合物之合計量，將馬來酸酐改質聚烯烴設為100質量份時，為5~100質量份較佳，為5~60質量份再較佳，為10~30質量份更較佳。The total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in the production of the aforementioned reactant 1 and reactant 2, when the maleic anhydride-modified polyolefin is set to 100 parts by mass, it is preferably 5-100 parts by mass , Is more preferably 5-60 parts by mass, more preferably 10-30 parts by mass.

且，得到前述反應物1及前述反應物2時所產生之反應之方法有馬來酸酐改質聚烯烴與2官能環氧樹脂之反應、馬來酸酐改質聚烯烴與2官能酚化合物之反應、將馬來酸酐間連結環氧之反應、熱可塑性環氧樹脂末端之環氧基與馬來酸酐之反應、熱可塑性環氧樹脂骨架中之二級羥基與馬來酸酐之反應等各式各樣，且無法總括地表現基於其組合之具體型態。因此，作為前述反應物1、前述反應物2，將所得之改質聚烯烴以構造或特性來直接限定是不可能或非實際的。In addition, the methods of the reaction generated when obtaining the aforementioned reactant 1 and the aforementioned reactant 2 include the reaction of maleic anhydride-modified polyolefin and bifunctional epoxy resin, the reaction of maleic anhydride-modified polyolefin and bifunctional phenol compound, The reaction between maleic anhydride and the epoxy, the reaction between the epoxy group at the end of the thermoplastic epoxy resin and maleic anhydride, the reaction between the secondary hydroxyl group in the thermoplastic epoxy resin skeleton and the maleic anhydride, etc. , And it is impossible to express the specific type based on its combination in an all-inclusive manner. Therefore, as the aforementioned reactant 1 and the aforementioned reactant 2, it is impossible or impractical to directly define the resulting modified polyolefin in terms of structure or characteristics.

前述熱可塑性環氧樹脂與聚烯烴之混合物能夠藉由一般方法將前述反應物2之製造所使用者相同之熱可塑性環氧樹脂與聚烯烴混合所得。The mixture of the aforementioned thermoplastic epoxy resin and polyolefin can be obtained by mixing the same thermoplastic epoxy resin and polyolefin used in the manufacture of the aforementioned reactant 2 by a general method.

(聚烯烴) 作為前述混合物之形成所使用之聚烯烴，能夠直接使用作為被接合體時所使用之聚烯烴。聚烯烴並無特別限定，為一般的合成樹脂即可。例如聚乙烯、聚丙烯等。(Polyolefin) As the polyolefin used for the formation of the aforementioned mixture, the polyolefin used as the joined body can be used as it is. The polyolefin is not particularly limited, and may be a general synthetic resin. For example, polyethylene, polypropylene, etc.

樹脂塗布層被積層於材料層之表面上。如上述，樹脂塗布層亦可被積層於沒有施予前處理之材料層之表面，亦可被積層於施予前處理之材料層之表面。或者，亦可積層於後述含官能基之層之表面。The resin coating layer is laminated on the surface of the material layer. As mentioned above, the resin coating layer can also be laminated on the surface of the material layer that has not been pre-treated, or can be laminated on the surface of the material layer that has been pre-treated. Alternatively, it may be laminated on the surface of the functional group-containing layer described later.

[熱可塑性環氧樹脂層32] 能夠將前述樹脂塗布層3以前述改質聚烯烴層與其以外之層之複數層來構成，並將其改質聚烯烴層以外之層中至少1層以由包含熱可塑性環氧樹脂之樹脂組成物所形成之熱可塑性環氧樹脂層32來構成。 包含前述熱可塑性環氧樹脂之樹脂組成物中，包含熱可塑性環氧樹脂40質量%以上較佳，包含70質量%以上再較佳。[Thermoplastic epoxy resin layer 32] The resin coating layer 3 can be composed of multiple layers of the modified polyolefin layer and other layers, and at least one of the layers other than the modified polyolefin layer can be composed of a resin containing a thermoplastic epoxy resin It is composed of a thermoplastic epoxy resin layer 32 formed by an object. In the resin composition containing the aforementioned thermoplastic epoxy resin, the thermoplastic epoxy resin preferably contains 40% by mass or more, and more preferably 70% by mass or more.

(熱可塑性環氧樹脂) 熱可塑性環氧樹脂與前述反應物2之製造時所使用之熱可塑性環氧樹脂相同，藉由2官能環氧樹脂與2官能酚化合物在觸媒存在下進行複加成反應，而形成熱可塑構造，亦即線形聚合物構造之樹脂，且與構成架橋構造之3次元網狀之熱硬化性樹脂相異，具有熱可塑性。 熱可塑性環氧樹脂由於具有如此之特徵，藉由現場聚合，能夠形成與材料層之接著性優異，且與改質聚烯烴層31之接著性優異之熱可塑性環氧樹脂層32。(Thermoplastic epoxy resin) The thermoplastic epoxy resin is the same as the thermoplastic epoxy resin used in the manufacture of the aforementioned reactant 2. By the multi-addition reaction of the bifunctional epoxy resin and the bifunctional phenol compound in the presence of a catalyst, a thermoplastic resin is formed The structure, that is, the resin of the linear polymer structure, is different from the thermosetting resin of the three-dimensional network that constitutes the bridge structure, and has thermoplasticity. Due to the characteristics of the thermoplastic epoxy resin, by in-situ polymerization, it is possible to form a thermoplastic epoxy resin layer 32 having excellent adhesion to the material layer and excellent adhesion to the modified polyolefin layer 31.

因此，製造複合積層體時，在下層之表面上，藉由使包含熱可塑性環氧樹脂之單體之組成物進行複加成反應，形成熱可塑性環氧樹脂層32較佳。 前述包含熱可塑性環氧樹脂之單體之組成物之複加成反應在作為下層之後述含官能基之層之表面上進行較佳。以如此之型態形成之包含熱可塑性環氧樹脂層之樹脂塗布層3，與材料層之接著性優異，且與後述接合對象之接合性優異。Therefore, when manufacturing the composite laminate, it is preferable to form the thermoplastic epoxy resin layer 32 on the surface of the lower layer by subjecting the composition containing the monomer of the thermoplastic epoxy resin to the compound addition reaction. The compound addition reaction of the aforementioned composition containing the monomer of the thermoplastic epoxy resin is preferably carried out on the surface of the functional group-containing layer as the lower layer. The resin coating layer 3 including the thermoplastic epoxy resin layer formed in such a form has excellent adhesion to the material layer and excellent adhesion to the bonding object described later.

藉由包含熱可塑性環氧樹脂之單體之組成物來形成熱可塑性環氧樹脂層32之塗布方法並無特別限定，但有舉例如噴霧塗布法、浸漬法等。The coating method for forming the thermoplastic epoxy resin layer 32 by a composition containing a monomer of a thermoplastic epoxy resin is not particularly limited, but there are, for example, a spray coating method, a dipping method, and the like.

且，包含熱可塑性環氧樹脂之單體之組成物中，為了使熱可塑性環氧樹脂之複加成反應充分進行，且形成所期望之樹脂塗布層，亦可包含溶劑，或因應必要包含著色劑等之添加劑。此時，前述組成物之溶劑以外之含有成分中，熱可塑性環氧樹脂之單體為主成分較佳。前述主成分意指熱可塑性環氧樹脂之含有率為50~100質量%。前述含有率較佳為60質量%以上，再較佳為80質量%以上。In addition, in the composition containing the monomer of the thermoplastic epoxy resin, in order to make the compound addition reaction of the thermoplastic epoxy resin fully proceed and form the desired resin coating layer, a solvent may be included, or a coloring may be included if necessary Additives such as agents. In this case, among the components other than the solvent of the aforementioned composition, the monomer of the thermoplastic epoxy resin is preferably the main component. The aforementioned main component means that the content of the thermoplastic epoxy resin is 50-100% by mass. The aforementioned content is preferably 60% by mass or more, and more preferably 80% by mass or more.

用於得到熱可塑性環氧樹脂之單體為2官能環氧樹脂與2官能酚性化合物之組合較佳。The monomer used to obtain the thermoplastic epoxy resin is preferably a combination of a bifunctional epoxy resin and a bifunctional phenolic compound.

前述複加成反應因應反應化合物等之種類而異，但在120~200℃下加熱5~90分鐘來進行較佳。具體來說，塗布前述樹脂組成物後，使適當溶劑揮發，之後，藉由加熱且進行複加成反應，能夠形成熱可塑性環氧樹脂層。The aforementioned multi-addition reaction differs depending on the type of reaction compound, etc., but it is preferable to perform it by heating at 120 to 200°C for 5 to 90 minutes. Specifically, after coating the aforementioned resin composition, a suitable solvent is volatilized, and then, by heating and performing a complex addition reaction, a thermoplastic epoxy resin layer can be formed.

[熱硬化性樹脂層33] 能夠將前述樹脂塗布層3以包含前述改質聚烯烴層之複數層來構成，並將改質聚烯烴層以外之層以由包含熱硬化性樹脂之樹脂組成物所形成之熱硬化性樹脂層33來構成。[Thermosetting resin layer 33] The resin coating layer 3 can be composed of multiple layers including the modified polyolefin layer, and the layer other than the modified polyolefin layer can be a thermosetting resin layer formed of a resin composition containing a thermosetting resin 33 to constitute.

且，包含前述熱硬化性樹脂之樹脂組成物中，為了使前述熱硬化性樹脂之硬化反應充分地進行，且形成所期望之樹脂塗布層，亦可包含溶劑，或因應必要包含著色劑等之添加劑。此時，前述樹脂組成物之溶劑以外之含有成分中，前述熱硬化性樹脂為主成分較佳。前述主成分意指前述熱硬化性樹脂之含有率為40~100質量%。前述含有率較佳為60質量%以上，再較佳為70質量%以上，更較佳為80質量%以上。In addition, in the resin composition containing the aforementioned thermosetting resin, in order to fully advance the curing reaction of the aforementioned thermosetting resin and form the desired resin coating layer, a solvent may be included, or if necessary, a colorant or the like may be included. additive. In this case, among the components other than the solvent of the resin composition, the thermosetting resin is preferably the main component. The aforementioned main component means that the content of the aforementioned thermosetting resin is 40-100% by mass. The aforementioned content is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more.

作為前述熱硬化性樹脂，有舉例如胺甲酸乙酯樹脂、環氧樹脂、乙烯酯樹脂、不飽和聚酯樹脂。Examples of the thermosetting resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.

熱硬化性樹脂層33亦可由此等之樹脂中單獨1種所形成，亦可混合2種以上來形成。或者，能夠將熱硬化性樹脂層33以複數層來構成，並將各層以包含相異種類之熱硬化性樹脂之樹脂組成物來形成。The thermosetting resin layer 33 may be formed of one type of these resins alone, or may be formed by mixing two or more types. Alternatively, the thermosetting resin layer 33 may be composed of a plurality of layers, and each layer may be formed of a resin composition containing different kinds of thermosetting resins.

藉由包含前述熱硬化性樹脂之單體之組成物，形成熱硬化性樹脂層33之塗布方法並無特別限定，但有舉例如噴霧塗布法、浸漬法等。The coating method for forming the thermosetting resin layer 33 from the composition containing the monomer of the thermosetting resin is not particularly limited, but there are, for example, a spray coating method, a dipping method, and the like.

且，本實施型態中所述之熱硬化性樹脂廣泛地意指交聯硬化之樹脂，不限定於加熱硬化型，亦包含常溫硬化型或光硬化型。於此，本說明書中，常溫意指5~35℃，較佳為15~25℃。 前述光硬化型能夠藉由可見光或紫外線之照射並在短時間下硬化。亦可將前述光硬化型與加熱硬化型及/或常溫硬化型併用。作為前述光硬化型，有舉例如昭和電工股份公司製「Ripoxy(註冊商標)LC-760」、同「Ripoxy(註冊商標)LC-720」等之乙烯酯樹脂。In addition, the thermosetting resin mentioned in the present embodiment broadly refers to a cross-linked and hardened resin, and is not limited to a heat-curing type, but also includes a room-temperature-curing type or a light-curing type. Here, in this specification, normal temperature means 5 to 35°C, preferably 15 to 25°C. The aforementioned light-curing type can be cured in a short time by irradiation of visible light or ultraviolet light. The aforementioned photo-curing type, heat-curing type and/or room-temperature curing type may also be used in combination. As the aforementioned light-curing type, there are vinyl ester resins such as "Ripoxy (registered trademark) LC-760" manufactured by Showa Denko Co., Ltd. and the same "Ripoxy (registered trademark) LC-720".

