TW201127618A - Resin/metal composite laminate, resin/metal composite injection molded article, and method of manufacturing the same - Google Patents

Resin/metal composite laminate, resin/metal composite injection molded article, and method of manufacturing the same Download PDF

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Publication number
TW201127618A
TW201127618A TW099123431A TW99123431A TW201127618A TW 201127618 A TW201127618 A TW 201127618A TW 099123431 A TW099123431 A TW 099123431A TW 99123431 A TW99123431 A TW 99123431A TW 201127618 A TW201127618 A TW 201127618A
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Taiwan
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resin
metal composite
layer
resin layer
composite laminate
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TW099123431A
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Chinese (zh)
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TWI507287B (en
Inventor
Hisao Tajima
Shunichi Nishihara
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Mitsubishi Plastics Inc
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    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0011—Electromagnetic wave shielding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3431—Telephones, Earphones
    • B29L2031/3437—Cellular phones
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2571/00—Protective equipment

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention relates to a resin/metal composite laminate having a resin layer laminated on the surface of a metal plate, in which raised portions formed of a synthetic resin can be integrally formed on the resin layer with a high bonding strength by injection molding. The resin/metal composite laminate of the present invention has a metal plate and a resin layer a mainly composed of a polyamide-based resin and laminated on at least one surface of the metal plate. The resin layer a has a crystallization index of 0.40-0.80. crystallization index = |Hm1|-|Hc1|/|Hm2|... (I) (Hm1, Hc1, and Hm2 are the amounts of first melting heat, first generated heat, and second melting heat of crystallization, determined by DSC.)

Description

201127618 六、發明說明： 【發明所屬之技術領域】 本發明係樹脂/金屬複合積層材及其製造方法， , 於金屬板之至少一面積層以聚醯胺系樹脂作為主係關 脂層a的樹脂/金屬複合積層材，或者於此樹脂層&刀之柄 步積層以聚碳酸酯系樹脂與聚酯系樹脂之混合樹沪作為 成分之樹脂層b的樹脂/金屬複合積層材，在此 ”、、主 樹脂層b上經由模内（in-mould)成形或***成望月曰層&或 形，一體形成由合成樹脂所構成的凸部，適合製、^射出成 材（特別是OA機器和電子機哭 、艳各種構造 金屬複合射出成形體王之構成材料）的樹脂/ 其製造方法。之基材她編/金屬複合積層材及 匕本發明㈣於在此樹脂/金屬複合積純之樹闕a或樹 月曰層b上卩射出成形體形成由合成樹脂所構成之凸部 的樹脂/金屬縣料柄彡體及其製造方法。 X月亦關於由此樹脂/金屬複合射出成形體所構成之 OA機器用或電子機器用之框體。 【先前技術】 OA機哭、密工 ^ °°电千機器之框體（外殼），尤其如行動電話和筆 里電月甸之搞帶式機器的框體，近年來，日漸期望薄型小型 、 十於°亥等框體，亦被要求絕緣性、進一步要求電磁 波屏蔽性，並且力^ 任其内面側由於必須形成補強用肋材和鎖住 099123431 4 201127618 螺絲用凸座(boss)等之凸部，故在圖謀薄型小型化之外，對 於框體本體亦進行使該等凸部強固地—體成形的研究開發 (參照專利文獻1)。 以往，對於行動電話的框體，係採用圖6a、6b所示之構 _ 成者。 .圖6a中所示之框體n，係玻璃纖維補強聚醯胺系樹脂(特 別為MXD 6尼龍)般之高強度樹脂製者，具有可經由射出成 形而一體成形本體部11a與凸部llb的優點，另一方面，即 使為高強度樹脂，為了使樹脂滿足作為框體的必要強度，需 要至少1mm左右的厚度，於薄型化上亦有限度之缺點。 圖6b所示之框體12,係對金屬製之框體本體Ua施以用 於形成凸部的開孔加工，其後，使樹脂流入，經由物理性繫 合，形成樹脂製之凸部12b。此框體π因本體部12a為金 屬製’故可薄型化至厚度為0.3mm左右。又，亦可取得金 屬造成的電磁波屏蔽性、和樹脂部造成的絕緣性，但在本體 部12a的開孔加工上耗費手續，於設計方面亦成為大的限 制。更且，樹脂製凸部12b對於金屬製本體部12a形成的孔 . 部係以物理性繫合形成，故此繫合部的氣密性差，且具有防 . 水性差的缺點。 對於此種習知的框體，於專利文獻2中，提案將以被覆樹 脂被覆板面的金屬板***·固定至射出成形模具的腔體 内，並對此金屬板的被覆樹脂面射出溶融樹脂，形成射出成 099123431 5 201127618 形部分，而使金屬板與射出成形部分—體化。 若為此方法，藉由將預先形成樹脂層a的金屬才反予以適當 力口工者，配置在射出成形模具内’將凸部形成用之糊: 予以射出’對被«脂-體成形’則可不經過複雜的步驟， 而形成凸部。 又，如此處理所得之框體具備金屬製之本體部和樹脂層 a ’具有絕緣性、電磁波屏蔽性’又，亦可薄型化，並且可 以-體化至樹脂層a的凸部來形成補強用肋材和鎖住螺絲 用凸座。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平6_29669號公報 [專利文獻2]日本專利特開2〇〇1_315159號公報 【發明内容】 (發明所欲解決之問題） 於專利文獻2中’作為被覆樹脂，可列舉6尼龍等之聚酿 胺系樹脂，但對其結晶化度進而炫點的檢討並未進行，故對 於此被覆樹脂層a以射出成形㈣叙凸部的接黏強度，有 無法充分取得之缺點。 『對於被覆樹脂層，為了經由炫融樹脂的射出成形 體成形高接黏強度的凸部，因此在射出成形時，必須以^ 樹脂的熱使被覆樹脂適度㈣，與炫融樹脂呈現相溶狀; 099123431 6 201127618 冷部固化，因此，必須充分控制被覆樹脂的結晶化度進而熔 點，但在專利文獻2中，並未進行此種檢討。 更且，對於被覆樹脂層，要求與射出熔融樹脂之接黏性高 之同％•，要求加壓加工性優異，可承受模具溫度(8〇〜12〇。〇 的财熱f生不會經由射出壓力引起變开)的材料強度等，但 在專利文獻2中，並未進行此種檢討。 另外，於專利文獻2中，作成被覆樹脂為聚醋系樹脂、凸 部形成用樹脂為聚碳_(pc)與娜樹脂之混合物的組 合’就相溶性方面為佳，但pC/现樹脂有日夺亦無法充分 足作為補強用肋材、鎖住螺絲用凸座的必要強度，因此目前 f求以高強度工程塑料型式受到注目的MXD6尼龍形成凸 &和又’於此情況中，選擇可實現高接黏強度的被覆樹脂層 ^明係有鑑於上述先前之實狀而完成者，目的在於提供 屬板表面積層有樹脂層“咖旨/金屬複合積層材，在 曰層a上，經由射出成形可將合成樹脂所形成的凸部以 月"/金屬I 成賴脂/金屬複合積層材，以及在此樹 •月旨所形成之凸邱予^I上’經由射出成形將合成樹 合作為OA機W忠―租形成而成的各種構造材，尤其是適 合射出成形體 機器框體之構成材料的樹脂/金屬複 (解決問題之手段） 099123431 201127618 本發明者等人為了解決上述課題致力檢討，結果發現，若 以結晶化指數調整至指定範圍之聚醯胺系樹脂層、或以此種 聚醯胺系樹脂層作為中間層並以於其上積層形成之聚碳酸 酯系樹脂與聚酯系樹脂之混合樹脂作為主成分的樹脂層，則 所欲之凸部可以高接黏強度而一體成形。 本發明係根據此種發現而達成者，要旨如下。 本發明（第1態樣)之樹脂/金屬複合積層材，係具有金屬板 和在該金屬板的至少一面積層之以聚酿胺系樹脂作為主成 分之樹脂層的樹脂/金屬複合積層材，其特徵為，下述式(I) 所算出之上述樹脂層a的結晶化指數為0.40〜0.80。 [數1] 結晶化指數…⑴201127618 VI. Description of the Invention: [Technical Field] The present invention is a resin/metal composite laminate and a method for producing the same, and a resin having a polyamine-based resin as a main grease layer a in at least one area of a metal plate /Metal composite laminate, or a resin/metal composite laminate of a resin layer b containing a mixture of a polycarbonate resin and a polyester resin as a component of the resin layer & And the main resin layer b is formed by in-mould molding or inserting into a moiré layer or a shape, and integrally forming a convex portion composed of a synthetic resin, which is suitable for making and projecting a material (especially an OA machine and Resin of electronic machine crying, framing various structural metal composite injection molding body materials / manufacturing method thereof. The substrate is her braided / metal composite laminated material and 匕 The present invention (4) In this resin / metal composite pure tree A resin/metal stalk body in which a molded body is formed by 成形a or a tree 曰 layer b, and a convex portion composed of a synthetic resin is formed, and a method for producing the same. The X month is also related to the resin/metal composite injection molded body. OA machine or electronic machine frame. [Prior Art] OA machine crying, secret work ^ ° ° electric thousand machine frame (shell), especially such as mobile phones and pens In recent years, the frame of the machine has been increasingly expected to be thin and small, and the frame is made of the same size, and is required to be insulated, and further required electromagnetic wave shielding, and the inner surface side must be formed with reinforcing ribs and locked. 099123431 4 201127618 The convex portion such as the boss is used for the screw, and the research and development of the convex body is also performed on the frame body in addition to the thinning and miniaturization of the frame body (see Patent Document 1). In the past, the frame of the mobile phone was constructed as shown in Figs. 6a and 6b. The frame n shown in Fig. 6a is a glass fiber reinforced polyamine resin (especially MXD 6 nylon). As a general high-strength resin, there is an advantage that the main body portion 11a and the convex portion 11b can be integrally molded by injection molding. On the other hand, even if it is a high-strength resin, in order to satisfy the required strength as a frame, the resin needs at least 1 mm. Left and right thickness There is a limitation in the reduction in thickness. The frame 12 shown in Fig. 6b is formed by performing a hole forming process for forming a convex portion on the metal body Ua, and then flowing the resin through the physical property. The ribs 12b are formed by the resin. The frame π is made of metal by the main body portion 12a, so that the thickness can be reduced to about 0.3 mm. Further, the electromagnetic wave shielding property by the metal and the resin portion can be obtained. Although it is insulative, it takes a lot of trouble to perform the drilling of the main body portion 12a, and is also greatly limited in design. Further, the resin convex portion 12b is formed of a hole formed in the metal main body portion 12a. The combination is formed, so that the joint portion has poor airtightness and has the disadvantage of poor water resistance. In the conventional frame, it is proposed to insert and fix a metal plate coated with a resin-coated surface to a cavity of an injection molding die, and to eject a molten resin to the coated resin surface of the metal plate. Formed into a 099123431 5 201127618 shaped portion, and the metal plate and the injection molded portion are formed. For this method, the metal in which the resin layer a is formed in advance is appropriately applied to the worker, and the paste for forming the convex portion is disposed in the injection molding die: to be injected into the 'fat-body forming' The convex portion can be formed without complicated steps. Further, the frame body thus obtained is provided with a metal body portion and a resin layer a' having insulating properties and electromagnetic wave shielding properties, and can be made thinner, and can be formed into a convex portion of the resin layer a to form a reinforcing portion. Ribs and locking screws for the bosses. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. In the case of the coating resin, a polyamine-based resin such as nylon or the like is used as the coating resin. However, the evaluation of the degree of crystallization and the resilience of the resin is not performed. Therefore, the coating resin layer a is formed by injection molding (four). The bonding strength is not sufficient. In the case of the coating resin layer, in order to form a convex portion having a high adhesive strength through the injection molded body of the blister resin, it is necessary to appropriately coat the resin with the heat of the resin during the injection molding (four), and it is compatible with the smoldering resin. 099123431 6 201127618 The cold portion is solidified. Therefore, it is necessary to sufficiently control the degree of crystallization of the coating resin and the melting point. However, in Patent Document 2, such a review is not performed. In addition, it is required that the resin layer is required to have a high adhesion to the molten resin, and it is required to have excellent press workability and can withstand the mold temperature (8 〇 to 12 〇. The material strength and the like in which the injection pressure is caused to change, but in Patent Document 2, such a review is not performed. Further, in Patent Document 2, the combination of the coating resin is a polyester resin and the resin for forming a convex portion is a mixture of polycarbon-(pc) and naphthalene resin is preferable in terms of compatibility, but pC/current resin has It is also not enough to be used as a reinforcing rib and to lock the necessary strength of the boss for the screw. Therefore, it is currently required to form a convex & MXD6 nylon with a high-strength engineering plastic type and in this case, The coating resin layer capable of achieving high adhesion strength is completed in view of the above-described previous solid state, and an object of the invention is to provide a resin layer "correspondence/metal composite laminate material" on the surface layer of the surface of the plate, via the layer a, via Injection molding can form a synthetic resin with a convex portion formed by a month"/metal I lysate/metal composite laminate, and a convex qiu formed on the tree Cooperation is a variety of structural materials formed by the OA machine W-loyalty, especially the resin/metal complex that is suitable for the constituent material of the injection molding machine frame. (Means for solving the problem) 099123431 201127618 The inventors have solved In view of the above-mentioned problems, it has been found that a polyamine-based resin layer adjusted to a specified range by a crystallization index or a polycarbonate-based resin layer having an organic layer as an intermediate layer and formed thereon is laminated. In the resin layer containing the resin of the resin and the polyester resin as a main component, the desired convex portion can be integrally molded with high adhesive strength. The present invention has been achieved based on such findings, and the present invention is as follows. The resin/metal composite laminate of the aspect) is a resin/metal composite laminate having a metal plate and a resin layer having a polystyrene resin as a main component in at least one area layer of the metal plate, characterized in that The crystallization index of the above-mentioned resin layer a calculated by the above formula (I) is 0.40 to 0.80. [Number 1] Crystallization index...(1)

Hm2 (上述(I)式中，Hml、Hcl分別係以示差掃描型熱量計(DSC) 將該樹脂層a於30~300°C之溫度範圍中以升溫速度l〇°C/ 分鐘升溫時所測定的結晶溶解熱量（第1次結晶溶解熱量）、 結晶化發熱量（第1次結晶化發熱量），Hm2為其後放冷至 30°C後，再將該樹脂層a於30〜300°C之溫度範圍中以升溫 速度l〇°C/分鐘升溫時所測定的結晶熔解熱量（第2次結晶熔 解熱量）。） 第2態樣之樹脂/金屬複合積層材係於第1態樣之樹脂/金 屬複合積層材中，上述樹脂層a所含之聚醯胺系樹脂為6 099123431 8 201127618 尼龍。 第3態樣之樹脂/金屬複合積層材係於第1態樣或第2態 樣之樹脂/金屬複合積層材中，上述樹脂層a的厚度為5〜1〇〇 Am，上述金屬板的厚度為0.03〜3.〇mm。 第4態樣之樹脂/金屬複合積層材係於第ι態樣至第3態 樣之樹脂/金屬複合積層材之任—者巾，上述㈣層&上， 進-步具有以聚碳酸酯系樹脂與聚料樹脂之混合樹脂作 為主成分的第2樹脂層b。 第5態樣之樹脂/金屬複合積層材係於第*態樣之樹脂/金 屬複合積層材巾，上職脂層b所含之聚碳_系樹脂與聚 脂的混合比為聚碳酸I系樹脂：聚醋系樹脂 80〜70 : 30 〇 第6態樣之樹脂/金屬複合積層材係於第*態樣或第$態 樣之樹脂/金屬複合積層材中，上述樹脂層b所含之聚醋系 樹脂為聚對苯二甲酸丁二s|的樹脂/金屬複合積層材。’、 第7態樣之樹脂/金屬複合積層材係於第4態樣至第6態 樣之樹脂/金屬複合積之任—者巾，使祕模内成形。 第8態樣之樹脂/金屬複合積層材係於第ι態樣至第3態 樣之樹脂/金屬複合積層材之任—者中，用以在上述樹脂廣^ 上，經由射出成形將合成樹脂所形成之凸部—體形成的樹脂 /金屬複合積層材。 第9態樣之樹脂/金屬複合積層材係於第4態樣至第7態 099123431 9 201127618 樣之樹脂/金屬複合積層材之任一者中，用以在上述樹脂層b 上，經由射出成形將合成樹脂所形成之凸部一體形成的樹脂 /金屬複合積層材。 第10態樣之樹脂/金屬複合積層材係於第8態樣或第9態 樣之樹脂/金屬複合積層材中，上述樹脂層a、上述樹脂層b、 或構成上述樹脂層a及樹脂層b之樹脂熔點比構成上述凸部 之合成樹脂熔點更低10〜60°C。 第11態樣之樹脂/金屬複合積層材係於第10態樣之樹脂/ 金屬複合積層材中，構成上述凸部之合成樹脂為MXD 6尼 龍。 第12態樣之樹脂/金屬複合積層材係於第10態樣之樹脂/ 金屬複合積層材中，構成上述凸部之合成樹脂為聚碳酸酯系 樹脂。 第13態樣之樹脂/金屬複合積層材係於第1態樣至第12 態樣之樹脂/金屬複合積層材之任一者中，將上述金屬板之 形成有上述樹脂層a或上述樹脂層a及樹脂層b的面之反側 面，予以防姓銘（alumite)加工處理。 第14態樣之樹脂/金屬複合積層材係於第1態樣至第13 態樣之樹脂/金屬複合積層材之任一者中，在上述金屬板之 形成有上述樹脂層a或上述樹脂層a及樹脂層b的面之反側 面，依序具有塗佈用薄膜層和樹脂塗佈層。 本發明（第15態樣)之樹脂/金屬複合射出成形體係在本發 099123431 10 201127618 明（第1態樣至第14態樣之任一者)之樹脂/金屬複合積層材 之樹脂層a或樹脂層b上’將合成樹脂之熔融樹脂予以射出 成形’使该合成樹脂所構成之凸部一體成形。 本發明（第16態樣)之OA機器用或電子機器用之框體係 包含本發明（第15態樣)之樹脂/金屬複合射出成形體。 • 第17態樣之OA機器用或電子機器用之框體係於第丨6態 樣之OA機器用或電子機器用之框體中，為行動電話的框 體。 本發明（第18態樣)之樹脂/金屬複合積層材之製造方法， 係製造本發明（第1態樣至第14態樣之任一者)之樹脂/金屬 複合積層材之方法，其特徵為具有將樹脂薄膜熔黏至上述金 屬板之積層步驟。 本發明（第19態樣)之樹脂/金屬複合射出成形體之製造方 法，係製造本發明（第15態樣)之樹脂/金屬複合射出成形體 之方法，其特徵為具有在配置上述樹脂/金屬複合積層材之 射出成形模具内’將上述溶融樹脂射出並且一體成形上述凸 部的步驟° . (發明效釆） . 構成本發明之樹脂/金屬複合積層材之樹脂層a的樹脂， 係以聚醯胺系樹脂作為主成分，並將其結晶化指數控制於特 定範圍，因此在凸部形成用樹脂之射出成形時，此樹脂層a 的樹脂係以溶融樹脂的熱予以適度熔融，並以與射出之熔融 099123431 201127618 樹脂充分相溶的狀態冷卻硬化，因此可在此樹脂層a上以高 接黏強度形成合成樹脂的凸部。 