(胺甲酸乙酯樹脂) 前述胺甲酸乙酯樹脂通常為藉由異氰酸酯化合物之異氰酸基與多元醇化合物之羥基之反應所得之樹脂，在ASTM D16中，為相當於定義成「包含媒液不揮發成分10wt%以上之聚異氰酸酯之塗料」之胺甲酸乙酯樹脂較佳。前述胺甲酸乙酯樹脂亦可為一液型或二液型。(Urethane resin) The aforementioned urethane resin is usually a resin obtained by the reaction between the isocyanate group of the isocyanate compound and the hydroxyl group of the polyol compound. In ASTM D16, it is equivalent to the definition of "containing 10wt% or more of the non-volatile content of the vehicle The urethane resin of "polyisocyanate coating" is preferable. The aforementioned urethane resin may also be a one-component type or a two-component type.

作為一液型胺甲酸乙酯樹脂，有舉例如油改質型(由不飽和脂肪酸基之氧化聚合所硬化者)、濕氣硬化型(由異氰酸基與空氣中之水之反應所硬化者)、嵌段型(嵌段劑藉由加熱所解離且再生之異氰酸基與羥基反應所硬化者)、噴漆型(藉由溶劑揮發並乾燥所硬化者)等。此等中，以操作容易性等之觀點，適合使用濕氣硬化型一液胺甲酸乙酯樹脂。具體來說，有舉出昭和電工股份公司製「UM-50P」等。As one-component urethane resins, there are, for example, oil-modified type (hardened by the oxidative polymerization of unsaturated fatty acid groups), moisture hardening type (hardened by the reaction of isocyanate groups with water in the air). ), block type (the blocking agent is cured by the reaction between the isocyanate group dissociated and regenerated by heating and the hydroxyl group), spray paint type (the one is cured by solvent volatilization and drying), etc. Among these, from the viewpoint of ease of handling, etc., a moisture-curable one-liquid urethane resin is suitably used. Specifically, "UM-50P" manufactured by Showa Denko Co., Ltd. is mentioned.

作為二液型胺甲酸乙酯樹脂，有舉例如觸媒硬化型(異氰酸基與空氣中之水等在觸媒存在下反應所硬化者)、多元醇硬化型(藉由異氰酸基與多元醇化合物之羥基之反應所硬化者)等。As the two-component urethane resin, there are, for example, a catalyst-curing type (the isocyanate group and water in the air are cured by the reaction in the presence of a catalyst), and the polyol-curing type (by isocyanate group Hardened by the reaction with the hydroxyl group of the polyol compound) and so on.

作為前述多元醇硬化型之多元醇化合物，有舉例如聚酯多元醇、聚醚多元醇、酚樹脂等。 且，作為前述多元醇硬化型之具有異氰酸基之異氰酸酯化合物，有舉例如六亞甲基二異氰酸酯(HDI)、四亞甲基二異氰酸酯、二聚酸二異氰酸酯等之脂肪族異氰酸酯；2,4-或2,6-甲伸苯基二異氰酸酯(TDI)或其混合物、p-伸苯基二異氰酸酯、二甲苯撐基二異氰酸酯、二苯基甲烷二異氰酸酯(MDI)或其多核體混合物之聚合物型MDI等之芳香族異氰酸酯；異佛爾酮二異氰酸酯(IPDI)等之脂環族異氰酸酯等。 前述多元醇硬化型之二液型胺甲酸乙酯樹脂中前述多元醇化合物與前述異氰酸酯化合物之摻混比，以羥基/異氰酸基之莫耳當量比為0.7~1.5之範圍較佳。Examples of the polyol compound of the polyol curing type include polyester polyols, polyether polyols, phenol resins, and the like. Moreover, as the aforementioned polyol-curable isocyanate compound having an isocyanate group, there are, for example, aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimer acid diisocyanate; 2 ,4- or 2,6-toluene diisocyanate (TDI) or its mixture, p-phenylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate (MDI) or its polynuclear mixture Aromatic isocyanate such as polymer type MDI; alicyclic isocyanate such as isophorone diisocyanate (IPDI). The blending ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in molar equivalent ratio of hydroxyl group/isocyanate group.

作為前述二液型胺甲酸乙酯樹脂中所使用之胺甲酸乙酯化觸媒，有舉例如三伸乙基二胺、四甲基胍、N,N,N’,N’-四甲基己烷-1,6-二胺、二甲基醚胺、N,N,N’,N”,N”-五甲基二伸丙基-三胺、N-甲基嗎呋啉、雙(2-二甲基胺基乙基)醚、二甲基胺基乙氧基乙醇、三乙基胺等之胺系觸媒；二正丁基二乙酸酯、二正丁基二月桂酸酯、二正丁基硫基羧酸酯、二正丁基二馬來酸酯等之有機錫系觸媒等。 前述多元醇硬化型中，一般來說，相對於前述多元醇化合物100質量份，前述胺甲酸乙酯化觸媒以0.01~10質量份摻混較佳。As the urethane catalyst used in the aforementioned two-component urethane resin, there are, for example, triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethyl Hexane-1,6-diamine, dimethyl ether amine, N,N,N',N",N"-pentamethyldipropylene-triamine, N-methylmorpholine, bis( Amine catalysts such as 2-dimethylaminoethyl ether, dimethylaminoethoxyethanol, triethylamine, etc.; di-n-butyl diacetate, di-n-butyl dilaurate , Di-n-butylthio carboxylate, di-n-butyl dimaleate and other organotin catalysts. In the polyol curing type, generally, the urethane catalyst is preferably blended in 0.01 to 10 parts by mass relative to 100 parts by mass of the polyol compound.

(環氧樹脂) 前述環氧樹脂為1分子中至少具有2個環氧基之樹脂。 作為前述環氧樹脂之硬化前之預聚合物，有舉例如醚系雙酚型環氧樹脂、酚醛清漆型環氧樹脂、聚酚型環氧樹脂、脂肪族型環氧樹脂、酯系之芳香族環氧樹脂、環狀脂肪族環氧樹脂、醚･酯系環氧樹脂等，此等中，適合使用雙酚A型環氧樹脂。此等中，亦可單獨使用1種，亦可併用2種以上。 作為雙酚A型環氧樹脂，具體來說，有舉出三菱Chemical股份公司製「jER(註冊商標)828」、同「jER(註冊商標)1001」等。 作為酚醛清漆型環氧樹脂，具體來說有舉出The Dow Chemical Company製「D.E.N.(註冊商標)438(註冊商標)」等。(Epoxy resin) The aforementioned epoxy resin is a resin having at least two epoxy groups in one molecule. As the prepolymer before curing of the aforementioned epoxy resin, there are, for example, ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, and ester-based aromatic resin. Group epoxy resins, cycloaliphatic epoxy resins, ether and ester epoxy resins, etc. Among these, bisphenol A type epoxy resins are suitably used. Among these, one type may be used alone, or two or more types may be used in combination. Specific examples of bisphenol A epoxy resins include "jER (registered trademark) 828" manufactured by Mitsubishi Chemical Co., Ltd., "jER (registered trademark) 1001", and the like. Specific examples of novolak-type epoxy resins include "D.E.N. (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.

作為前述環氧樹脂所使用之硬化劑，有舉例如脂肪族胺、芳香族胺、酸酐、酚樹脂、硫醇類、咪唑類、陽離子觸媒等之公知硬化劑。前述硬化劑藉由與長鏈脂肪族胺或/及硫醇類之併用，能夠得到伸張率變大，且耐衝擊性優異之效果。 作為前述硫醇類之具體例，有舉出與作為用來形成後述含官能基之層之硫醇化合物所例示者相同之化合物。此等中，以伸張率及耐衝撃性之觀點，為五丁四醇肆(3-氫硫基丁酸酯)(例如昭和電工股份公司製「KarenzMT(註冊商標) PE1」)較佳。Examples of the hardener used for the epoxy resin include known hardeners such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, mercaptans, imidazoles, and cationic catalysts. The aforementioned curing agent can be used in combination with a long-chain aliphatic amine or/and mercaptans to achieve the effect of increasing the elongation and having excellent impact resistance. As specific examples of the aforementioned thiols, there are exemplified the same compounds as those exemplified as the thiol compound for forming the functional group-containing layer described later. Among these, from the viewpoint of elongation and impact resistance, pentaerythritol (3-hydrothiobutyrate) (for example, "KarenzMT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.) is preferable.

(乙烯酯樹脂) 前述乙烯酯樹脂係將乙烯酯化合物溶解於聚合性單體(例如苯乙烯等)者。亦稱作環氧(甲基)丙烯酸酯樹脂，但前述乙烯酯樹脂亦包含胺甲酸乙酯(甲基)丙烯酸酯樹脂。 作為前述乙烯酯樹脂，亦能夠使用例如「聚酯樹脂手冊」(日刊工業新聞社，1988年發行)、「塗料用語辭典」(色材協會，1993年發行)等記載者，且具體來說，有舉出昭和電工股份公司製「Ripoxy(註冊商標)R-802」、同「Ripoxy(註冊商標)R-804」、同「Ripoxy(註冊商標)R-806」等。(Vinyl ester resin) The aforementioned vinyl ester resin is one in which a vinyl ester compound is dissolved in a polymerizable monomer (for example, styrene). It is also called epoxy (meth)acrylate resin, but the aforementioned vinyl ester resin also includes urethane (meth)acrylate resin. As the aforementioned vinyl ester resin, it is also possible to use, for example, "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Paint Terms" (Colored Materials Association, published in 1993), etc., and specifically, Examples include Showa Denko Corporation "Ripoxy (registered trademark) R-802", the same "Ripoxy (registered trademark) R-804", and the same "Ripoxy (registered trademark) R-806".

作為前述胺甲酸乙酯(甲基)丙烯酸酯樹脂，有舉例如使異氰酸酯化合物與多元醇化合物反應後，再使含羥基之(甲基)丙烯酸單體(及因應必要之含羥基之烯丙基醚單體)反應所得之含自由基聚合性不飽和基之寡聚物。具體來說有舉出昭和電工股份公司製「Ripoxy(註冊商標)R-6545」等。As the aforementioned urethane (meth)acrylate resin, for example, after reacting an isocyanate compound with a polyol compound, a hydroxyl-containing (meth)acrylic monomer (and, if necessary, a hydroxyl-containing allyl Ether monomer) The oligomer containing radical polymerizable unsaturated group obtained by the reaction. Specifically, there is "Ripoxy (registered trademark) R-6545" manufactured by Showa Denko Corporation.

前述乙烯酯樹脂能夠在有機過氧化物等之觸媒存在下藉由加熱並以自由基聚合使其硬化。 作為前述有機過氧化物，並無特別限定，但有舉例如酮過氧化物類、過氧縮酮類、氫過氧化物類、二烯丙基過氧化物類、二醯基過氧化物類、過氧酯類、過氧二聚碳酸酯類等。此等藉由與鈷金屬鹽等組合，能夠在常溫下硬化。 作為前述鈷金屬鹽，並無特別限定，但有舉例如環烷酸鈷、辛基酸鈷、氫氧化鈷等。此等之中，為環烷酸鈷或/及辛基酸鈷較佳。The aforementioned vinyl ester resin can be cured by heating and radical polymerization in the presence of a catalyst such as an organic peroxide. There are no particular limitations on the aforementioned organic peroxides, but examples include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, and diacyl peroxides. , Peroxy esters, peroxy dipolycarbonate, etc. These can be hardened at room temperature by combining with cobalt metal salt and the like. The cobalt metal salt is not particularly limited, but for example, cobalt naphthenate, cobalt octylate, cobalt hydroxide, and the like are mentioned. Among these, cobalt naphthenate or/and cobalt octylate are preferred.

(不飽和聚酯樹脂) 前述不飽和聚酯樹脂係將多元醇化合物與不飽和多元酸(及因應必要之飽和多元酸)之酯化反應所得之縮合生成物(不飽和聚酯)溶解於聚合性單體(例如苯乙烯等)者。 作為前述不飽和聚酯樹脂，亦能夠使用「聚酯樹脂手冊」(日刊工業新聞社，1988年發行)、「塗料用語辭典」(色材協會，1993年發行)等記載者，且具體來說有舉出昭和電工股份公司製「Rigolac(註冊商標)」等。(Unsaturated polyester resin) The aforementioned unsaturated polyester resin is a condensation product (unsaturated polyester) obtained by the esterification reaction of a polyol compound and an unsaturated polybasic acid (and if necessary saturated polybasic acid) is dissolved in a polymerizable monomer (such as styrene) Etc.). As the aforementioned unsaturated polyester resin, it is also possible to use those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Paint Terms" (Color Material Association, published in 1993), and more specifically Examples include "Rigolac (registered trademark)" manufactured by Showa Denko Corporation.

前述不飽和聚酯樹脂能夠在與前述乙烯酯樹脂相同之觸媒存在下藉由加熱並以自由基聚合使其硬化。The aforementioned unsaturated polyester resin can be cured by heating and radical polymerization in the presence of the same catalyst as the aforementioned vinyl ester resin.

樹脂塗布層係在材料層之表面上以優異之接著性而形成，且與聚烯烴一同發揮優異之接著性。且，該材料層之表面有經保護，且能夠抑制該材料層之表面上附著汙垢。The resin coating layer is formed on the surface of the material layer with excellent adhesiveness, and exhibits excellent adhesiveness together with polyolefin. In addition, the surface of the material layer is protected, and the adhesion of dirt on the surface of the material layer can be inhibited.

因此，藉由樹脂塗布層，能夠賦予材料層與接合對象之聚烯烴之優異接合性。進而，如上述，以材料層之表面受到保護之狀態，經過數個月之長期間，也能夠得到可維持能得優異之接著性之狀態之複合積層體。Therefore, the resin coating layer can impart excellent bonding properties between the material layer and the polyolefin to be bonded. Furthermore, as described above, in a state where the surface of the material layer is protected, it is possible to obtain a composite laminate in a state where excellent adhesiveness can be maintained over a long period of several months.

如上述，樹脂塗布層達到對材料層賦予對接合對象之聚烯烴之優異接合性之作用。樹脂塗布層亦可稱作複合積層體之底塗層。 於此所述底塗層意指例如後述接合體，材料層與樹脂材等接合對象經接合一體化時，介在該材料層與接合對象之間，且使材料層之對接合對象之接著性提升之層。As described above, the resin coating layer has the effect of imparting excellent adhesion to the polyolefin to be joined to the material layer. The resin coating layer may also be referred to as the primer layer of the composite laminate. The primer layer here means, for example, the bonded body described later. When the material layer and the bonding object such as the resin material are bonded and integrated, it is interposed between the material layer and the bonding object, and improves the adhesion of the material layer to the bonding object.的层。 The layer.

＜含官能基之層4＞ 如圖2所示，在前述材料層2與前述樹脂塗布層3之間，能夠具有與前述材料層2與前述樹脂塗布層3鄰接而積層之一層或複數層之含官能基之層4。 具有含官能基之層時，該含官能基之層所具有之官能基會分別與前述材料層之表面之羥基及構成前述樹脂塗布層之樹脂所具有之官能基反應，藉由所形成之化學鍵結，能夠得到使材料層之表面與樹脂塗布層之接著性提升之效果，且能夠對與接合對象之接合性之提升有貢獻。<Functional group-containing layer 4> As shown in FIG. 2, between the material layer 2 and the resin coating layer 3, there can be one or more functional group-containing layers 4 adjacent to the material layer 2 and the resin coating layer 3 to be laminated. When there is a functional group-containing layer, the functional groups of the functional group-containing layer will react with the hydroxyl groups on the surface of the material layer and the functional groups of the resin constituting the resin coating layer, respectively, through the formed chemical bond As a result, the effect of improving the adhesion between the surface of the material layer and the resin coating layer can be obtained, and it can contribute to the improvement of the adhesion with the bonding object.

《處理》 含官能基之層4係將材料層2之表面使用選自下述(1’)~(7’)所成群中至少1種來處理所形成者較佳，前述處理為選自下述(2”)~(5”)中至少1種再較佳。 (1’) 含有選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基之矽烷偶合劑 (2’) 選自環氧化合物及硫醇化合物中至少1種與具有胺基之矽烷偶合劑之組合 (3’) 具有選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種與具有氫硫基之矽烷偶合劑之組合 (4’) 硫醇化合物與具有(甲基)丙烯醯基之矽烷偶合劑之組合 (5’) 選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種與具有環氧基之矽烷偶合劑之組合 (6’) 異氰酸酯化合物 (7’) 硫醇化合物"deal with" The functional group-containing layer 4 is preferably formed by treating the surface of the material layer 2 with at least one selected from the group of (1')~(7') below. The aforementioned treatment is selected from the following ( At least one of 2”)~(5”) is more preferable. (1') Silane coupling agent containing at least one functional group selected from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2’) A combination of at least one selected from epoxy compounds and thiol compounds and a silane coupling agent with an amine group (3') Among the group of compounds having an epoxy compound, an amine compound, an isocyanate compound, a compound having a (meth)acryloyl group and an epoxy group, and a compound having a (meth)acryloyl group and an amino group At least one combination with silane coupling agent with hydrogen sulfide group (4') Combination of mercaptan compound and silane coupling agent with (meth)acrylic acid group (5') A combination of at least one selected from the group of compounds having amine groups and (meth)acrylic acid groups, amine compounds, and thiol compounds, and a silane coupling agent having epoxy groups (6’) Isocyanate compound (7’) Thiol compound

(2”) 以具有胺基之矽烷偶合劑處理後，加成選自環氧化合物及硫醇化合物中至少1種之處理 (3”) 以具有氫硫基之矽烷偶合劑處理後，加成選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種之處理 (4”) 以具有(甲基)丙烯醯基之矽烷偶合劑處理後，加成硫醇化合物之處理 (5”) 以具有環氧基之矽烷偶合劑處理後，加成具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種之處理(2") After treatment with silane coupling agent with amine group, at least one selected from epoxy compound and thiol compound is added. (3") After treatment with a silane coupling agent having a hydrogen sulfide group, the addition is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (methyl) ) Treatment of at least one of the groups of acryl and amine compounds (4") After treatment with (meth)acrylic silane coupling agent, the treatment of adding thiol compound (5") After treating with epoxy-containing silane coupling agent, adding at least one of the group of compounds with amine groups and (meth)acrylic groups, amine compounds, and thiol compounds

《官能基》 含官能基之層4係包含藉由前述處理所導入之官能基較佳，具體來說，包含選自下述(1)~(7)所成群中至少1種官能基較佳。 (1)來自矽烷偶合劑，且選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基 (2)使來自矽烷偶合劑之胺基與選自環氧化合物及硫醇化合物中至少1種反應而成之官能基 (3)使來自矽烷偶合劑之氫硫基與選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種反應而成之官能基 (4)使來自矽烷偶合劑之(甲基)丙烯醯基與硫醇化合物反應而成之官能基 (5)使來自矽烷偶合劑之環氧基與選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種反應而成之官能基 (6)來自異氰酸酯化合物之異氰酸基 (7)來自硫醇化合物之氫硫基"Functional Group" The functional group-containing layer 4 preferably contains the functional group introduced by the aforementioned treatment. Specifically, it preferably contains at least one functional group selected from the group of (1) to (7) below. (1) It is derived from a silane coupling agent and is selected from at least one functional group from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2) A functional group formed by reacting an amine group derived from a silane coupling agent with at least one selected from epoxy compounds and thiol compounds (3) The sulfhydryl group derived from the silane coupling agent is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and A functional group formed by the reaction of at least one of a group of amine-based compounds (4) Functional group formed by reacting (meth)acrylic acid group derived from silane coupling agent with thiol compound (5) A functional group formed by reacting an epoxy group derived from a silane coupling agent with at least one compound selected from the group consisting of an amine group and a (meth)acrylic acid group, an amine compound, and a thiol compound (6) Isocyanate group from isocyanate compound (7) Hydrosulfide group from thiol compound

在材料層形成含官能基之層4之前，能夠對材料層之表面施予前處理。作為前處理，為選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種較佳。 藉由施予前處理，藉由微細凹凸之固定效果，與含官能基之層所具有之官能基分別與前述材料層之表面之羥基及構成前述樹脂塗布層3之樹脂所具有之官能基反應所形成之化學鍵結的相乘效果，能夠提升材料層之表面與樹脂塗布層之接著性及與接合對象之接合性。Before the material layer is formed into the functional group-containing layer 4, pretreatment can be applied to the surface of the material layer. The pretreatment is preferably at least one selected from the group consisting of degreasing treatment, UV ozone treatment, air jet treatment, grinding treatment, plasma treatment, and corona discharge treatment. By applying the pre-treatment, with the fixing effect of the fine concavities and convexities, the functional groups of the layer containing functional groups react with the hydroxyl groups on the surface of the material layer and the functional groups of the resin constituting the resin coating layer 3, respectively. The synergistic effect of the formed chemical bond can improve the adhesion between the surface of the material layer and the resin coating layer and the adhesion with the bonding object.

以前述矽烷偶合劑、前述異氰酸酯化合物或前述硫醇化合物等來形成含官能基之層之方法並無特別限定，但有舉例如噴霧塗布法、浸漬法等。具體來說，能夠藉由將材料層浸漬於濃度5~50質量%之矽烷偶合劑等常溫~100℃之溶液中1分鐘~5天後，再使其於常溫~100℃下乾燥1分鐘~5小時等之方法來進行。The method of forming the functional group-containing layer using the silane coupling agent, the isocyanate compound, or the thiol compound, etc., is not particularly limited, but examples include spray coating methods, dipping methods, and the like. Specifically, the material layer can be immersed in a solution at room temperature to 100°C, such as a silane coupling agent with a concentration of 5-50% by mass, for 1 minute to 5 days, and then dried at room temperature to 100°C for 1 minute~ 5 hours and so on.

[矽烷偶合劑] 作為前述矽烷偶合劑，能夠使用例如玻璃纖維之表面處理等中所使用之公知者。使矽烷偶合劑水解所生成之矽醇基，或此等寡聚物化之矽醇基會藉由與存在材料層2之表面之羥基反應並鍵結，能夠對材料層賦予(導入)基於能夠與樹脂塗布層3進行化學鍵結之該矽烷偶合劑之構造之官能基。[Silane Coupling Agent] As the aforementioned silane coupling agent, for example, known ones used in the surface treatment of glass fibers and the like can be used. The silanol group generated by the hydrolysis of the silane coupling agent, or these oligomerized silanol groups, will react and bond with the hydroxyl groups on the surface of the material layer 2 to give (introduction) to the material layer based on the ability to interact with The resin coating layer 3 chemically bonds the functional groups of the structure of the silane coupling agent.

前述矽烷偶合劑並無特別限定，但能夠使用具有環氧基之矽烷偶合劑、具有胺基之矽烷偶合劑、具有氫硫基之矽烷偶合劑、具有(甲基)丙烯醯基之矽烷偶合劑等。作為具有環氧基之矽烷偶合劑，有舉例如2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等。作為具有胺基之矽烷偶合劑，有舉出N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷等。作為具有氫硫基之矽烷偶合劑，有舉出3-氫硫基丙基甲基二甲氧基矽烷、二硫醇三嗪丙基三乙氧基矽烷等。作為具有(甲基)丙烯醯基之矽烷偶合劑，有舉出3-甲基丙烯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯氧基丙基三甲氧基矽烷、3-甲基丙烯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等。且，作為其他有效之矽烷偶合劑，有舉出3-異氰酸基丙基三乙氧基矽烷、乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、p-苯乙烯基三甲氧基矽烷等之具有乙烯基之矽烷偶合劑、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯苄基)-2-胺基丙基三甲氧基矽烷之鹽酸鹽、參-(三甲氧基矽烷基丙基)聚異氰酸酯、3-脲基丙基三烷氧基矽烷。此等亦可單獨併用1種，亦可併用2種以上。The aforementioned silane coupling agent is not particularly limited, but it is possible to use a silane coupling agent having an epoxy group, a silane coupling agent having an amine group, a silane coupling agent having a hydrogen sulfide group, and a silane coupling agent having a (meth)acryloyl group. Wait. As the silane coupling agent having an epoxy group, there are, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-condensation Glyceryloxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. As the silane coupling agent having an amino group, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, etc. As the silane coupling agent having a sulfhydryl group, there are exemplified 3-sulfhydrylpropylmethyldimethoxysilane, dithiol triazinepropyltriethoxysilane, and the like. As the silane coupling agent having a (meth)acryloyl group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. And, as other effective silane coupling agents, there are 3-isocyanatopropyltriethoxysilane, ethylene trimethoxysilane, ethylene triethoxysilane, p-styryltrimethoxysilane, etc. Silane coupling agent with vinyl group, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxy Silane, N-(vinylbenzyl)-2-aminopropyltrimethoxysilane hydrochloride, ginseng-(trimethoxysilylpropyl) polyisocyanate, 3-ureidopropyltrialkoxysilane . These may be used together individually by 1 type, and may use 2 or more types together.

[異氰酸酯化合物] 前述異氰酸酯化合物，藉由該異氰酸酯化合物中之異氰酸基與存在材料層2之表面之羥基反應並鍵結，能夠對材料層賦予(導入)基於能夠與樹脂塗布層3進行化學鍵結之該異氰酸酯化合物之構造之官能基。[Isocyanate compound] In the aforementioned isocyanate compound, the isocyanate group in the isocyanate compound reacts with and bonds with the hydroxyl group on the surface of the material layer 2, and the material layer can be given (introduced) based on the isocyanate that can chemically bond with the resin coating layer 3. The functional group of the structure of the compound.