又，若在此種樹脂層a上進一步積層形成以聚碳酸酯系樹 脂與聚If、樹脂之混合樹脂作為主成分之樹脂層b的樹^ 金屬複合積層材，則與射出成形之樹脂(例如聚碳酸酯系樹 脂）的接黏性高，且柔軟，故加壓加工性亦優，更且亦具^ 可承受模具溫度（80〜12(rc)的耐熱性。 此種在本發明之樹脂/金屬複合積層材之樹脂層&或樹脂 層b上，將合成樹脂找融樹脂經由射出成形而—體形成合 成樹脂製之凸部所構成之本發明之樹脂/金屬複合射出成形 體，因具備金屬板與樹脂層，故具有電磁波屏蔽性、絕緣性， 且因以金屬㈣為㈣，故可在充分強度下薄魏，且對於 樹脂層可使補強用肋材、鎖住螺絲用凸座等凸部強固地—體 成形，故適於作為各種構造材，特別是〇A機器和電子機= 之框體’尤其作為行動電話之框體，可有效提高其薄型小^ 化0 【實施方式】 以下，洋細說明本發明之實施形態。 [樹脂/金屬複合積層材] 層a、或者樹脂層a與在此樹脂層 屬樹脂/金屬複合積層材’係具有金屬板、在該金 ^板至二面積層之以聚__旨作為主成分的樹脂 a上進一步積層之以聚碳 099123431 12 201127618 酸醋系樹脂和聚醋系樹脂之混合樹脂作為主成分之樹脂層 b的樹脂/金屬複合積層材，其特徵為下述式(I)所算出之上 述樹脂層&的結晶化指數為0.40〜0.80。 [數2] • 結晶化指數…① |Hm2| (上述(I)式中，Hm】、Hel分別係以示差掃描型熱量計(dsc) 將該樹脂層a於30〜30(rc之溫度範圍中以升溫速度1〇。〇/ 分鐘升溫時所測定的結晶熔解熱量（第丨次結晶熔解熱量）、 、’° BB化叙熱1(第1次結晶化發熱量），Hm2為其後放冷至30 C後，再將該樹脂層a於3〇〜3〇(rC2溫度範圍中以升溫速 度10C/分鐘升溫時所測定的結晶熔解熱量（第2次結晶熔解 熱量）。） 圖la、lb係示出本發明之樹脂/金屬複合積層材之實施形 態之一例的剖面圖，此樹脂/金屬複合積層材la、lb係在金 屬板1A的一面透過底漆層lc形成樹脂層1B。圖la之樹 脂/金屬複合積層材la中，樹脂層1B為樹脂層a(圖la中， 以符號「lB-a」表示）的單層構造。圖lb之樹脂/金屬複合 積層材lb中，樹脂層1B以樹脂層a(圖lb中，以符號「1B_a」 表示)作為中間層（塗底層），且以樹脂層b(圖】b中，以符號 「lB-b」表示)作為表面層的2層積層構造。 <金屬板> 099123431 201127618 可列舉純鋁板、|g合金 作為本發明之金屬板之具體例 板、不銹鋼板、鋼板、純鈦板、鈦合金板、鎂合金板、鎳、 鋅、銅等之金屬予以單層鑛敷而成的單層賴鋼板、將續等 金屬之2種以上予以複層錄而成的複層鍍敷鋼板、該等金 屬之2種以上而成之合料，敷而成的合金鍍數鋼板等。 又，可列舉對該等鋼板及錢數鋼板形成由絡水合氣化物所 構成之單層皮膜之重減溶液㈣解處理，或形成上層為絡 水合氧化物而下層為金屬鉻所構成之2層皮狀電騎酸 處理等之化成處理’而形成—的各種表面處_板、不銹 鋼板、紹合金板’施以形成鉻水合氧化物所構成之單声皮膜 之上述化成處理或其他化錢理之浸潰鉻酸處理、鱗祕酸 處理、以及以驗溶液或酸溶液之㈣處理、陽極氧化處理等 的銘板、紹合金板、銅、銅合金等。 該等金屬板中’由高強度且耐餘性優異方面而言，以挪 304等之不錄鋼板或其表面處理板(例如鍍 又，由輕量方面而言，以鋁板、鋁 為 σ1板或其表面處理板為 金屬板的厚度係根據樹脂/金屬複合積層材及使用此樹用 /金屬複合積層材之樹脂/金屬複合射出成形體的使用目 的，以取得必要強度和厚度般適當決定，… 0.03〜3.0mm、特別為 〇1〜2 〇mm。 ’ 特別，如行動電話之框體般之要求薄型化之用途中，金屬 099123431 14 201127618 板的厚度為0.H 〇mm左右為佳，且金屬板為SUs綱等 之不錄鋼板之情沉為G ^/醜、於链或紹合金板之情況為 0.3〜1.0mm左右為佳。 .金屬板的厚度若過薄，則無法取得必要之強度，並且因射 出成t 4的糾日壓力而發生變形，成形後，經由樹脂收縮而 •發生金屬板變形，若過厚則無法達成薄型化。 <底漆層> 圖la lb +的底漆層lc並非必定需要，但在提高金屬板 1A與樹脂層1B之密合性的目的下，以中介存在各種底漆 層接黏^層為佳。作為底漆層和接黏劑，可使用先前公知 之銘系、鈦系、魏系等偶合劑’丙烯酸樹脂系接黏劑、胺 基甲酸賴脂系接黏劑、環氧樹脂系接黏劑、《樹脂系接 黏劑等2伽上’但並非限定於該等例示者。 底漆層、接黏層的厚度，以不阻礙薄型化，並且充分取得 提高金屬板與樹脂層a之密合性的效果方面而言，通常為 0.1〜15 // m左右。 <樹脂層a> 本發明之樹月旨層a(圖la、lb中之樹脂層i㈣，係以聚酸 胺系樹脂作為主成分所構成，且上述之結晶化指數為 0.40〜0.80為其特徵。 另外，此處所謂「主成分」係指佔有構成樹脂層a之樹脂 之5〇質量％以上、較佳為⑽質量％以上、特佳為95質量％ 099123431 15 201127618 以上的樹脂。 (聚醯胺系樹脂） 於本發明中，作為構成樹脂層a的聚醯胺系樹脂，可列舉 6尼4、11尼龍、12尼龍、66尼龍、61〇尼龍、612尼龍、 46尼龍、間二甲苯二胺與己二酸之聚縮合反應生成之含有 構造單位90莫耳％以上的芳香族聚醯胺系樹脂等。又，亦 可列舉該等樹脂之賴酐等之酸改質物、甲基丙烯酸環氧丙 酯等之環氧改質物等之單獨或混合物等。 聚醯胺系樹脂係因與後述樹脂/金屬複合射出成形體之凸 邛形成用樹脂的相溶性、熔黏性優異方面為佳，因加工性優 異、樹脂/金屬複合積層材之彎曲加工和深拉伸加工時難龜 裂等方面為佳，因耐熱性優異，因即使於後述射出成形時之 模具溫度（通常1〇〇〜16〇。〇亦可充分承受方面為佳。 其中，就容易滿足本發明所規定之結晶化指數，且與構成 後述本發明之樹脂/金屬複合射出成形體之凸部之合成樹脂 的相溶性、溶黏性優異方面而言，以6尼龍為佳。 (其他成分） 另外，構成樹脂層a之樹脂亦可為與聚醯胺系樹脂以外之 祕月日的合物。此時，作為聚酿胺系樹脂以外之樹脂的具體 例，可列舉聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等之 聚酯系樹脂；以聚乙烯、聚丙烯、乙烯作為主成分之共聚合 體等之烯烴系樹脂。但是，本發明之樹脂層a，就控制結晶 〇99丨23431 201127618 化指數及與構成後述凸部之合成樹脂的相溶性、熔黏性方面 而言，以僅以聚醯胺系樹脂作為樹脂成分所形成者為佳，特 別以僅以6尼龍作為樹脂成分所形成者為佳。 本發明之樹脂層a係可在上述聚醯胺系樹脂作為主成分 之樹脂中，進一步視需要配合賦予接黏性劑、滑劑、顏料等 之樹脂添加劑而形成。 (結晶化指數） 本發明之樹脂層a的結晶化指數若超過0.80,則在後述的 射出成形時，以射出之炫融樹脂的熱的溶解性不夠充分，無 法以高接黏強度一體成形凸部。若結晶化指數未滿0.40,則 變成耐熱性差者且不佳。因此，樹脂層a之結晶化指數為 0.40〜0.80、較佳為 0.6〜0.75。 另外，樹脂層a的結晶化指數，具體而言可以後述實施例 項中記載之方法所測定、算出。 作為將樹脂層a之結晶化指數作成上述範圍之方法，可列 舉選擇適當之聚醯胺系樹脂，並且如後述，適當調整於金屬 板形成樹脂層a後之冷卻條件的方法。又，亦有除了在選擇 之聚醯胺系樹脂中添加填充劑等以外，亦調整冷卻條件而將 結晶化指數作成上述範圍的方法。 (熔點） 構成樹脂層a的樹脂係滿足上述結晶化指數，且其熔點比 用以經由後述之射出成形而形成凸部之合成樹脂之熔點更 099123431 17 201127618 低10〜60C、特別為10~贼、尤其為15〜4〇<t者為佳。構 成樹脂層a之樹脂溶點若過高，則在後述之射出成形時，以 射出之㈣樹脂的熱祕解性不夠充分，無法以高接黏強度 収成形凸部。但’此溶點若過低，則變成耐熱性差者，無 法承受射出成形模具的溫度，較不佳。 (厚度）Hm2 (In the above formula (I), Hml and Hcl are respectively heated by a differential scanning calorimeter (DSC) at a temperature increase rate of 10 °C to 300 °C in a temperature range of 30 to 300 °C. The measured crystal heat of dissolution (first crystal heat of dissolution), crystallization heat generation (first crystallization heat generation), Hm2 is followed by cooling to 30 ° C, and then the resin layer a is 30 to 300 In the temperature range of °C, the heat of crystal melting (the second heat of crystal melting) measured at a temperature increase rate of l〇°C/min.) The second aspect of the resin/metal composite laminate is in the first aspect. In the resin/metal composite laminate, the polyamine resin contained in the resin layer a is 6 099123431 8 201127618 nylon. The resin/metal composite laminate of the third aspect is in the resin/metal composite laminate of the first aspect or the second aspect, wherein the thickness of the resin layer a is 5 to 1 〇〇Am, and the thickness of the metal sheet is It is 0.03~3.〇mm. The resin/metal composite laminate of the fourth aspect is a resin/metal composite laminate of the ι to the third aspect, and the above (4) layer & A second resin layer b containing a mixed resin of a resin and a polymer resin as a main component. The resin/metal composite laminate of the fifth aspect is a resin/metal composite laminate towel of the first aspect, and the mixing ratio of the polycarbon-based resin and the polyester contained in the upper lipid layer b is a polycarbonate I system. Resin: Polyacetate resin 80 to 70: 30 〇 The sixth aspect of the resin/metal composite laminate is in the first aspect or the first aspect of the resin/metal composite laminate, and the resin layer b is contained therein. The polyacetal resin is a resin/metal composite laminate of polybutylene terephthalate s|. The resin/metal composite laminate of the seventh aspect is a resin/metal composite product of the fourth aspect to the sixth aspect, which is formed into a secret mold. The resin/metal composite laminate of the eighth aspect is used in any of the resin/metal composite laminates of the ι to the third aspect, and is used for the synthetic resin on the above-mentioned resin by injection molding. The formed convex-body formed resin/metal composite laminate. The ninth aspect of the resin/metal composite laminate is used in any one of the fourth aspect to the seventh state 099123431 9 201127618-like resin/metal composite laminate for forming on the resin layer b via injection molding. A resin/metal composite laminate in which a convex portion formed of a synthetic resin is integrally formed. The resin/metal composite laminate of the tenth aspect is the resin layer/metal composite laminate of the eighth aspect or the ninth aspect, the resin layer a, the resin layer b, or the resin layer a and the resin layer. The melting point of the resin of b is 10 to 60 ° C lower than the melting point of the synthetic resin constituting the above convex portion. The resin/metal composite laminate of the eleventh aspect is the resin/metal composite laminate of the tenth aspect, and the synthetic resin constituting the convex portion is MXD 6 nylon. The resin/metal composite laminate of the twelfth aspect is the resin/metal composite laminate of the tenth aspect, and the synthetic resin constituting the convex portion is a polycarbonate resin. The resin/metal composite laminate of the thirteenth aspect is any one of the resin/metal composite laminate of the first aspect to the twelfth aspect, wherein the metal layer is formed with the resin layer a or the resin layer The opposite side of the surface of a and the resin layer b is treated with alumite. The resin/metal composite laminate according to the fourteenth aspect is any one of the resin/metal composite laminate of the first aspect to the thirteenth aspect, wherein the resin layer a or the resin layer is formed on the metal plate. The opposite side of the surface of a and the resin layer b has a coating film layer and a resin coating layer in this order. The resin/metal composite injection molding system of the present invention (the fifteenth aspect) is a resin layer a of the resin/metal composite laminate of the present invention, which is in the form of any one of the first aspect to the fourteenth aspect, or On the resin layer b, 'the molten resin of the synthetic resin is injection molded', and the convex portion formed of the synthetic resin is integrally molded. A frame system for an OA machine or an electronic device according to a sixteenth aspect of the present invention comprises the resin/metal composite injection molded article of the present invention (the fifteenth aspect). • The frame system for the OA machine or electronic device in the 17th aspect is the frame of the mobile phone in the frame for the OA machine or electronic device in the sixth aspect. The method for producing a resin/metal composite laminate according to the present invention (the eighth aspect) is a method for producing a resin/metal composite laminate of the present invention (any of the first aspect to the fourteenth aspect), which is characterized It is a lamination step of having a resin film adhered to the above metal plate. A method for producing a resin/metal composite injection molded body according to a nineteenth aspect of the present invention, which is a method for producing a resin/metal composite injection molded article of the present invention (the fifteenth aspect), characterized in that the resin is disposed In the injection molding die of the metal composite laminate, the step of ejecting the molten resin and integrally molding the convex portion is obtained. (Inventive effect) The resin constituting the resin layer a of the resin/metal composite laminate of the present invention is Since the polyamine resin is used as a main component and the crystallization index is controlled to a specific range, the resin of the resin layer a is appropriately melted by the heat of the molten resin during the injection molding of the resin for forming the convex portion, and The film is cooled and hardened in a state in which the melted 090921431 201127618 resin is sufficiently compatible, so that the convex portion of the synthetic resin can be formed on the resin layer a with high adhesive strength. In addition, when a resin composite layer of a resin layer b containing a polycarbonate resin and a mixed resin of poly If and a resin as a main component is further laminated on the resin layer a, the resin is formed by injection molding (for example, The polycarbonate resin has high adhesion and is soft, so it is excellent in press workability, and also has mold resistance (80 to 12 (rc) heat resistance. This resin in the present invention) In the resin layer of the metal composite laminate, or the resin layer b, the resin/metal composite injection molded body of the present invention comprising the synthetic resin resin is formed by injection molding to form a convex portion made of a synthetic resin. Since it has a metal plate and a resin layer, it has electromagnetic wave shielding properties and insulation properties, and since metal (4) is (4), it can be thinned at a sufficient strength, and the reinforcing rib can be used for the resin layer, and the boss for locking the screw can be locked. The convex portion is strongly formed into a body, so it is suitable as a variety of structural materials, in particular, the frame of the machine A and the electronic machine = especially as a frame of a mobile phone, which can effectively improve its thinness and small size. 】 below, fine Embodiments of the present invention. [Resin/Metal Composite Laminate] The layer a, or the resin layer a, and the resin layer/resin composite laminate of the resin layer have a metal plate, and the metal plate to the two-layer layer A resin/metal composite laminate of a resin layer b having a polycarbon 099123431 12 201127618 mixed resin of a vinegar-based resin and a polyester resin as a main component, which is further laminated on the resin a as a main component. The crystallization index of the above resin layer & calculated by the following formula (I) is 0.40 to 0.80. [Number 2] • Crystallization index...1 | Hm2| (In the above formula (I), Hm], Hel respectively The resin layer a was subjected to a differential scanning calorimeter (dsc) at a temperature rise rate of 30 to 30 (the temperature range of rc was 1 Torr. The heat of crystal melting measured at the temperature increase of 〇/min (the heat of the second-order crystal melting) , '° BB crystallization heat 1 (first crystallization heat generation), Hm2 is followed by cooling to 30 C, and then the resin layer a is 3 〇 3 〇 (rC2 temperature range at the temperature increase rate) The heat of crystal melting measured at a temperature rise of 10 C/min (the second heat of crystal melting).) And lb is a cross-sectional view showing an example of an embodiment of the resin/metal composite laminate of the present invention. The resin/metal composite laminates la and lb are formed on the surface of the metal sheet 1A through the primer layer lc to form the resin layer 1B. In the resin/metal composite laminate la of Fig. 1a, the resin layer 1B is a single layer structure of the resin layer a (indicated by the symbol "lB-a" in Fig. 1a). In the resin/metal composite laminate lb of Fig. 1b, The resin layer 1B has a resin layer a (indicated by the symbol "1B_a" in FIG. 1b) as an intermediate layer (coating layer), and a resin layer b (indicated by the symbol "lB-b" in FIG. The 2-layer laminate structure. <Metal Plate> 099123431 201127618 A pure aluminum plate and a |g alloy are exemplified as a specific example of the metal plate of the present invention, a stainless steel plate, a steel plate, a pure titanium plate, a titanium alloy plate, a magnesium alloy plate, nickel, zinc, copper, or the like. A single-layer steel sheet obtained by laminating a single layer of a metal, a multi-layered plated steel sheet in which two or more kinds of metals are re-laminated, and a mixture of two or more of these metals. The alloy is plated with several steel plates. Further, a method of decomposing a heavy-reduction solution (4) of a single-layer film composed of a complex hydrated vapor formed by the steel plate and the number of steel plates, or a layer of a metal chrome formed by forming a lower layer of a complex hydrated oxide and a lower layer may be mentioned. The above-mentioned chemical conversion treatment or other chemical treatment of a single acoustic film composed of chromium hydrated oxide is applied to various surfaces at the surface of the formation process of the skin-like electro-acupuncture treatment, such as forming a plate. It is impregnated with chromic acid treatment, scaly acid treatment, and the name plate, the alloy plate, copper, copper alloy, etc. of the test solution or the acid solution (4) treatment, anodizing treatment, and the like. In these metal sheets, in terms of high strength and excellent durability, it is not necessary to record steel sheets or surface treatment boards thereof (for example, plating, and in terms of lightweight, aluminum sheets and aluminum are σ1 boards). The thickness of the metal sheet is determined according to the purpose of the resin/metal composite laminate and the resin/metal composite injection molded body using the tree/metal composite laminate, and is appropriately determined to obtain the necessary strength and thickness. ... 