作為前述異氰酸酯化合物，並無特別限定，但有舉例如多官能異氰酸酯之二苯基甲烷二異氰酸酯(MDI)、六亞甲基二異氰酸酯(HDI)、甲伸苯基二異氰酸酯(TDI)、異佛爾酮二異氰酸酯(IPDI)等之外，也有具有自由基反應性基之異氰酸酯化合物之2-異氰酸酯乙基甲基丙烯酸酯(例如昭和電工股份公司製「KarenzMOI(註冊商標)」)、2-異氰酸酯乙基丙烯酸酯(例如昭和電工股份公司製「KarenzAOI(註冊商標)」、同「AOI-VM(註冊商標)」)、1,1-(雙丙烯醯基氧基乙基)乙基異氰酸酯(例如昭和電工股份公司製「KarenzBEI(註冊商標)」)等。The isocyanate compound is not particularly limited, but there are, for example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophore, which are polyfunctional isocyanates. In addition to ketone diisocyanate (IPDI), etc., there are also 2-isocyanate ethyl methacrylate (such as "Karenz MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.) and 2-isocyanate, which are isocyanate compounds with radical reactive groups. Ethyl acrylate (e.g. "KarenzAOI (registered trademark)" manufactured by Showa Denko Corporation, the same as "AOI-VM (registered trademark)"), 1,1-(bisacryloxyethyl) ethyl isocyanate (e.g. Showa Denko Corporation (“KarenzBEI (registered trademark)”), etc.

[硫醇化合物] 前述硫醇化合物，藉由該硫醇化合物中之氫硫基與存在材料層2之表面之羥基反應並鍵結，能夠對材料層賦予(導入)基於能夠與樹脂塗布層或接合對象進行化學鍵結之該硫醇化合物之構造之官能基。[Thiol compound] The aforementioned thiol compound can be provided (introduced) to the material layer based on the ability to chemically bond with the resin coating layer or the bonding object by reacting and bonding with the sulfhydryl group in the thiol compound and the hydroxyl group on the surface of the material layer 2 The functional group of the structure of the thiol compound.

作為前述硫醇化合物，並無特別限定，但有舉例如五丁四醇肆(3-氫硫基丙酸酯)(例如三菱化學股份公司製「QX40」、東Toray Fine Chemical股份公司製「QE-340M」)、醚系一級硫醇(例如Cognis公司製「Cupcure3-800」)、1,4-雙(3-氫硫基丁醯基氧基)丁烷(例如昭和電工股份公司製「KarenzMT(註冊商標) BD1」)、五丁四醇肆(3-氫硫基丁酸酯)(例如昭和電工股份公司製「KarenzMT (註冊商標) PE1」)、1,3,5-參(3-氫硫基丁基氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(例如昭和電工股份公司製「KarenzMT(註冊商標) NR1」)等。The thiol compound is not particularly limited, but for example, pentaerythritol 4 (3-hydrothiopropionate) (for example, "QX40" manufactured by Mitsubishi Chemical Co., Ltd., "QE" manufactured by Toray Fine Chemical Co., Ltd. -340M''), ether-based first-class mercaptans (e.g. "Cupcure3-800" manufactured by Cognis), 1,4-bis(3-hydrothiobutanoyloxy)butane (e.g. ``KarenzMT (registered (Trademark) BD1''), Pentaerythritol 4 (3-Hydroxythiobutyrate) (e.g. "KarenzMT (registered trademark) PE1" manufactured by Showa Denko Co., Ltd.), 1,3,5-gin (3-Hydroxysulfide) Butyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g. "KarenzMT (registered trademark) NR1" manufactured by Showa Denko Corporation), etc. .

[接合體5] 如圖3所示，本實施型態之接合體5係如上述，複合積層體1之樹脂塗布層3以作為底塗層之該底塗層側之面與聚烯烴6經接合一體化者。[Joint body 5] As shown in FIG. 3, the joined body 5 of the present embodiment is as described above, in which the resin coating layer 3 of the composite laminate 1 has the surface of the primer layer side as the primer layer and the polyolefin 6 integrated by bonding.

前述底塗層之厚度(乾燥後之厚度)會因前述接合對象之材質或接合部分之接觸面積而異，接合對象非薄膜時，以得到與接合對象之優異接合強度之觀點及以藉由材料間之熱收縮差異，抑制應力集中在界面之樹脂端部之觀點，為1μm~10mm較佳。再較佳為20μm~3mm，更較佳為40μm~1mm。且，前述底塗層為複數層時，底塗層之厚度(乾燥後之厚度)設為各層合計之厚度。 接合對象為薄膜時，前述底塗層之厚度(乾燥後之厚度)為0.1μm~1mm較佳，再較佳為0.1μm~100μm。The thickness of the primer layer (thickness after drying) varies with the material of the bonding object or the contact area of the bonding part. When the bonding object is not a thin film, the viewpoint of obtaining excellent bonding strength with the bonding object and the use of the material The thermal shrinkage difference between the two and the viewpoint of suppressing stress concentration at the resin end of the interface is preferably 1μm~10mm. It is more preferably 20 μm to 3 mm, and more preferably 40 μm to 1 mm. In addition, when the aforementioned primer layer is a plurality of layers, the thickness of the primer layer (thickness after drying) shall be the total thickness of each layer. When the bonding object is a film, the thickness of the aforementioned primer layer (thickness after drying) is preferably 0.1 μm to 1 mm, and more preferably 0.1 μm to 100 μm.

前述接合體中之聚烯烴並無特別限定，為一般的合成樹脂即可。例如有聚乙烯、聚丙烯等。 聚丙烯一般來說，有被分類成僅聚合丙烯之剛性較高之均聚合物、共聚合少量乙烯之透明性較高且柔軟之隨機聚合物、橡膠成分(EPR)均勻且細微地分散於均･隨機聚合物之耐衝撃性較高之嵌段共聚合物，但可為其任一者。且，亦可為以含有滑石、玻璃纖維、碳纖維之型態而使強度提高者。作為含有滑石者，有Sunallomer公司製商品名TRC104N，作為含有玻璃纖維者，有Daicelpolymer公司製商品名PP-GF40-01 F02，作為含有碳纖維者，有Daicelpolymer公司製商品名PP-CF40-11 F008等。The polyolefin in the aforementioned joined body is not particularly limited, and may be a general synthetic resin. For example, there are polyethylene, polypropylene and so on. Generally speaking, polypropylene is classified into a homopolymer with higher rigidity that only polymerizes propylene, a random polymer with higher transparency and softness that copolymerizes a small amount of ethylene, and the rubber component (EPR) is uniformly and finely dispersed in the homogeneous polymer. ･The random polymer is a block copolymer with higher impact resistance, but it can be any one. Moreover, it may be a form containing talc, glass fiber, and carbon fiber to increase the strength. As those containing talc, there is a trade name TRC104N manufactured by Sunallomer Corporation, as those containing glass fibers, there is a trade name PP-GF40-01 F02 manufactured by Daicelpolymer, and as those containing carbon fibers, there are trade name PP-CF40-11 F008 manufactured by Daicelpolymer, etc. .

作為製造前述接合體之方法，能夠將複合積層體與前述樹脂材之成形體個別製作者接著，並使其接合一體化。 且，能夠將前述樹脂材以射出成形、噴霧成形、轉印成形等之方法成形之同時，使複合積層體之前述底塗層側之面與前述樹脂材接合一體化。具體來說，有舉出在前述複合積層體之底塗層側之面，以選自超音波溶著法、振動溶著法、電磁誘導法、高周波法、雷射法及熱壓法所成群中至少1種方法，將前述聚烯烴溶著之方法，或在前述複合積層體之底塗層側之面將聚烯烴射出溶著之方法。 [實施例]As a method of manufacturing the aforementioned joined body, the composite laminate and the aforementioned molded body of the resin material can be separately produced and joined and integrated. In addition, the resin material can be molded by injection molding, spray molding, transfer molding, or the like, and the surface of the undercoat layer side of the composite laminate can be joined and integrated with the resin material. Specifically, the surface on the undercoat layer side of the aforementioned composite laminate is selected from the group consisting of ultrasonic fusion method, vibration fusion method, electromagnetic induction method, high frequency method, laser method, and hot pressing method. At least one method in the group, a method of melting the aforementioned polyolefin, or a method of dissolving the polyolefin on the surface of the undercoat layer of the aforementioned composite laminate. [Example]

接著，針對本發明之具體實施例進行說明，但本發明不特別限定於此等實施例。Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

＜製造例1＞ 於燒瓶中添加入馬來酸酐改質聚丙烯(三菱Chemical股份公司製Modic(註冊商標)ER321P)：5g、二甲苯：95g，一邊攪拌一邊升溫至125℃來溶解。接著將2官能環氧樹脂(三菱Chemical股份公司製jER(註冊商標)1001：雙酚A與表氯醇之重縮合物)：1.01g、雙酚A：0.24g、2,4,6-參(二甲基胺基甲基)酚：0.006g放入燒瓶中，於125℃攪拌30分鐘，得到熱可塑性環氧樹脂、2官能環氧樹脂、以2官能酚化合物改質之馬來酸酐改質聚丙烯：改質PP-1。＜Manufacturing example 1＞ Maleic anhydride-modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g and xylene: 95 g were added to the flask, and the flask was heated to 125°C for dissolution while stirring. Next, bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.: heavy condensate of bisphenol A and epichlorohydrin): 1.01 g, bisphenol A: 0.24 g, 2, 4, 6 (Dimethylaminomethyl)phenol: 0.006g is put into the flask and stirred at 125°C for 30 minutes to obtain thermoplastic epoxy resin, bifunctional epoxy resin, and maleic anhydride modified with bifunctional phenol compound. Quality polypropylene: modified PP-1.

＜製造例2＞ 於燒瓶中添加入馬來酸酐改質聚丙烯(三菱Chemical股份公司製Modic(註冊商標)ER321P)：5g、二甲苯：95g，一邊攪拌一邊升溫至125℃來溶解。接著，將2官能環氧樹脂(三菱Chemical股份公司製jER(註冊商標)1004)：0.49g、雙酚A：0.06g、2,4,6-參(二甲基胺基甲基)酚：0.003g放入燒瓶中，於125℃攪拌30分鐘，得到熱可塑性環氧樹脂、2官能環氧樹脂、以2官能酚化合物改質之馬來酸酐改質聚丙烯：改質PP-2。＜Manufacturing example 2＞ Maleic anhydride-modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g and xylene: 95 g were added to the flask, and the flask was heated to 125°C for dissolution while stirring. Next, bifunctional epoxy resin (jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd.): 0.49 g, bisphenol A: 0.06 g, 2,4,6-ginseng (dimethylaminomethyl)phenol: 0.003g was put into the flask and stirred at 125°C for 30 minutes to obtain a thermoplastic epoxy resin, a bifunctional epoxy resin, and a maleic anhydride modified polypropylene modified with a bifunctional phenol compound: modified PP-2.

＜製造例3＞ 於燒瓶中添加入含滑石之聚丙烯(Sunallomer股份公司製TRC104N)：5g、二甲苯：95g，一邊攪拌一邊升溫至125℃來溶解。接著將2官能環氧樹脂(三菱Chemical股份公司製jER(註冊商標)1001)：1.01g、雙酚A：0.24g、2,4,6-參(二甲基胺基甲基)酚：0.006g放入燒瓶中，於125℃攪拌30分鐘，得到熱可塑性環氧樹脂(20質量%)與聚丙烯之混合物：改質PP-3。＜Manufacturing example 3＞ A talc-containing polypropylene (TRC104N manufactured by Sunallomer Co., Ltd.): 5 g and xylene: 95 g were added to the flask, and the flask was heated to 125°C for dissolution while stirring. Next, bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.): 1.01 g, bisphenol A: 0.24 g, 2,4,6-ginseng (dimethylaminomethyl)phenol: 0.006 g was put into a flask and stirred at 125°C for 30 minutes to obtain a mixture of thermoplastic epoxy resin (20% by mass) and polypropylene: modified PP-3.

＜製造例4＞ 於燒瓶中添加入二甲苯：95g、2官能環氧樹脂(三菱Chemical股份公司製jER1007)：1.20g、雙酚A：0.066g、2,4,6-參(二甲基胺基甲基)酚：0.003g，於125℃攪拌30分鐘，反應後得到熱可塑性環氧樹脂溶液。接著於燒瓶中放入馬來酸酐改質聚丙烯(三菱Chemical股份公司製Modic(註冊商標)ER321P)：5g並溶解，得到以熱可塑性環氧樹脂(20質量%)改質之馬來酸酐改質聚丙烯：改質PP-4。＜Manufacturing example 4＞ Xylene: 95 g, bifunctional epoxy resin (jER1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.20 g, bisphenol A: 0.066 g, 2,4,6-ginseng (dimethylaminomethyl) were added to the flask. Phenol: 0.003g, stirred at 125°C for 30 minutes, after the reaction, a thermoplastic epoxy resin solution was obtained. Next, put maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g and dissolve in the flask to obtain a maleic anhydride modified polypropylene modified with a thermoplastic epoxy resin (20% by mass). Quality polypropylene: modified PP-4.

＜實施例1-1＞ (前處理步驟) 將18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)表面以丙酮進行脫脂處理。<Example 1-1> (Pre-processing steps) The surface of a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) of 18 mm×45 mm and a thickness of 1.2 mm was degreased with acetone.