0.03~3.0mm, especially 〇1~2 〇mm. 'Specially, in the case of thinning of the frame of a mobile phone, the thickness of the metal 099123431 14 201127618 is preferably about 0.H 〇mm. Moreover, it is preferable that the metal plate is a non-recorded steel plate of the SUs class, and it is preferably G^/ugly, and the case of the chain or the alloy plate is about 0.3 to 1.0 mm. If the thickness of the metal plate is too thin, the necessity cannot be obtained. The strength is deformed by the weathering pressure of the injection of t 4 , and after the molding, the metal sheet is deformed by the shrinkage of the resin, and if it is too thick, the thickness cannot be reduced. < Primer layer> Fig. la lb + The primer layer lc is not necessarily required. In order to improve the adhesion between the metal plate 1A and the resin layer 1B, it is preferred to intervene various primer layer adhesive layers. As the primer layer and the adhesive, the previously known Ming system and the titanium system can be used. , Wei system and other coupling agents 'acrylic resin adhesive, urethane lysate adhesive, epoxy resin adhesive, "resin adhesive, etc. 2 gamma" but not limited to these examples The thickness of the primer layer and the adhesive layer is usually about 0.1 to 15 // m in terms of the effect of not reducing the thickness and sufficiently improving the adhesion between the metal plate and the resin layer a. Resin layer a> The resin layer i (four) in Fig. 1a and 1b is composed of a polyamic acid-based resin as a main component, and the above-mentioned crystallization index is 0.40 to 0.80. In addition, the term "main component" as used herein means a resin containing 5 〇 mass% or more, preferably 10% by mass or more, and particularly preferably 95% by mass of 099123431 15 201127618 or more of the resin constituting the resin layer a. Resin) In the present invention, as a polyamine which constitutes the resin layer a The resin may be a mixture of 6 ny 4, 11 nylon, 12 nylon, 66 nylon, 61 〇 nylon, 612 nylon, 46 nylon, m-xylene diamine and adipic acid to form a structural unit of 90 mol% or more. The aromatic polyamine-based resin, etc., may be exemplified by an acid-modified substance such as lysine or the like, or an epoxy modified product such as glycidyl methacrylate. The resin is excellent in compatibility with the resin for forming a tenon of the resin/metal composite injection molded product to be described later, and is excellent in meltability, and is excellent in workability, bending and deep drawing of the resin/metal composite laminate. It is preferable that it is difficult to crack or the like, and it is excellent in heat resistance, and the mold temperature (usually 1 〇〇 to 16 通常) at the time of injection molding described later. It is better to be able to fully withstand the aspect. In particular, it is easy to satisfy the crystallization index defined by the present invention, and it is excellent in compatibility and solubility with respect to the synthetic resin constituting the convex portion of the resin/metal composite injection molded article of the present invention to be described later. good. (Other components) The resin constituting the resin layer a may be a compound other than the polyamide resin. In this case, specific examples of the resin other than the polystyrene-based resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate; and polyethylene, polypropylene, and ethylene. An olefin-based resin such as a copolymer of a main component. However, the resin layer a of the present invention controls the crystallization 〇99丨23431 201127618 index and the compatibility with the synthetic resin constituting the convex portion described later, and the melt viscous property, and only the polyamide resin is used as the resin component. It is preferable to form it, and it is especially preferable to form only a nylon resin as a resin component. The resin layer a of the present invention can be formed by further adding a resin additive such as a tackifier, a slip agent or a pigment to the resin containing the polyamine resin as a main component. (Crystalization Index) When the crystallization index of the resin layer a of the present invention exceeds 0.80, the heat solubility of the molten resin to be injected is insufficient at the time of injection molding to be described later, and it is not possible to integrally form the convex with high adhesive strength. unit. If the crystallization index is less than 0.40, it becomes poor in heat resistance and is not preferable. Therefore, the crystallization index of the resin layer a is 0.40 to 0.80, preferably 0.6 to 0.75. Further, the crystallization index of the resin layer a can be specifically measured and calculated by the method described in the following examples. As a method of setting the crystallization index of the resin layer a to the above-mentioned range, a method of selecting an appropriate polyamine-based resin and adjusting the cooling conditions after the resin layer a is formed on the metal plate as described later can be mentioned. Further, in addition to the addition of a filler to the selected polyamine-based resin, the cooling conditions are adjusted to form a crystallization index in the above range. (melting point) The resin constituting the resin layer a satisfies the above crystallization index, and its melting point is 10 to 60 C, especially 10 thief, which is lower than the melting point of the synthetic resin which is formed by the injection molding described later by injection molding. Especially for 15~4〇<t is better. When the resin melting point of the resin layer a is too high, the heat-disintegrating property of the (four) resin which is emitted at the time of injection molding described later is insufficient, and the convex portion cannot be formed with high adhesive strength. However, if the melting point is too low, the heat resistance is poor, and the temperature at which the molding die is injected cannot be withstood. (thickness)

於本發明中，樹脂層a的厚度若過薄，則在後述凸部之射 出成形中，無法以高接黏強度一體成形凸部，X，在樹r/ 金屬複合積層材之加工時產生發生針孔_㈣)等不U Γ樹脂層a之厚度若過厚，則在樹脂/金屬複合積層材之 2加工等之加工時’樹脂層a易剝離，且會阻礙樹脂/金 複合積層材、甚至樹脂/金屬複合射出成形體的薄型化： 因此，樹脂層a的厚度’亦根據此樹脂層3上是否㈣ 之用途、此樹脂層a上形成凸部之形狀和構造等 為佳’特別於樹脂層3上未顺^ 二：闕3的厚度—m為佳’― 又，在Μ脂層a上形成樹脂層 Α ς 心渭，兄，樹脂層a的厚度 為5〜50 // m、特別為〗π 予 ㈣為10〜4〇㈣、尤其為 〈樹脂層b&gt; Mm為佳。 3上積層形成樹脂 以上述樹脂層a作為中間層並在樹脂層 099123431 201127618 層b(圖lb中之樹脂層lB-b)之情況，該樹脂層b可由以聚 碳酸酯系樹脂及聚酯系樹脂之混合樹脂作為主成分的樹脂 組成物所形成。 於聚碳酸酯系樹脂單體之情況，加壓加工性有問題，加工 後會產生裂痕等，但經由使用聚碳酸酯系樹脂與聚酯系樹脂 之混合樹脂，可改善加壓加工性。 (聚碳酸酯系樹脂） 聚碳酸酯系樹脂係由碳酸和二醇或二價酚所構成，若以一 般式：-(0-R-0-C0-)n-所示者(R為二價脂肪酸或芳香族基) 即可。 可列舉例如使用由酚和丙酮所合成之雙酚A的界面聚合 法、以酯交換法、吡啶法等所製造者；雙酚A與二羧酸衍 生物、例如與對（異）苯二曱酸二氯等之共聚所得者；雙酚A 之衍生物，例如四亞曱基雙酚A等之聚合所得者等。 亦可使用將一部分或全部之雙酚A以其他之二價酚予以 取代之構造者。 此時，作為其他之二價酚，可列舉氫醌、4,4-二羥基聯苯、 雙(4-羥苯基）甲烷、1-雙(4-羥苯基）乙烷等之雙(4-羥苯基)烷 屬烴類；1，1-雙(4-羥苯基)環己烷等之雙(4-羥苯基)環烷屬烴 類；雙(4-羥苯基)硫、雙(4-羥苯基)砜、雙(4-羥苯基）亞砜、 雙(4-羥苯基)醚等之化合物；2,2-雙(3-曱基-4-羥苯基）丙烷等 之烷基化雙酚類；2,2-雙(3,5-二溴基-4-羥笨基）丙烷等之鹵 099123431 19 201127618 化雙酚類。 聚碳酸酯系樹脂之黏度平均分子量並無特別限定，以 10,000〜100,000、特別以20,000〜30,000、其中亦特別以 23,000〜28,000之範圍者為佳。 又，聚碳酸酯系樹脂之熔體流動速率並無特別限定，根據 JISK7210，於300°C、1.2公斤荷重中測定的熔體流動速率 為5〜20者為佳。 作為聚碳酸酯系樹脂，可列舉例如三菱工程塑料公司製 「Upilon」系列、住友Dow公司製「Kaliber」系列等。 另外，作為聚碳酸酯系樹脂可單獨使用1種聚碳酸酯系樹 脂，且亦可混合使用2種以上之聚碳酸酯系樹脂。 (聚酯系樹脂） 作為聚酯系樹脂，可為二羧酸成分與二醇成分縮合聚合而 成的樹脂，其中就耐熱性方面而言，以芳香族二羧酸成分與 二醇成分縮合聚合而成的芳香族聚酯系樹脂為佳。 此處，作為上述之「芳香族二羧酸成分」之代表者可列舉 對苯二酸、間苯二酸、萘二羧酸等，但亦可為對苯二酸之一 部分經「其他之二羧酸成分」所取代者。 此時，作為「其他之二羧酸成分」可列舉草酸、丙二酸、 琥珀酸、己二酸、壬二酸、癸二酸、新戊酸、間苯二酸、萘 二羧酸、二苯醚二羧酸、對-羥基苯曱酸等。其可為1種或 2種以上之混合物，又，亦可適當選擇經取代之其他二羧酸 099123431 20 201127618 的份量。 作為上述「二醇成分」之代表者，可列舉乙二醇、二乙二 醇、三乙二醇、環己烷二曱醇等，但乙二醇之一部分亦可經 「其他之二醇成分」所取代。 '此時，作為「其他之二醇成分」，可列舉丙二醇、丁二醇、 三亞曱基二醇、四亞曱基二醇、六亞曱基二醇、二伸乙基二 醇、新戊二醇、聚伸烷基二醇、1，4-環己烷二曱醇、甘油、 季戊四醇、三羥曱基、曱氧基聚伸烷基二醇等。其可為1 種或2種以上之混合物，又，亦可適當選擇經取代之其他二 醇的份量。 又，作為其他之聚酯系樹脂，亦可使用含有對苯二酸以外 之其他二羧酸成分及/或乙二醇以外之其他二醇成分的「共 聚聚S旨」。 本發明所用之芳香族聚酯系樹脂等之聚酯系樹脂的分子 量並無特別限定，以苯酚/四氯乙烯=50/50(體積比）溶液中， 30°C之固有黏度為0.600〜1.400左右者為佳。 作為此種芳香族共聚聚酯之具體的製品例，可列舉例如聚 • 對苯二酸乙二酯之改質體：三菱化學公司製「Novapex」系 • 列（例如，Novapex PS600)、聚對苯二酸丁二酯之改質體： 三菱工程塑料公司製之「Novadulan」系列（例如，Novadulan 5008)。又，可列舉將聚對苯二酸乙二酯中之約30莫耳％乙 二醇以1，4-環己烧二曱醇取代之聚自旨樹脂：Eastman 099123431 21 201127618In the present invention, when the thickness of the resin layer a is too small, the convex portion cannot be integrally formed with high adhesive strength in the injection molding of the convex portion described later, and X occurs in the processing of the tree r/metal composite laminate. When the thickness of the resin layer a is not too large, the resin layer a is easily peeled off during processing such as processing of the resin/metal composite laminate, and the resin/gold composite laminate is hindered. Even the resin/metal composite injection molded body is thinned: Therefore, the thickness ' of the resin layer a is also preferably based on the use of the resin layer 3 (4), the shape and structure of the convex portion formed on the resin layer a, and the like. On the resin layer 3, the thickness of the second layer: 阙3 is preferably - m, and a resin layer 形成 ς is formed on the enamel layer a. The thickness of the resin layer a is 5 to 50 // m, In particular, π π (4) is 10 to 4 〇 (4), and particularly <resin layer b> Mm is preferred. 3, the upper layer forming resin is the resin layer a as the intermediate layer and in the case of the resin layer 099123431 201127618 layer b (the resin layer 1B-b in FIG. 1b), the resin layer b may be made of a polycarbonate resin and a polyester system. A resin composition of a resin is formed as a resin component as a main component. In the case of a polycarbonate resin monomer, there is a problem in press workability, and cracks or the like are formed after the processing. However, the pressurization processability can be improved by using a mixed resin of a polycarbonate resin and a polyester resin. (Polycarbonate Resin) The polycarbonate resin is composed of carbonic acid and a diol or a divalent phenol, and is represented by the general formula: -(0-R-0-C0-)n- (R is two Valuable fatty acid or aromatic group). For example, an interfacial polymerization method using bisphenol A synthesized from phenol and acetone, a transesterification method, a pyridine method, or the like; a bisphenol A and a dicarboxylic acid derivative, for example, a p-isobenzophenone; A product obtained by copolymerization of acid dichloride or the like; a derivative of bisphenol A, for example, a polymerization product obtained from tetradecyl bisphenol A or the like. It is also possible to use a constructer that replaces some or all of bisphenol A with other divalent phenols. In this case, examples of the other divalent phenol include hydroquinone, 4,4-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, and 1-bis(4-hydroxyphenyl)ethane. 4-hydroxyphenyl)alkane; bis(4-hydroxyphenyl)cycloalkane such as 1,1-bis(4-hydroxyphenyl)cyclohexane; bis(4-hydroxyphenyl) a compound such as sulfur, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ether; 2,2-bis(3-indolyl-4-hydroxyl) Alkylation of bisphenols such as phenyl)propane; halogens of 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, etc. 099123431 19 201127618 Bisphenols. The viscosity average molecular weight of the polycarbonate resin is not particularly limited, and is preferably 10,000 to 100,000, particularly 20,000 to 30,000, and particularly preferably 23,000 to 28,000. Further, the melt flow rate of the polycarbonate resin is not particularly limited, and it is preferably from 5 to 20 in terms of a melt flow rate measured at 300 ° C and a load of 1.2 kg in accordance with JIS K7210. Examples of the polycarbonate resin include the "Upilon" series manufactured by Mitsubishi Engineering Plastics Co., Ltd. and the "Kaliber" series manufactured by Sumitomo Dow Co., Ltd., and the like. Further, as the polycarbonate resin, one type of polycarbonate resin may be used alone, or two or more types of polycarbonate resins may be used in combination. (Polyester-based resin) The polyester-based resin is a resin obtained by condensation polymerization of a dicarboxylic acid component and a diol component, and in terms of heat resistance, a condensation polymerization of an aromatic dicarboxylic acid component and a diol component An aromatic polyester resin is preferred. Here, as a representative of the above-mentioned "aromatic dicarboxylic acid component", terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc. may be mentioned, but one part of terephthalic acid may be used as the other two. Replaced by a carboxylic acid component. In this case, examples of the "other dicarboxylic acid component" include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, pivalic acid, isophthalic acid, naphthalene dicarboxylic acid, and Phenoxyether dicarboxylic acid, p-hydroxybenzoic acid, and the like. It may be a mixture of one kind or two or more kinds, and a part of the other substituted dicarboxylic acid 099123431 20 201127618 may be appropriately selected. Examples of the "diol component" include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexanediketanol. However, one part of the ethylene glycol may be subjected to "other diol components." Replaced by. In this case, examples of the "other diol component" include propylene glycol, butanediol, tridecyl diol, tetradecylene diol, hexamethylene diol, diethylene glycol, and pentylene. A diol, a polyalkylene glycol, 1,4-cyclohexaneditanol, glycerin, pentaerythritol, a trihydroxyindole group, a decyloxy polyalkylene glycol, and the like. It may be one or a mixture of two or more kinds, and the amount of the other diol to be substituted may be appropriately selected. Further, as the other polyester-based resin, "copolymerization" is also possible, which includes a dicarboxylic acid component other than terephthalic acid and/or a glycol component other than ethylene glycol. The molecular weight of the polyester-based resin such as the aromatic polyester-based resin used in the present invention is not particularly limited, and the intrinsic viscosity at 30 ° C in the phenol/tetrachloroethylene = 50/50 (volume ratio) solution is 0.600 to 1.400. The left and right are better. Specific examples of such an aromatic copolyester include, for example, poly(ethylene terephthalate) modified product: "Novapex" series manufactured by Mitsubishi Chemical Corporation (for example, Novapex PS600), and poly pairs. Modified butyl dibenzoate: "Novadulan" series made by Mitsubishi Engineering Plastics Co., Ltd. (for example, Novadulan 5008). Further, a poly(resin) resin in which about 30 mol% of ethylene glycol in polyethylene terephthalate is substituted with 1,4-cyclohexanol is used: Eastman 099123431 21 201127618