(含官能基之層形成步驟) 接著，使前述丙酮脫脂處理後之玻璃基材浸漬於使3-胺基丙基三甲氧基矽烷(信越Silicone股份公司製「KBM-903」；矽烷偶合劑)2g溶解於工業用乙醇1000g之70℃之含矽烷偶合劑之溶液中20分鐘後，取出該玻璃基材使其乾燥，於該玻璃基材表面形成含官能基之層。(Formation step of functional group-containing layer) Next, the glass substrate after the aforementioned acetone degreasing treatment was immersed in 70 of 3-aminopropyltrimethoxysilane ("KBM-903" manufactured by Shin-Etsu Silicone Co., Ltd.; silane coupling agent) dissolved in 1000 g of industrial ethanol. After 20 minutes in the silane coupling agent-containing solution at ℃, the glass substrate was taken out to dry, and a functional group-containing layer was formed on the surface of the glass substrate.

(樹脂塗布層形成步驟) 接著，將製造例1所得之改質PP-1塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面上形成有厚度30μm之改質PP-1之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-1 obtained in Production Example 1 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a layer on the surface of the functional group-containing layer. A composite laminate of a resin coating layer of modified PP-1 with a thickness of 30μm.

＜實施例1-2＞ 於實施例1-1所製作之複合積層體之樹脂塗布層側之表面，藉由將含滑石之聚丙烯樹脂(PP樹脂)(Sunallomer股份公司製TRC104N)(接合對象)以射出成形機(住友重機械工業股份公司製SE100V；氣缸溫度200℃、工具溫度30℃、注入速度50mm/sec、波峰/保持壓力60/55[MPa/MPa])進行射出成形，製作根據ISO19095之拉伸試驗用試驗片(PP樹脂、10mm×45mm×3mm、接合部之重複長度5mm、寬度10mm)(玻璃-聚烯烴接合體)。<Example 1-2> On the surface of the resin coating layer side of the composite laminate produced in Example 1-1, talc-containing polypropylene resin (PP resin) (TRC104N manufactured by Sunallomer Co., Ltd.) (joint object) was used in an injection molding machine (Sumitomo) SE100V manufactured by Heavy Machinery Industry Co., Ltd.; cylinder temperature 200°C, tool temperature 30°C, injection speed 50mm/sec, peak/hold pressure 60/55[MPa/MPa]) for injection molding, and production of tensile test in accordance with ISO19095 Sheet (PP resin, 10mm×45mm×3mm, repeated length of joint 5mm, width 10mm) (glass-polyolefin joint).

[接著性評價] 關於實施例1-2所製作之試驗片(玻璃-聚烯烴接合體)，於常溫(23℃)下放置1天後，根據ISO19095 1-4，以拉伸試驗機(股份公司島津製作所製萬能試驗機自動立體測圖儀「AG-IS」；荷重元10kN、拉伸速度10mm/min、溫度23℃、50%RH)，進行拉伸剪斷接合強度試驗，測定接合強度。將測定結果表示於下述表1。[Subsequent Evaluation] Regarding the test piece (glass-polyolefin junction) produced in Example 1-2, after leaving it at room temperature (23°C) for 1 day, the tensile tester (manufactured by Shimadzu Co., Ltd.) was used in accordance with ISO19095 1-4 for 1 day. The testing machine is an automatic stereograph "AG-IS"; load element 10kN, tensile speed 10mm/min, temperature 23℃, 50%RH), conduct tensile shear joint strength test, and measure joint strength. The measurement results are shown in Table 1 below.

＜實施例2-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 2-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟：第1層) 於前述含官能基之層之表面以噴霧法塗布將2官能環氧樹脂(三菱Chemical股份公司製jER(註冊商標)1001)：100g、雙酚A：24g及三乙基胺：0.4g溶解於丙酮250g中而成之熱可塑性環氧樹脂組成物，使其乾燥後之厚度成為30μm。藉由在空氣中並於常溫(23℃)下放置30分鐘，使溶劑揮發後，於150℃之爐中放置30分鐘，進行複加成反應，放冷至常溫(23℃)，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層32)。(Formation step of resin coating layer: first layer) Spray coating on the surface of the functional group-containing layer, and dissolve bifunctional epoxy resin (jER (registered trademark) 1001, manufactured by Mitsubishi Chemical Co., Ltd.): 100 g, bisphenol A: 24 g, and triethylamine: 0.4 g in A thermoplastic epoxy resin composition made from 250 g of acetone has a thickness of 30 μm after drying. Place the solvent in the air at room temperature (23°C) for 30 minutes. After volatilizing the solvent, place it in an oven at 150°C for 30 minutes to perform the multi-addition reaction. Let it cool to room temperature (23°C) to form the first Layer of resin coating layer (thermoplastic epoxy resin layer 32).

(樹脂塗布層形成步驟：第2層) 接著，將製造例2所得之改質PP-2塗布於前述熱可塑性環氧樹脂層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作前述熱可塑性環氧樹脂層之表面有形成厚度30μm之改質PP-2之樹脂塗布層(改質聚烯烴層31)之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the modified PP-2 obtained in Production Example 2 was coated on the surface of the aforementioned thermoplastic epoxy resin layer to volatilize xylene and kept at 150°C for 30 minutes to form the surface of the aforementioned thermoplastic epoxy resin layer. A composite laminate of a resin coating layer of modified PP-2 (modified polyolefin layer 31) with a thickness of 30 μm.

＜實施例2-2＞ 於實施例2-1所製作之複合積層體之第2層之樹脂塗布層側之表面，進行與實施例1-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表1。<Example 2-2> On the surface of the resin coating layer side of the second layer of the composite laminate produced in Example 2-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

＜實施例3-1＞ (前處理步驟) 對18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)，進行UV臭氧處理。<Example 3-1> (Pre-processing steps) UV ozone treatment was performed on a glass substrate (manufactured by Nidec Glass Co., Ltd., chemically strengthened glass) of 18 mm × 45 mm and a thickness of 1.2 mm.

(含官能基之層形成步驟) 接著，將前述UV臭氧處理後之玻璃基材浸漬於將3-甲基丙烯氧基丙基三甲氧基矽烷(信越Silicone股份公司製KBM-503；矽烷偶合劑)0.5g溶解於工業用乙醇100g之70℃之矽烷偶合劑溶液中5分鐘後，取出該玻璃基材使其乾燥，於該玻璃基材表面導入來自矽烷偶合劑之官能基。 之後，進而在70℃下浸漬於將2官能硫醇化合物1,4雙(3-氫硫基丁醯基氧基)丁烷(昭和電工股份公司製KarenzMT BD1)：0.6g、2,4,6-參(二甲基胺基甲基)酚(DMP-30)：0.05g溶解於甲苯150g中之溶液10分鐘後，撈起並乾燥。藉此形成二層之含官能基之層。(Formation step of functional group-containing layer) Next, the glass substrate after the aforementioned UV ozone treatment was immersed in 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Silicone Co., Ltd.; silane coupling agent) dissolved in 100 g of industrial ethanol After 5 minutes in the silane coupling agent solution at 70°C, the glass substrate was taken out to dry, and functional groups derived from the silane coupling agent were introduced on the surface of the glass substrate. After that, it was immersed in the bifunctional thiol compound 1,4-bis(3-hydrothiobutanoyloxy)butane (KarenzMT BD1 manufactured by Showa Denko Co., Ltd.) at 70°C: 0.6g, 2,4,6- Ginseng (Dimethylaminomethyl)phenol (DMP-30): A solution of 0.05g dissolved in 150g of toluene for 10 minutes, then picked up and dried. Thereby, a two-layer functional group-containing layer is formed.

(樹脂塗布層形成步驟) 接著，將製造例3所得之改質PP-3塗布於前述玻璃基材之含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-3之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-3 obtained in Production Example 3 was coated on the surface of the functional group-containing layer of the aforementioned glass substrate to volatilize xylene and kept at 150°C for 30 minutes to prepare the surface of the aforementioned functional group-containing layer There is a composite laminate with a 30μm thick modified PP-3 resin coating layer on the surface.

＜實施例3-2＞ 於實施例3-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例1-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表1。<Example 3-2> On the surface of the resin coating layer side of the composite laminate produced in Example 3-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

＜實施例4-1＞ (前處理步驟) 對18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)，進行濕式噴氣處理，於前述玻璃基材之表面形成微細之凹凸。<Example 4-1> (Pre-processing steps) A glass substrate of 18 mm×45 mm and a thickness of 1.2 mm (chemically strengthened glass manufactured by Nidec Glass Co., Ltd.) was subjected to wet air jet treatment to form fine irregularities on the surface of the glass substrate.

(樹脂塗布層形成步驟：第1層) 於前述凹凸之表面進行與實施例2-1相同之操作，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層)。(Formation step of resin coating layer: first layer) The same operation as in Example 2-1 was performed on the surface of the aforementioned concavities and convexities to form the first resin coating layer (thermoplastic epoxy resin layer).

(樹脂塗布層形成步驟：第2層) 接著，進行與實施例2-1相同之操作，製作於前述熱可塑性環氧樹脂層之表面形成有厚度40μm之改質PP-2之樹脂塗布層之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the same operation as in Example 2-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

＜實施例4-2＞ 於實施例4-1所製作之複合積層體之樹脂塗布層側之表面進行與實施例1-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表1。<Example 4-2> The same operation as in Example 1-2 was performed on the surface of the resin coating layer side of the composite laminate produced in Example 4-1 to produce a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

＜比較例1-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Comparative Example 1-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

＜比較例1-2＞ 於比較例1-1所製作之丙酮脫脂處理後之玻璃基材表面不設置含官能基之層及樹脂塗布層，雖然進行與實施例1-2相同之射出成形操作，但前述PP樹脂不接著於前述玻璃基材表面，無法製作出玻璃-聚烯烴接合體。<Comparative Example 1-2> No functional group-containing layer and resin coating layer were provided on the surface of the glass substrate after acetone degreasing made in Comparative Example 1-1. Although the injection molding operation was performed as in Example 1-2, the aforementioned PP resin was not adhered On the surface of the aforementioned glass substrate, a glass-polyolefin joint could not be produced.

＜比較例2-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Comparative Example 2-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟) 接著，將馬來酸酐改質聚丙烯(三菱Chemical股份公司製Modic(註冊商標)ER321P)：5g溶解於二甲苯：95g之溶液塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之馬來酸酐改質聚丙烯層之複合積層體。(Steps for forming resin coating layer) Next, maleic anhydride modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Co., Ltd.): 5 g dissolved in xylene: 95 g of a solution was coated on the surface of the functional group-containing layer to volatilize xylene. Maintained at 150°C for 30 minutes, a composite laminate with a maleic anhydride modified polypropylene layer with a thickness of 30 μm formed on the surface of the aforementioned functional group-containing layer was fabricated.

＜比較例2-2＞ 於比較例2-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例1-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表1。＜Comparative example 2-2＞ On the surface of the resin coating layer side of the composite laminate produced in Comparative Example 2-1, the same operation as in Example 1-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.

Figure 02_image001
Figure 02_image001

＜實施例5-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 5-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，將前述丙酮脫脂處理後之玻璃基材浸漬於將3-縮水甘油氧基丙基三甲氧基矽烷(信越Silicone股份公司製「KBM-403」；矽烷偶合劑)2g溶解於工業用乙醇1000g之70℃之矽烷偶合劑含有溶液中20分鐘後，取出該玻璃基材使其乾燥，於該玻璃基材表面形成含官能基之層。(Formation step of functional group-containing layer) Next, the glass substrate after the acetone degreasing treatment was immersed in 2 g of 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.; silane coupling agent) dissolved in 1000 g of industrial ethanol After 20 minutes of containing the silane coupling agent at 70°C in the solution, the glass substrate was taken out to dry, and a functional group-containing layer was formed on the surface of the glass substrate.

(樹脂塗布層形成步驟) 接著，將製造例4所得之改質PP-4塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-4之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-4 obtained in Production Example 4 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a thickness on the surface of the functional group-containing layer A composite laminate of 30μm modified PP-4 resin coating layer.

＜實施例5-2＞ 於實施例5-1所製作之複合積層體之樹脂塗布層側之表面，將具有玻璃纖維之聚丙烯樹脂(PP樹脂)(Daicelpolymer股份公司製pp-GF40-01 F02)(接合對象)以與實施例1-2相同之條件進行射出成形，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表2。<Example 5-2> On the surface of the resin coating layer side of the composite laminate produced in Example 5-1, a polypropylene resin (PP resin) with glass fibers (pp-GF40-01 F02 manufactured by Daicelpolymer Co., Ltd.) (joint object) was combined with The injection molding was performed under the same conditions as in Example 1-2, and a test piece for tensile test was produced. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

＜實施例6-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 6-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例5-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Then, the same operation as in Example 5-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟：第1層) 於前述含官能基之層之表面，除了將環氧樹脂變更為三菱Chemical股份公司製jER(註冊商標)1004以外，其餘進行與實施例2-1相同之操作，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層)。(Formation step of resin coating layer: first layer) On the surface of the aforementioned functional group-containing layer, except that the epoxy resin was changed to jER (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd., the same operations as in Example 2-1 were performed to form the first resin coating layer (Thermoplastic epoxy resin layer).