Chemical公司製「Eastai· 6763」、由相同成分所構成之炫融 黏度稍低之「Eastar GN119」為首的「Eastar」系列。 特別作為改善聚碳酸S旨系樹脂之加工性，且可維持财熱性 之聚酯系樹脂，以使用丁二醇作為二醇成分、對苯二酸作為 芳香族二羧酸成分的聚對苯二酸丁二酯(PBT)為最佳。 聚對苯二酸丁二酯為結晶性樹脂，故耐熱性和強度優異， 又，與聚碳酸酯系樹脂完全相溶作成聚合物合金方面等而 言，則作為構成樹脂層b之聚酯系樹脂為特佳。 作為此種聚對苯二酸丁二酯之具體的製品例，可列舉例如 Wintic Polymer公司製「Julanex」系列、三菱工程塑料公司 製之「Novadulan」系列。 另外，亦可使用聚對苯二酸丁二酯與上述之共聚聚酯的混 合物。 (混合比率） 構成樹脂層b之聚酯系樹脂與聚碳酸酯系樹脂的混合比 率，以重量比為20 : 80〜70 : 30、更且以20 : 80〜60 : 40、 特別以30 : 70〜50 : 50、其中特別以35 : 65〜45 : 55之範圍 為佳。若為此混合比率之範圍内，則加壓加工時亦不會發生 裂痕，且於射出成形時亦不會使薄膜表面熔融方面而言為 佳。 (熔點） 構成樹脂層b之樹脂，其熔點比用以經由後述之射出成形 099123431 22 201127618 形成凸部之合成樹脂的溶點更低1Wc、特別以ι〇〜4〇 C、尤其以15〜4Gt者為佳。構成樹脂層b之樹祕點若過 南，則在後述的射出成科，以所射出之㈣樹脂之熱的炼 解性不夠充分，凸部無法以高接黏強度—體絲。但，此炼 點若過低龍摘触差者，成為無法承受射㈣形模具的 溫度，為不佳。 另外，在樹脂層a上形成樹脂層b之情況，關於樹脂層a 的溶點，並非被限定於-定比用以經由後述之射出成形形成 凸部之合成樹脂的炼點更低者，樹脂層a的炫點若過低’則 以射出成形時之成形樹脂及模具的熱，樹脂層a有由金屬板 剝離之虞’為不佳。由此種觀點而言，樹脂層…炼點亦比 用以經由後述之射出成形形成凸部之合成樹脂的料更低 10〜60t、特別以1G〜贼、尤其以15〜贼者為佳。 (厚度） 樹脂層b的厚度為10〜200#m為佳。樹脂層b的厚度若 未滿l〇#m，則施行深拉伸加工、彎曲加工等時，有發2針 孔且無法提高與射出成形部分之接雜之虞。相反，若過厚 至超過2叫m，則加壓加工性降低，於經濟上亦為不利二 在樹脂層a上積層形成此種樹脂層5之本發明的樹脂/金 屬複合積層材’由於具有與表面樹脂層b射出之炫融樹脂的 接黏性尚，且加壓加工性優異，更且可承受模具溫度（8〇〜η。 °C)之耐熱性和不會經由射出壓力引起變形之材料強度等優 09912343] 23 201127618 異之特長，故可適人 樹脂並將射以^作為經由模内成形’在其表面射出溶融 &lt;其他之構成層/㈣—體化的樹脂/金屬複合積層材。 本發明之樹脂/金 陽極氧化 層的加工法 、染色、44 封孔處理等，在鋁表面成形出防蝕鋁 屬板之情合積層材當在使賴合金板作為金 或樹脂層a及^旨板之形成樹脂層面（即，形成樹脂層a 工。經由b的面之反側面）亦可進行防餘紹加 機器框體時所要則可對金屬板表面賦予使用作為電子 防触加1^傷性、防銹性、著色性。 b的樹脂金屬複合早面形成樹脂層a或樹脂層a及樹脂層 工、陽極氧化、仇T層材，經由進行表面修飾加工、脫脂加 作為表面修飾力 砂處理之霧面修飾S可列舉以磨光研磨之鏡面修飾、以噴 化錄水溶液之霧轉^線修飾等之物理加卫，更且，使職 瑣酸水溶液之化學研磨、、使用韻_硫酸水雜、或、碟酸-抱并。 1、使用磷酸水溶液之電解研磨等亦可 作為脫脂加工， 的電解脫脂等。 可列舉以硫酸脫脂、於氫氧化鈉水溶液中 於陽極氧化方面，可採用硫酸法、草酸法、麟酸法等。若 說明關於具體的條件，例如硫酸法中，細旨/金屬複合積 曰材連接電極，並⑦潰於調整至之⑺〜列質量％的 099123431 24 201127618 硫酸水溶液，以電流密度50〜300A/m2通電則可在金屬板表 面形成氧化鋁層。所生成之氧化鋁層厚度並無特別限定，但 若過薄則無法發揮充分的性能，反之若過厚則處理時間變 長，較不經濟。較佳之氧化鋁層的厚度為丨〜⑼以爪之範圍。 視需要，在進行封孔處理前，可進行防蝕鋁層的染色。作 為染色法，可列舉使用有機染料予以染色之方法、浸潰於含 有金屬鹽之染色液中予以染色的方法等。 作為封孔處理，可列舉曝露於水蒸氣的方法和浸潰於沸水 的方法’藉此’防姓紹層變成水合物’可大幅提高耐腐蝕性。 防#铭加工可在進行射出成形前或後之任一階段進行，於 射出成形時’為了避免金屬面接觸模具發生外觀不良，在射 出成形後進行防钕铭加工為佳。 本發明之樹脂/金屬複合積層材當在金屬板之形成樹脂層 之面（即，形成樹脂層a或樹脂層a及樹脂層b的面之反側 面）以塗佈進行加飾之情況，在其面上依序具有塗佈用薄膜 層和樹脂塗佈層。經由作成此種構成，對形成樹脂層a或樹 脂層a及樹脂層b面進行射出成形後，對塗佈用薄膜層面進 行塗佈，可形成樹脂塗佈層。 未積層塗佈用薄膜層而對金屬板直接進行塗佈之情況，必 須使焊接溫度為120〜130°C ’若於射出成形後進行塗佈，則 成形樹脂軟化、變形。又，金屬與塗佈之接黏力—般多為不 充分，且若使用則有易剝離之問題。 099123431 25 201127618 相對地，若在金屬板上積層塗佈用薄膜層，則可使用 聚碳酸醋或誦6尼龍等所使用的塗料。經由積層此= 佈用薄膜層，則可將乾燥溫度抑制於6Q〜贼左右，乾_ 不會發生成形樹脂之軟化、變形，更且，可大幅提 接黏力。 的 作為塗佈用薄膜層可使用的樹脂，可列舉聚碳酸醋系樹 脂、聚酿胺系樹脂、聚醋系樹脂、胺基？酸醋樹脂、細 系樹脂、㈣酸系樹脂。塗佈用薄膜層的厚度為5〜50_ 左右為佳。塗佈用薄膜層的厚度若為5〜5仏㈣上之範圍， 則可表現與塗料的接黏力，且經濟上亦為有利的。 作為塗佈用薄膜層對於金屬板之形成積層方法，可列舉將 形成塗佈用薄膜用樹脂之熔融樹脂在金屬板表面以薄膜狀 押出並予以積層形成的方法、將預先形成之㈣用薄膜積層 至金屬板的方法等。 匕作為樹脂塗佈層可使用的塗料，可列舉胺基甲酸醋系樹 脂、丙烯酸系樹脂、聚醯胺系樹脂，且可以喷霧等任意方法 予以塗佈。在樹脂塗佈層的最表層亦可設置硬塗層。樹脂塗 佈層的厚度並無特別限制，可減其目的適當選擇厚度。 特別’使構成塗佈用薄膜層之樹脂與形成凸部之樹脂一致 之It况例如，將構成塗佈用薄膜層之樹脂與形成凸部之樹 脂選擇相同物質’在樹脂層a上，將MXD 6尼龍所構成之 凸部予以射出成形之情況，選擇MXD6尼龍用之等級作為 099123431 26 201127618 樹脂塗佈層所使用的塗料，藉此可將進行射出成形之凸部與 塗佈用薄膜層-併予以塗佈，故可使步驟簡單化。同樣地: 將構成塗佈用薄膜層之樹脂與構成樹脂層b之樹脂選擇相 同物質之情況中，在樹脂層b上將聚碳酸酉旨所構成二部= •以射出成形’並且選擇聚碳酸㈣之等級料樹脂塗佈層所 使用的塗料，可將進行射出成形之凸部與塗佈用薄膜層一併 予以塗佈，故可將步驟簡單化。 又，將樹脂層a與樹脂層匕予以積層形成而作為樹脂層之 情況，在樹脂層a與樹脂層b之間，亦可形成對於兩樹脂層 接黏性高之樹脂層’作為接黏層。作為此種接黏層，可列舉 聚I系樹脂、環氧系樹脂、胺基甲酸酷系樹脂等所構成的接 黏層，且以聚酯系樹脂所構成的接黏層為佳。 &lt;樹脂/金屬複合積層材之厚度&gt; 構成本發明之樹脂/金屬複合積層材之金屬板及樹脂層 (即’樹脂層a、或樹脂層a與樹脂層b)、與視需要設置之 底漆層或麵層、其他構之適#厚度係如上述，本發明 之樹脂/金屬複合積層材之總厚度亦根據其用途而異，通常 為（U〜3.0麵、特別為om，且如行動電話之框體般 要求薄型化之用途令，以0.1〜1.0mm左右為佳。 &lt;树爿曰/金屬複合積層材之製造方法&gt; 本發明之樹脂/金屬複合積層材係在金屬板的至少一面， 形成以滿足上述結晶化指數之聚酿胺系樹脂作為主成分的 099123431 27 201127618 樹脂層a、或此樹脂層a與上述之樹脂層b而製造。 作為對於金屬板形成樹脂層a的方法，可列舉將形成樹脂 層a用樹脂之熔融樹脂，在金屬板表面以薄膜狀押出予以積 層形成的方法；將預先成形之形成樹脂層a用樹脂的薄膜積 層成形至金屬板的方法等。 又，作為將樹脂層a與樹脂層b對於金屬板積層形成之方 法，可列舉將形成樹脂層a用樹脂之熔融樹脂與形成樹脂層 b用樹脂之熔融樹脂，在金屬板表面與薄膜同時共同押出予 以積層形成的方法；在根據上述方法預先形成樹脂層a之金 屬板的樹脂層a上，將形成樹脂層b用樹脂之炫融樹脂以薄 膜狀押出並且積層形成樹脂層b的方法，將預先成形之形成 樹脂層a用樹脂與形成樹脂層b用樹脂之積層薄膜對金屬板 積層成形的方法等。 圖3示出樹脂薄膜積層成形至金屬板，製造本發明之樹脂 /金屬複合積層材之步驟的示意圖，由金屬板的回捲體21將 金屬板22夾於1對輥23、23間以箭頭方向送出，通過加熱 爐24加熱後，由樹脂薄膜的回捲體25送出的樹脂薄膜(形 成樹脂層a用樹脂之薄膜、或形成樹脂層a用樹脂與形成樹 脂層b用樹脂的積層薄膜)26予以積層並夾於一對輥27、27 間按壓，再以再加熱爐28予以再加熱使樹脂薄膜26溶黏一 體化至金屬板22，作成樹脂/金屬複合積層材29，並將其捲 取至回捲體30。 099123431 28 201127618 金屬板亦可預先形成底漆層，又，亦可對此樹脂薄膜之積 層步驟所送出之金屬板形成底漆層。 又’树月曰薄膜在提高與金屬板之接黏性的目的下，亦可施 行電暈放電處理等之表面處理。 於此種樹脂薄膜之積層步驟中，經由控制樹脂薄膜炫黏後 的再加熱條件（再加熱爐28的加熱溫度與加熱時間（線速 度)），則可调整所形成樹脂層a的結晶化指數。#，若提高 再加熱溫度且縮短再加熱時間，則形成結晶化指數小的樹脂 層a’相反地經由減低再加熱溫度及/或延長再加熱時間，則 形成結晶化指數大的樹脂層a，故經由控制此再加熱條件， 則可形成結晶化指數為0.40〜〇.80之樹脂層a並取得本發明 之樹脂/金屬複合積層材。 於本發明中，樹脂薄膜對於金屬板積層時的加熱條件，亦 根據構成樹脂層（樹脂層a、或樹脂層&amp;和樹脂層b)的樹脂 種類而異’通常金屬板的加熱溫度(加熱爐24的加熱溫度） 為300〜500 C、樹脂薄膜熔黏後之再加熱溫度（再加熱爐28 的溫度）為250〜450°C，且再加熱時間（積層材通過再加熱爐 28内的時間）為3〜10秒左右為佳。 [樹脂/金屬複合射出成形體] 本發明之樹脂/金屬複合射出成形體，係在如上述之本發 明之樹脂/金屬複合積層材之樹脂層（樹脂層a或樹脂層b) 上’將合成樹脂之溶融樹脂射出成形，使該合成樹脂所形成 099123431 29 201127618 之凸部一體形成而成者。 圖2示出本發明之樹脂/金屬複合射出成形體之一例的剖 面圖，此樹脂/金屬複合射出成形體2，係在金屬板1A之一 面形成樹脂層（樹脂層a、或樹脂層a及樹脂層b)lB而成之 本發明的樹脂/金屬複合積層材予以彎曲加工後，經由射出 成形將合成樹脂所形成的凸部3予以一體成形者。 &lt;凸部形成用合成樹脂&gt; 作為用以經由射出成形形成凸部的合成樹脂，並無特別限 制，可列舉聚苯乙烯、ABS樹脂、MBS樹脂等之苯乙烯系 樹脂、聚甲基丙烯酸甲酯等之丙烯酸系樹脂、聚酯系樹脂、 聚烯烴系樹脂、聚醯胺系樹脂、聚碳酸酯、聚苯氧、及該等 樹脂之混合物。特別，金屬板上的樹脂層僅由上述樹脂層a 構成之情況，由高強度且機械特性優異方面而言，以使用 MXD 6尼龍(偏二曱苯二胺(MXDA)與己二酸所得之結晶性 熱可塑性樹脂）為佳。又，金屬板上之樹脂層由樹脂層a與 樹脂層b所構成，且表面層為樹脂層b之情況，由與樹脂層 b之相溶性優異方面而言，以聚碳酸酯系樹脂、ABS樹脂、 或、聚碳酸酯系樹脂與上述樹脂中之1種或2種以上之混合 物為適當，尤其以聚碳酸酯系樹脂為佳。 另外，此凸部形成用合成樹脂，通常與樹脂/金屬複合積 層材之樹脂層的樹脂不同。 經由射出成形所形成之凸部形狀和大小並無特別限制，可 099123431 30 201127618 根據其目的適當決定。 鎖住螺絲用 、樞體内之 另外’此凸部並非限定於上述之補強用肋材、 凸座’可形成作為框體内之分隔板、絕緣板、或 構件的保護壁、包圍構件等。 &lt;樹脂/金屬複合射出成形體之製造方法&gt; 以下，參照圖4a至4e說明使用本發明之樹月旨/金屬1"Eastai·6763" manufactured by Chemical Co., Ltd., the "Eastar" series headed by "Eastar GN119" which is composed of the same components and has a slightly lower viscous viscosity. In particular, as a polyester resin which improves the processability of a polycarbonate S-based resin and maintains heat, a butylene glycol is used as a diol component, and terephthalic acid is used as an aromatic dicarboxylic acid component. Butylene diester (PBT) is the best. Polybutylene terephthalate is a crystalline resin, and is excellent in heat resistance and strength, and is completely compatible with a polycarbonate resin to form a polymer alloy. Resin is especially good. Specific examples of such a polybutylene terephthalate product include the "Julanex" series manufactured by Wintic Polymer Co., Ltd. and the "Novadulan" series manufactured by Mitsubishi Engineering Plastics Co., Ltd. Further, a mixture of polybutylene terephthalate and the above-mentioned copolymerized polyester can also be used. (mixing ratio) The mixing ratio of the polyester resin constituting the resin layer b to the polycarbonate resin is 20:80 