(樹脂塗布層形成步驟：第2層) 接著，進行與實施例2-1相同之操作，製作於前述熱可塑性環氧樹脂層之表面有形成厚度30μm之改質PP-2之樹脂塗布層之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the same operation as in Example 2-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

＜實施例6-2＞ 於實施例6-1所製作之複合積層體之第2層之樹脂塗布層側之表面，進行與實施例5-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表2。<Example 6-2> On the surface of the resin coating layer side of the second layer of the composite laminate produced in Example 6-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

＜實施例7-1＞ (前處理步驟) 對18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)，以與實施例4-1相同之操作進行濕式噴氣處理，於前述玻璃基材之表面形成微細之凹凸。<Example 7-1> (Pre-processing steps) A glass substrate of 18mm×45mm and a thickness of 1.2mm (chemically strengthened glass manufactured by Nippon Electric Glass Co., Ltd.) was subjected to wet air jet treatment in the same manner as in Example 4-1 to form fine particles on the surface of the glass substrate. The bumps.

(含官能基之層形成步驟) 接著，對前述玻璃基材進行與實施例3-1相同之操作，形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 3-1 was performed on the aforementioned glass substrate to form a functional group-containing layer.

(樹脂塗布層形成步驟) 接著，進行與實施例1-1相同之操作，製作於前述含官能基之層之表面上形成有厚度30μm之改質PP-1之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Example 1-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-1 with a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜實施例7-2＞ 於實施例7-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例5-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表2。<Example 7-2> On the surface of the resin coating layer side of the composite laminate produced in Example 7-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

＜實施例8-1＞ (前處理步驟) 對18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)，以與實施例4-1相同之操作進行濕式噴氣處理，於前述玻璃基材之表面形成微細之凹凸。<Example 8-1> (Pre-processing steps) A glass substrate of 18mm×45mm and a thickness of 1.2mm (chemically strengthened glass manufactured by Nippon Electric Glass Co., Ltd.) was subjected to wet air jet treatment in the same manner as in Example 4-1 to form fine particles on the surface of the glass substrate. The bumps.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述玻璃基材之表面形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned glass substrate.

(樹脂塗布層形成步驟：第1層) 進行與實施例6-1相同之操作，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層)。(Formation step of resin coating layer: first layer) The same operation as in Example 6-1 was performed to form the first resin coating layer (thermoplastic epoxy resin layer).

(樹脂塗布層形成步驟：第2層) 接著，進行與實施例2-1相同之操作，製作於前述熱可塑性環氧樹脂層之表面形成有厚度40μm之改質PP-2之樹脂塗布層之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the same operation as in Example 2-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

＜實施例8-2＞ 於實施例8-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例5-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表2。<Example 8-2> On the surface of the resin coating layer side of the composite laminate produced in Example 8-1, the same operation as in Example 5-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

＜比較例3-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Comparative Example 3-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

＜比較例3-2＞ 於比較例3-1所製作之丙酮脫脂處理後之玻璃基材表面，不設置含官能基之層及樹脂塗布層，雖然進行與實施例5-2相同之射出成形操作，但前述PP樹脂不接著於前述玻璃基材表面，無法製作出玻璃-聚烯烴接合體。＜Comparative example 3-2＞ On the surface of the glass substrate after the acetone degreasing treatment made in Comparative Example 3-1, the functional group-containing layer and the resin coating layer were not provided. Although the injection molding operation was performed as in Example 5-2, the aforementioned PP resin was not Then, on the surface of the aforementioned glass substrate, a glass-polyolefin joint could not be produced.

＜比較例4-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Comparative Example 4-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟) 接著，進行與比較例2-1相同之操作，製作於前述含官能基之層之表面有形成厚度30μm之馬來酸酐改質聚丙烯層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Comparative Example 2-1 was performed to produce a composite laminate in which a maleic anhydride modified polypropylene layer having a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜比較例4-2＞ 於比較例4-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例5-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表2。＜Comparative example 4-2＞ The same operation as in Example 5-2 was performed on the surface of the resin coating layer side of the composite laminate produced in Comparative Example 4-1 to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 2 below.

Figure 02_image003
Figure 02_image003

＜實施例9-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 9-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟) 接著，進行與實施例5-1相同之操作，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-4之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Example 5-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-4 with a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜實施例9-2＞ 於實施例9-1所製作之複合積層體之樹脂塗布層側之表面，將具有碳纖維之聚丙烯樹脂(PP樹脂)(Daicelpolymer股份公司製pp-GF40-01 F008)(接合對象)以與實施例1-2相同之條件進行射出成形，製作出拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表3。<Example 9-2> On the surface of the resin coating layer side of the composite laminate produced in Example 9-1, polypropylene resin (PP resin) with carbon fibers (pp-GF40-01 F008 manufactured by Daicelpolymer Co., Ltd.) (joint object) The injection molding was performed under the same conditions as in Example 1-2, and a test piece for tensile test was produced. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

＜實施例10-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 10-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面上形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the glass substrate after the aforementioned acetone degreasing treatment.

(樹脂塗布層形成步驟：第1層) 於前述含官能基之層之表面，除了將環氧樹脂變更為三菱Chemical股份公司製jER(註冊商標)1007以外，其餘進行與實施例2-1相同之操作，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層)。(Formation step of resin coating layer: first layer) On the surface of the aforementioned functional group-containing layer, except that the epoxy resin was changed to jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Co., Ltd., the same operations as in Example 2-1 were performed to form the first resin coating layer (Thermoplastic epoxy resin layer).

(樹脂塗布層形成步驟：第2層) 接著，進行與實施例2-1相同之操作，製作於前述熱可塑性環氧樹脂層之表面有形成厚度30μm之改質PP-2之樹脂塗布層之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the same operation as in Example 2-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 30 μm was formed on the surface of the thermoplastic epoxy resin layer.

＜實施例10-2＞ 對實施例10-1所製作之複合積層體之第2層之樹脂塗布層側之表面進行與實施例9-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表3。<Example 10-2> The same operation as in Example 9-2 was performed on the surface of the resin coating layer side of the second layer of the composite laminate produced in Example 10-1 to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

＜實施例11-1＞ (前處理步驟) 進行與實施例1-1相同之操作，將玻璃基材(18mm ×45mm，厚度1.2mm之日本電氣硝子股份公司製，化學強化玻璃)之表面以丙酮進行脫脂處理。<Example 11-1> (Pre-processing steps) The same operation as in Example 1-1 was performed, and the surface of the glass substrate (18 mm × 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述丙酮脫脂處理後之玻璃基材表面導入來自矽烷偶合劑之官能基。 且，進而於70℃下浸漬於將2-異氰酸酯乙基甲基丙烯酸酯(昭和電工股份公司製KarenzMOI(註冊商標))：1.2g、2,4,6-參(二甲基胺基甲基)酚(DMP-30)：0.05g溶解於甲苯150g中之溶液5分鐘後撈起並乾燥。藉此，形成將能夠化學鍵結之官能基往立體方向延伸之含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to introduce the functional group derived from the silane coupling agent on the surface of the glass substrate after the acetone degreasing treatment. Furthermore, it was immersed in 2-isocyanate ethyl methacrylate (Karenz MOI (registered trademark) manufactured by Showa Denko Co., Ltd.): 1.2 g, 2,4,6-ginseng (dimethylaminomethyl) at 70°C. ) Phenol (DMP-30): A solution of 0.05 g dissolved in 150 g of toluene is picked up and dried after 5 minutes. Thereby, a functional group-containing layer is formed that extends the functional group capable of chemical bonding in the three-dimensional direction.

(樹脂塗布層形成步驟) 接著，進行與實施例1-1相同之操作，製作於前述含官能基之層之表面上形成有厚度30μm之改質PP-1之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Example 1-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-1 with a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜實施例11-2＞ 於實施例11-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例9-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表3。<Example 11-2> On the surface of the resin coating layer side of the composite laminate produced in Example 11-1, the same operation as in Example 9-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

＜實施例12-1＞ (前處理步驟) 對18mm×45mm且厚度1.2mm之玻璃基材(日本電氣硝子股份公司製，化學強化玻璃)，以與實施例4-1相同之操作進行濕式噴氣處理，於前述玻璃基材之表面形成微細之凹凸。<Example 12-1> (Pre-processing steps) A glass substrate of 18mm×45mm and a thickness of 1.2mm (chemically strengthened glass manufactured by NEG The bumps.

(含官能基之層形成步驟) 接著，進行與實施例1-1相同之操作，於前述玻璃基材之表面形成含官能基之層。(Formation step of functional group-containing layer) Next, the same operation as in Example 1-1 was performed to form a functional group-containing layer on the surface of the aforementioned glass substrate.

(樹脂塗布層形成步驟：第1層) 於前述含官能基之層之表面，以噴霧法塗布將環氧樹脂(三菱Chemical股份公司製jER(註冊商標)1007)：100g、雙酚A：5.6g及三乙基胺：0.4g溶解於丙酮196g中而成之熱可塑性環氧樹脂組成物，使乾燥後之厚度成為30μm。藉由在空氣中並於常溫(23℃)下放置30分鐘，使溶劑揮發後，於150℃之爐中放置30分鐘，進行複加成反應，放冷至常溫(23℃)，形成第1層之樹脂塗布層(熱可塑性環氧樹脂層)。(Formation step of resin coating layer: first layer) On the surface of the functional group-containing layer, epoxy resin (jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Co., Ltd.): 100 g, bisphenol A: 5.6 g, and triethylamine: 0.4 g were dissolved by spray coating. The thermoplastic epoxy resin composition in 196 g of acetone has a thickness of 30 μm after drying. Place the solvent in the air at room temperature (23°C) for 30 minutes. After volatilizing the solvent, place it in an oven at 150°C for 30 minutes to perform the multi-addition reaction. Let it cool to room temperature (23°C) to form the first Layer of resin coating layer (thermoplastic epoxy resin layer).

(樹脂塗布層形成步驟：第2層) 接著，進行與實施例2-1相同之操作，製作於前述熱可塑性環氧樹脂層之表面形成有厚度40μm之改質PP-2之樹脂塗布層之複合積層體。(Step of forming resin coating layer: 2nd layer) Next, the same operation as in Example 2-1 was performed to produce a composite laminate in which a resin coating layer of modified PP-2 with a thickness of 40 μm was formed on the surface of the thermoplastic epoxy resin layer.

＜實施例12-2＞ 於實施例12-1所製作之複合積層體之樹脂塗布層側之表面，進行與實施例9-2相同之操作，製作拉伸試驗用試驗片。 關於其試驗片，以與實施例1-2相同之手段測定接合強度。將測定結果表示於下述表3。<Example 12-2> On the surface of the resin coating layer side of the composite laminate produced in Example 12-1, the same operation as in Example 9-2 was performed to prepare a test piece for a tensile test. Regarding the test piece, the bonding strength was measured by the same method as in Example 1-2. The measurement results are shown in Table 3 below.

Figure 02_image005
Figure 02_image005

[試驗片用材料] 作為試驗片用材料，準備以下材料。 (1)CFRP：將昭和電工股份公司製CF-SMCRigolacRCS-1000BK(CF：50質量%)使用1500kN之加壓機，於140℃下加壓成形5分鐘。尺寸：18mm×45mm×1.5mm。 (2)陶瓷：Kyocera股份公司製厚膜用基板(氧化鋁)。尺寸：18mm×45mm×1.5mm。 (3)聚丙烯板(PP板)：以實施例1-2之成形法並根據ISO19095之用於製作拉伸試驗用試驗片之PP板，成形為10mm×45mm×3mm。[Materials for Test Pieces] As materials for the test piece, the following materials were prepared. (1) CFRP: CF-SMC RigolacRCS-1000BK (CF: 50% by mass) manufactured by Showa Denko Co., Ltd. was press-formed at 140° C. for 5 minutes using a 1500 kN press. Dimensions: 18mm×45mm×1.5mm. (2) Ceramics: Thick film substrates (alumina) manufactured by Kyocera Co., Ltd. Dimensions: 18mm×45mm×1.5mm. (3) Polypropylene board (PP board): The PP board used to make the test piece for tensile test according to the forming method of Example 1-2 and according to ISO19095 is formed into 10mm×45mm×3mm.

＜實施例13-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之CFRP以與實施例4-1相同之操作進行濕式噴氣處理，於前述CFRP表面形成微細之凹凸。<Example 13-1> (Pre-treatment step wet air jet treatment) The CFRP of 18 mm×45 mm and thickness of 1.5 mm was subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the aforementioned CFRP.

(含官能基之層 矽烷偶合劑處理) 將施予前述濕式噴氣處理之CFRP浸漬於使3-胺基丙基三甲氧基矽烷(信越Silicone股份公司製「KBM-903」；矽烷偶合劑)2g溶解於工業用乙醇1000g之70℃之含矽烷偶合劑之溶液中20分鐘後，取出該CFRP並使其乾燥，於該CFRP表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) The CFRP subjected to the aforementioned wet air jet treatment was immersed in a solution of 2 g of 3-aminopropyltrimethoxysilane ("KBM-903" manufactured by Shin-Etsu Silicone Co., Ltd.; silane coupling agent) dissolved in 1000 g of industrial ethanol at 70°C. After 20 minutes in the solution containing the silane coupling agent, the CFRP was taken out and dried to form a layer containing functional groups (amine groups) on the surface of the CFRP.

(樹脂塗布層形成步驟) 接著，將製造例1所得之改質PP-1塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面上形成有厚度30μm之改質PP-1之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-1 obtained in Production Example 1 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a layer on the surface of the functional group-containing layer. A composite laminate of a resin coating layer of modified PP-1 with a thickness of 30μm.

＜實施例13-2：CFRP-聚烯烴接合體＞ 接著，將CFRP之樹脂塗布層面與PP板以接合部重疊，且疊成長度5mm且寬度10mm之狀態，使用精電舎電子工業股份公司製超音波溶著機SONOPET-JII430T-M(28.5KHz)，進行超音波溶著，得到根據與實施例1相同大小之ISO19095之拉伸試驗用之試驗片：CFRP-PP接合體(CFRP：18mm×45mm×1.5mm，PP：10mm×45mm×3mm，接合部之重疊長度：5mm且寬度10mm)。<Example 13-2: CFRP-polyolefin junction body> Then, the resin coating layer of CFRP and the PP board are overlapped with the joint part, and the length is 5mm and the width is 10mm, using the ultrasonic melting machine SONOPET-JII430T-M (28.5KHz) manufactured by Seiden Electronics Industry Co., Ltd. , Carry out ultrasonic fusion, and obtain a test piece for tensile test according to ISO19095 of the same size as in Example 1: CFRP-PP joint (CFRP: 18mm×45mm×1.5mm, PP: 10mm×45mm×3mm, joint The overlapping length of the part: 5mm and width 10mm).

[拉伸剪斷強度] 關於所製作之試驗片(CFRP-聚烯烴接合體)，於常溫(23℃)下放置1天後，根據ISO19095 1-4，以拉伸試驗機(股份公司島津製作所製萬能試驗機自動立體測圖儀「AG-IS」；荷重元10kN、拉伸速度10mm/min、溫度23℃、50%RH)，進行拉伸剪斷接合強度試驗，測定接合強度。將測定結果表示於下述表4。[Tensile Shear Strength] Regarding the produced test piece (CFRP-polyolefin junction body), after placing it at room temperature (23°C) for 1 day, it was automatically measured with a tensile testing machine (universal testing machine manufactured by Shimadzu Corporation) in accordance with ISO19095 1-4. Graphing instrument "AG-IS"; load element 10kN, tensile speed 10mm/min, temperature 23℃, 50%RH), conduct tensile shear joint strength test to measure joint strength. The measurement results are shown in Table 4 below.

＜實施例14-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之CFRP以與實施例4-1相同之操作進行濕式噴氣處理，於前述CFRP表面形成微細之凹凸。<Example 14-1> (Pre-treatment step wet air jet treatment) The CFRP of 18 mm×45 mm and thickness of 1.5 mm was subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the aforementioned CFRP.

(含官能基之層 矽烷偶合劑處理) 接著，進行與實施例13-1相同之操作，於前述濕式噴氣處理後之CFRP表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) Then, the same operation as in Example 13-1 was performed to form a functional group (amine group)-containing layer on the surface of the CFRP after the wet air jet treatment.

(樹脂塗布層形成步驟) 接著，將製造例2所得之改質PP-2塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-2之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-2 obtained in Production Example 2 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a thickness on the surface of the functional group-containing layer A composite laminate of 30μm modified PP-2 resin coating layer.

＜實施例14-2：CFRP-聚烯烴接合體＞ 接著，進行與實施例13-2相同之操作，將實施例14-1所製作之複合積層體之樹脂塗布層側之面與PP板進行超音波溶著，製作試驗片。關於其試驗片，以與實施例13-2相同之手法測定接合強度。將測定結果表示於下述表4。<Example 14-2: CFRP-polyolefin junction body> Next, the same operation as in Example 13-2 was performed, and the surface on the resin coating layer side of the composite laminate produced in Example 14-1 and the PP board were ultrasonically fused to produce a test piece. Regarding the test piece, the bonding strength was measured in the same manner as in Example 13-2. The measurement results are shown in Table 4 below.

＜實施例15-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之陶瓷以與實施例4-1相同之操作進行濕式噴氣處理，於前述陶瓷表面形成微細之凹凸。<Example 15-1> (Pre-treatment step wet air jet treatment) The 18mm×45mm and thickness 1.5mm ceramics were subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the ceramics.

(含官能基之層 矽烷偶合劑處理) 接著，進行與實施例13-1相同之操作，於前述濕式噴氣處理後之陶瓷表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) Then, the same operation as in Example 13-1 was performed to form a functional group (amine group)-containing layer on the ceramic surface after the wet air jet treatment.

(樹脂塗布層形成步驟) 接著，將製造例3所得之改質PP-3塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-3之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-3 obtained in Production Example 3 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a thickness on the surface of the functional group-containing layer A composite laminate of 30μm modified PP-3 resin coating layer.

＜實施例15-2：陶瓷-聚烯烴接合體＞ 接著，將陶瓷之樹脂塗布層面與PP板以接合部重疊，且疊成長度5mm且寬度10mm之狀態，使用精電舎電子工業股份公司製超音波溶著機SONOPET-JII430T-M(28.5 KHz)，進行超音波溶著，得到根據與實施例1相同大小之ISO19095之拉伸試驗用之試驗片：陶瓷-PP接合體(陶瓷：18mm×45mm×1.5mm、PP：10mm×45mm×3mm、接合部之重疊長度：5mm、寬度10mm)。關於其試驗片，以與實施例13-2相同之手法測定接合強度。將測定結果表示於下述表4。<Example 15-2: Ceramic-polyolefin joint body> Then, the resin coating layer of the ceramic and the PP board are overlapped with the joint part, and the length is 5mm and the width is 10mm. The ultrasonic melting machine SONOPET-JII430T-M (28.5 KHz) manufactured by Seiden Electronics Industry Co., Ltd. is used. , Carry out ultrasonic fusion to obtain a test piece for tensile test according to ISO19095 of the same size as in Example 1: Ceramic-PP joint (ceramic: 18mm×45mm×1.5mm, PP: 10mm×45mm×3mm, joint The overlapping length of the part: 5mm, width 10mm). Regarding the test piece, the bonding strength was measured in the same manner as in Example 13-2. The measurement results are shown in Table 4 below.

＜實施例16-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之陶瓷以與實施例4-1相同之操作進行濕式噴氣處理，於前述陶瓷表面形成微細之凹凸。<Example 16-1> (Pre-treatment step wet air jet treatment) The 18mm×45mm and thickness 1.5mm ceramics were subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the ceramics.

(含官能基之層 矽烷偶合劑處理) 接著，進行與實施例13-1相同之操作，於前述濕式噴氣處理後之陶瓷表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) Then, the same operation as in Example 13-1 was performed to form a functional group (amine group)-containing layer on the ceramic surface after the wet air jet treatment.

(樹脂塗布層形成步驟) 接著，將製造例4所得之改質PP-4塗布於前述含官能基之層之表面，使二甲苯揮發，於150℃下保持30分鐘，製作於前述含官能基之層之表面有形成厚度30μm之改質PP-4之樹脂塗布層之複合積層體。(Steps for forming resin coating layer) Next, the modified PP-4 obtained in Production Example 4 was coated on the surface of the functional group-containing layer to volatilize xylene and kept at 150°C for 30 minutes to form a thickness on the surface of the functional group-containing layer A composite laminate of 30μm modified PP-4 resin coating layer.

＜實施例16-2：陶瓷-聚烯烴接合體＞ 接著，進行與實施例13-2相同之操作，將實施例16-1所製作之複合積層體之樹脂塗布層側之面與PP板進行超音波溶著，製作試驗片。關於其試驗片，以與實施例13-2相同之手法測定接合強度。將測定結果表示於下述表4。<Example 16-2: Ceramic-polyolefin joint body> Next, the same operation as in Example 13-2 was performed, and the surface of the resin coating layer side of the composite laminate produced in Example 16-1 and the PP board were ultrasonically fused to produce a test piece. Regarding the test piece, the bonding strength was measured in the same manner as in Example 13-2. The measurement results are shown in Table 4 below.

＜比較例5-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之CFRP以與實施例4-1相同之操作進行濕式噴氣處理，於前述CFRP表面形成微細之凹凸。<Comparative Example 5-1> (Pre-treatment step wet air jet treatment) The CFRP of 18 mm×45 mm and thickness of 1.5 mm was subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the aforementioned CFRP.

(含官能基之層 矽烷偶合劑處理) 接著，進行與實施例13-1相同之操作，於前述濕式噴氣處理後之CFRP表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) Then, the same operation as in Example 13-1 was performed to form a functional group (amine group)-containing layer on the surface of the CFRP after the wet air jet treatment.

(樹脂塗布層形成步驟) 接著，進行與比較例2-1相同之操作，製作於前述含官能基之層之表面有形成厚度30μm之馬來酸酐改質聚丙烯層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Comparative Example 2-1 was performed to produce a composite laminate in which a maleic anhydride modified polypropylene layer having a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜比較例5-2＞ 進行與實施例13-2相同之操作，將比較例5-1所製作之複合積層體之樹脂塗布層側之面與PP板進行超音波溶著，製作試驗片。關於其試驗片，以與實施例13-2相同之手法測定接合強度。將測定結果表示於下述表4。<Comparative Example 5-2> The same operation as in Example 13-2 was performed, and the surface on the resin coating layer side of the composite laminate produced in Comparative Example 5-1 and the PP board were ultrasonically fused to produce a test piece. Regarding the test piece, the bonding strength was measured in the same manner as in Example 13-2. The measurement results are shown in Table 4 below.

＜比較例6-1＞ (前處理步驟 濕式噴氣處理) 對18mm×45mm且厚度1.5mm之陶瓷以與實施例4-1相同之操作進行濕式噴氣處理，於前述陶瓷表面形成微細之凹凸。<Comparative Example 6-1> (Pre-treatment step wet air jet treatment) The 18mm×45mm and thickness 1.5mm ceramics were subjected to wet air jet treatment by the same operation as in Example 4-1, and fine unevenness was formed on the surface of the ceramics.

(含官能基之層 矽烷偶合劑處理) 接著，進行與實施例13-1相同之操作，於前述濕式噴氣處理後之陶瓷表面形成含官能基(胺基)之層。(Functional group-containing layer treated with silane coupling agent) Then, the same operation as in Example 13-1 was performed to form a functional group (amine group)-containing layer on the ceramic surface after the wet air jet treatment.

(樹脂塗布層形成步驟) 接著，進行與比較例2-1相同之操作，製作於前述含官能基之層之表面有形成厚度30μm之馬來酸酐改質聚丙烯層之複合積層體。(Steps for forming resin coating layer) Next, the same operation as in Comparative Example 2-1 was performed to produce a composite laminate in which a maleic anhydride modified polypropylene layer having a thickness of 30 μm was formed on the surface of the aforementioned functional group-containing layer.

＜比較例6-2＞ 進行與實施例13-2相同之操作，將比較例6-1所製作之複合積層體之樹脂塗布層側之面與PP板進行超音波溶著，製作試驗片。關於其試驗片，以與實施例13-2相同之手法測定接合強度。將測定結果表示於下述表4。<Comparative Example 6-2> The same operation as in Example 13-2 was performed, and the surface on the resin coating layer side of the composite laminate produced in Comparative Example 6-1 and the PP board were ultrasonically fused to produce a test piece. Regarding the test piece, the bonding strength was measured in the same manner as in Example 13-2. The measurement results are shown in Table 4 below.

Figure 02_image007
[產業利用性]
Figure 02_image007
[Industrial Utilization]

本發明相關之複合積層體與聚烯烴經接合一體化，且作為例如側門面板、引擎蓋頂、檔板、操縱吊架、A支柱、B支柱、C支柱、D支柱、沖撞盒、電能控制單元(PCU)外殼、電力壓縮機構件(內壁部、吸入埠部、排氣控制閥(ECV)***部、機架軸套部等)、鋰離子電池(LIB)間隔器、電池盒、LED前燈等之汽車用零件，或智慧型手機、筆記型電腦、平板電腦、智慧型手錶、大型液晶電視(LCD-TV)、屋外LED照明之構造體等來使用，但尤其是不限定於此等例示之用途。The composite laminate related to the present invention is joined and integrated with polyolefin, and is used as, for example, side door panels, hood tops, baffles, control hangers, A pillars, B pillars, C pillars, D pillars, crash boxes, and electric power control units (PCU) housing, electric compressor components (inner wall, suction port, exhaust control valve (ECV) insertion part, frame sleeve part, etc.), lithium ion battery (LIB) spacer, battery box, LED front Lamps and other automotive parts, or smart phones, notebook computers, tablet computers, smart watches, large liquid crystal televisions (LCD-TV), outdoor LED lighting structures, etc., but especially not limited to these Illustrated use.

1:複合積層體 2:材料層 21:微細之凹凸 3:樹脂塗布層(底塗層) 31:改質聚烯烴層 32:熱可塑性環氧樹脂層 33:熱硬化性樹脂層 4:含官能基之層 5:接合體 6:聚烯烴1: Composite laminate 2: Material layer 21: Subtle bumps 3: Resin coating layer (undercoating) 31: Modified polyolefin layer 32: Thermoplastic epoxy resin layer 33: Thermosetting resin layer 4: Layer containing functional groups 5: Conjugation 6: Polyolefin

[圖1]表示本發明之一實施形態中複合積層體之構成之說明圖。 [圖2]表示本發明之其他實施形態中複合積層體之構成之說明圖。 [圖3]表示本發明之一實施形態中接合體之構成之說明圖。[Fig. 1] An explanatory diagram showing the structure of a composite laminate in an embodiment of the present invention. [Fig. 2] An explanatory diagram showing the structure of a composite laminate in another embodiment of the present invention. [Fig. 3] An explanatory diagram showing the structure of the joined body in one embodiment of the present invention.

1:複合積層體 1: Composite laminate

2:材料層 2: Material layer

3:樹脂塗布層(底塗層) 3: Resin coating layer (undercoating)

21:微細之凹凸 21: Subtle bumps

31:改質聚烯烴層 31: Modified polyolefin layer

32:熱可塑性環氧樹脂層 32: Thermoplastic epoxy resin layer

33:熱硬化性樹脂層 33: Thermosetting resin layer

Claims (14)

一種複合積層體，其係具有 含有選自纖維強化塑膠、玻璃及陶瓷所成群中至少1種之材料層，與 積層於前述材料層上之1層或複數層之樹脂塗布層之複合積層體， 且，前述樹脂塗布層中至少1層係由包含改質聚烯烴之樹脂組成物所形成之改質聚烯烴層， 前述改質聚烯烴層係選自包含馬來酸酐改質聚烯烴與2官能環氧樹脂與2官能酚化合物之反應物1之層、包含馬來酸酐改質聚烯烴與熱可塑性環氧樹脂之反應物2之層及包含聚烯烴與熱可塑性環氧樹脂之混合物之層中至少1種。A composite laminated body, which has Contains at least one material layer selected from the group of fiber reinforced plastics, glass and ceramics, and A composite laminate of one or more resin coating layers laminated on the aforementioned material layer, In addition, at least one of the aforementioned resin coating layers is a modified polyolefin layer formed of a resin composition containing modified polyolefin, and The aforementioned modified polyolefin layer is selected from the group consisting of maleic anhydride modified polyolefin and the reactant 1 of a bifunctional epoxy resin and a bifunctional phenol compound, and a layer containing maleic anhydride modified polyolefin and thermoplastic epoxy resin. At least one of the reactant 2 layer and the layer containing a mixture of polyolefin and thermoplastic epoxy resin. 如請求項1之複合積層體，其中，前述反應物1係在包含馬來酸酐改質聚烯烴之溶液中，使2官能環氧樹脂與2官能酚化合物複加成反應而成。The composite laminate of claim 1, wherein the aforementioned reactant 1 is formed by a compound addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound in a solution containing maleic anhydride modified polyolefin. 如請求項1之複合積層體，其中，前述反應物2係使2官能環氧樹脂與2官能酚化合物之複加成反應所生成之熱可塑性環氧樹脂，與馬來酸酐改質聚烯烴反應而成。The composite laminate of claim 1, wherein the aforementioned reactant 2 is a thermoplastic epoxy resin produced by the multi-addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound, and reacts with maleic anhydride modified polyolefin Become. 如請求項1之複合積層體，其中，前述混合物係聚丙烯與熱可塑性環氧樹脂之混合物。The composite laminate of claim 1, wherein the aforementioned mixture is a mixture of polypropylene and thermoplastic epoxy resin. 如請求項1~4中任1項之複合積層體，其中，前述樹脂塗布層係含有包含前述改質聚烯烴層與前述改質聚烯烴層以外之層之複數層， 前述改質聚烯烴層以外之層之至少1層係選自由包含熱可塑性環氧樹脂之樹脂組成物所形成之熱可塑性環氧樹脂層及由包含熱硬化性樹脂之樹脂組成物所形成之熱硬化性樹脂層中至少1種。The composite laminate according to any one of claims 1 to 4, wherein the resin coating layer contains a plurality of layers including the modified polyolefin layer and layers other than the modified polyolefin layer, At least one of the layers other than the modified polyolefin layer is selected from a thermoplastic epoxy resin layer formed of a resin composition containing a thermoplastic epoxy resin and a thermal plastic epoxy layer formed of a resin composition containing a thermosetting resin At least one of the curable resin layers. 如請求項5之複合積層體，其中，前述熱硬化性樹脂係選自胺甲酸乙酯樹脂、環氧樹脂、乙烯酯樹脂及不飽和聚酯樹脂所成群中至少1種。The composite laminate of claim 5, wherein the thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. 如請求項1~6中任1項之複合積層體，其係在前述材料層與前述樹脂塗布層之間，具有鄰接於前述材料層與前述樹脂塗布層而積層之含官能基之層， 前述含官能基之層包含選自下述(1)~(7)所成群中至少1個官能基， (1)來自矽烷偶合劑，且選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基 (2)使來自矽烷偶合劑之胺基與選自環氧化合物及硫醇化合物中至少1種反應而成之官能基 (3)使來自矽烷偶合劑之氫硫基與選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種反應而成之官能基 (4)使來自矽烷偶合劑之(甲基)丙烯醯基與硫醇化合物反應而成之官能基 (5)使來自矽烷偶合劑之環氧基與選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種反應而成之官能基 (6)來自異氰酸酯化合物之異氰酸基 (7)來自硫醇化合物之氫硫基。The composite laminate of any one of claims 1 to 6, which is between the material layer and the resin coating layer, and has a functional group-containing layer laminated adjacent to the material layer and the resin coating layer, The aforementioned functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7), (1) It is derived from a silane coupling agent and is selected from at least one functional group from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2) A functional group formed by reacting an amine group derived from a silane coupling agent with at least one selected from epoxy compounds and thiol compounds (3) The sulfhydryl group derived from the silane coupling agent is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (meth)acrylic groups and A functional group formed by the reaction of at least one of a group of amine-based compounds (4) Functional group formed by reacting (meth)acrylic acid group derived from silane coupling agent with thiol compound (5) A functional group formed by reacting an epoxy group derived from a silane coupling agent with at least one compound selected from the group consisting of an amine group and a (meth)acrylic acid group, an amine compound, and a thiol compound (6) Isocyanate group from isocyanate compound (7) Hydrosulfide groups derived from thiol compounds. 如請求項1~7中任1項之複合積層體，其中，前述材料層係在其表面施予選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種前處理而成。Such as the composite laminate of any one of claims 1 to 7, wherein the aforementioned material layer is applied to its surface selected from degreasing treatment, UV ozone treatment, air jet treatment, grinding treatment, plasma treatment and corona discharge treatment. At least one kind of pre-treatment in the group. 一種複合積層體之製造方法，其係如請求項1~8中任1項之複合積層體之製造方法， 前述複合積層體係在前述材料層與前述樹脂塗布層之間，具有鄰接於前述材料層與前述樹脂塗布層而積層之含官能基之層， 前述含官能基之層係將前述材料層之表面使用選自下述(1’)~(7’)所成群中至少1種來處理而成， (1’) 具有選自環氧基、胺基、(甲基)丙烯醯基及氫硫基所成群中至少1種官能基之矽烷偶合劑 (2’) 選自環氧化合物及硫醇化合物中至少1種與具有胺基之矽烷偶合劑之組合 (3’) 具有選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種與具有氫硫基之矽烷偶合劑之組合 (4’) 硫醇化合物與具有(甲基)丙烯醯基之矽烷偶合劑之組合 (5’) 選自具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種與具有環氧基之矽烷偶合劑之組合 (6’) 異氰酸酯化合物 (7’) 硫醇化合物。A method for manufacturing a composite laminate, which is the method for manufacturing a composite laminate according to any one of claims 1 to 8, The composite laminate system has a functional group-containing layer laminated adjacent to the material layer and the resin coating layer between the material layer and the resin coating layer, The functional group-containing layer is formed by treating the surface of the material layer with at least one selected from the group of (1') to (7') below, (1') Silane coupling agent having at least one functional group selected from the group consisting of epoxy group, amino group, (meth)acryloyl group and sulfhydryl group (2’) A combination of at least one selected from epoxy compounds and thiol compounds and a silane coupling agent with an amine group (3') Among the group of compounds having an epoxy compound, an amine compound, an isocyanate compound, a compound having a (meth)acryloyl group and an epoxy group, and a compound having a (meth)acryloyl group and an amino group At least one combination with silane coupling agent with hydrogen sulfide group (4') Combination of mercaptan compound and silane coupling agent with (meth)acrylic acid group (5') A combination of at least one selected from the group of compounds having amine groups and (meth)acrylic acid groups, amine compounds, and thiol compounds, and a silane coupling agent having epoxy groups (6’) Isocyanate compound (7') Thiol compound. 如請求項9之複合積層體之製造方法，其中，前述處理係選自下述(2”)~(5”)中至少1種， (2”) 以具有胺基之矽烷偶合劑處理後，加成選自環氧化合物及硫醇化合物中至少1種之處理 (3”) 以具有氫硫基之矽烷偶合劑處理後，加成選自環氧化合物、胺化合物、異氰酸酯化合物、具有(甲基)丙烯醯基及環氧基之化合物，以及具有(甲基)丙烯醯基及胺基之化合物所成群中至少1種之處理 (4”) 以具有(甲基)丙烯醯基之矽烷偶合劑處理後，加成硫醇化合物之處理 5”) 以具有環氧基之矽烷偶合劑處理後，加成具有胺基及(甲基)丙烯醯基之化合物、胺化合物，以及硫醇化合物所成群中至少1種之處理。Such as the method for manufacturing a composite laminate of claim 9, wherein the aforementioned treatment is selected from at least one of the following (2”) to (5”), (2") After treatment with silane coupling agent with amine group, at least one selected from epoxy compound and thiol compound is added. (3") After treatment with a silane coupling agent having a hydrogen sulfide group, the addition is selected from epoxy compounds, amine compounds, isocyanate compounds, compounds having (meth)acrylic groups and epoxy groups, and compounds having (methyl) ) Treatment of at least one of the groups of acryl and amine compounds (4") After treatment with (meth)acrylic silane coupling agent, the treatment of adding thiol compound 5”) After treatment with a silane coupling agent having an epoxy group, at least one of the group of compounds having an amine group and a (meth)acrylic acid group, an amine compound, and a thiol compound is added. 如請求項9或10之複合積層體之製造方法，其中，在形成前述樹脂塗布層前，形成含官能基之層時，在形成含官能基之層之前，於前述材料層施予選自脫脂處理、UV臭氧處理、噴氣處理、研磨處理、電漿處理及電暈放電處理所成群中至少1種前處理。The method for manufacturing a composite laminate according to claim 9 or 10, wherein, before forming the resin coating layer, when forming the functional group-containing layer, before forming the functional group-containing layer, the material layer is subjected to a degreasing treatment selected from the material layer , UV ozone treatment, jet treatment, grinding treatment, plasma treatment and corona discharge treatment at least one kind of pretreatment. 一種接合體，其係如請求項1~8中任1項之複合積層體之樹脂塗布層側之面與聚烯烴經接合一體化。A joined body, which is a composite laminate according to any one of claims 1 to 8 on the resin coating layer side surface and polyolefin being joined and integrated. 一種接合體之製造方法，其係如請求項12之接合體之製造方法，其係以選自超音波溶著法、振動溶著法、電磁誘導法、高周波法、雷射法及熱壓法所成群中至少1種方法，於前述複合積層體之樹脂塗布層側之面溶著前述聚烯烴。A method of manufacturing a bonded body, which is the manufacturing method of a bonded body as in claim 12, which is selected from the group consisting of ultrasonic fusion method, vibration fusion method, electromagnetic induction method, high frequency method, laser method and hot pressing method In at least one method in the group, the polyolefin is melted on the surface of the resin coating layer side of the composite laminate. 一種接合體之製造方法，其係如請求項12之接合體之製造方法，以射出成形法於前述複合積層體之樹脂塗布層側之面溶著前述聚烯烴。A method of manufacturing a bonded body, which is the method of manufacturing a bonded body of claim 12, in which the polyolefin is melted on the surface of the resin coating layer side of the composite laminate by an injection molding method.
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