to 70:30, more preferably 20:80 to 60:40, and particularly 30: 70~50: 50, especially in the range of 35: 65~45: 55 is preferred. If it is within the range of the mixing ratio, cracking does not occur during press working, and it is preferable not to melt the surface of the film during injection molding. (melting point) The resin constituting the resin layer b has a melting point lower than a melting point of a synthetic resin for forming a convex portion by injection molding 099123431 22 201127618, which will be described later, particularly 1⁄4 〇C, especially 15 to 4 Gt. It is better. If the secret point of the resin layer b is too large, the heat-removing property of the (4) resin which is emitted will be insufficient, and the convex portion cannot be made to have a high adhesion strength-body filament. However, if the refining point is too low, it will not be able to withstand the temperature of the (four)-shaped mold, which is not good. In addition, in the case where the resin layer b is formed on the resin layer a, the melting point of the resin layer a is not limited to the lower than the refining point of the synthetic resin for forming the convex portion by injection molding described later, and the resin. If the dazzling point of the layer a is too low, the heat of the molding resin and the mold at the time of molding is formed, and the resin layer a is peeled off from the metal sheet, which is not preferable. From such a viewpoint, the refining point of the resin layer is preferably 10 to 60 t lower than that of the synthetic resin forming the convex portion by the injection molding described later, and particularly preferably 1 G to thief, especially 15 to thief. (Thickness) The thickness of the resin layer b is preferably 10 to 200 #m. When the thickness of the resin layer b is less than 〇#m, when deep drawing processing, bending processing, etc. are performed, there are two needle holes, and it is not possible to improve the connection with the injection molding portion. On the other hand, if it is too thick to exceed 2, m, the press workability is lowered, and it is economically disadvantageous. The resin/metal composite laminate of the present invention in which the resin layer 5 is laminated on the resin layer a has It has excellent adhesion to the molten resin which is emitted from the surface resin layer b, and is excellent in press workability, and can withstand heat resistance of the mold temperature (8 〇 to η ° ° C) and deformation without causing deformation by the injection pressure. The strength of the material is excellent, 09912343] 23 201127618 The special resin is suitable for the resin, and it can be used as a resin/metal composite layer which is formed by in-mold forming 'molding on its surface> other constituent layers/(iv)-formation material. The method for processing the resin/gold anodized layer of the present invention, dyeing, 44-sealing treatment, etc., forming an alumite sheet on the surface of the aluminum, and using the Lai alloy sheet as a gold or resin layer a and The formation of the resin layer (ie, the formation of the resin layer a. The opposite side of the surface via b) can also be used to prevent the use of the machine frame when the machine frame can be used as an electronic anti-touch 1 ^ injury Sex, rust resistance, coloring. The resin metal layer of b is formed on the early surface of the resin layer a or the resin layer a, and the resin layer, the anodized layer, and the surface layer of the resin are subjected to surface modification processing, degreasing, and surface modification sand as a surface modification sand. The mirror finish of the buffing and polishing, the physical modification of the spray-changing aqueous solution, and the chemical polishing of the aqueous solution of the acid solution, and the rhyme-sulfuric acid, or the acid-holding and. 1. Electrolytic polishing using an aqueous phosphoric acid solution or the like can also be used for degreasing, electrolytic degreasing, and the like. For example, a sulfuric acid method, an oxalic acid method, a linonic acid method, or the like can be used for degreasing with sulfuric acid and anodizing in an aqueous sodium hydroxide solution. If the specific conditions are specified, for example, in the sulfuric acid method, the fine/metal composite coffin is connected to the electrode, and 7 is crushed to the 099123431 24 201127618 aqueous sulfuric acid solution adjusted to (7) to column mass %, with a current density of 50 to 300 A/m 2 . When energized, an aluminum oxide layer can be formed on the surface of the metal plate. The thickness of the alumina layer to be formed is not particularly limited, but if it is too thin, sufficient performance cannot be exhibited. On the other hand, if it is too thick, the treatment time becomes long and it is uneconomical. Preferably, the thickness of the aluminum oxide layer is 丨~(9) in the range of the claws. If necessary, the alumite layer may be dyed before the sealing treatment. Examples of the dyeing method include a method of dyeing with an organic dye, a method of dyeing with a dyeing liquid containing a metal salt, and the like. As the sealing treatment, a method of exposing to water vapor and a method of impregnating with boiling water can be used, whereby the anti-small layer becomes a hydrate, and the corrosion resistance can be greatly improved. The anti-Ming processing can be carried out at any stage before or after the injection molding. In the case of injection molding, it is preferable to perform the anti-mite processing after the injection molding in order to avoid the appearance failure of the metal surface contact mold. The resin/metal composite laminate of the present invention is coated and decorated on the surface of the metal sheet on which the resin layer is formed (that is, the opposite side of the surface on which the resin layer a or the resin layer a and the resin layer b are formed). The surface of the film has a coating film layer and a resin coating layer in this order. By forming such a structure, the resin layer a, the resin layer a, and the resin layer b are formed by injection molding, and then the coating film layer is applied to form a resin coating layer. When the coating film layer is not laminated and the metal plate is directly applied, the soldering temperature must be 120 to 130 ° C. If the coating is applied after injection molding, the molding resin is softened and deformed. Moreover, the adhesion between the metal and the coating is generally insufficient, and if used, there is a problem of easy peeling. 099123431 25 201127618 In contrast, when a coating film layer is laminated on a metal plate, a coating material such as polycarbonate or ruthenium nylon can be used. By laminating the film layer for the cloth, the drying temperature can be suppressed to about 6Q to the thief, and the drying _ does not cause softening or deformation of the molding resin, and the adhesion can be greatly improved. Examples of the resin which can be used for the coating film layer include a polycarbonate resin, a polyamine resin, a polyester resin, and an amine group. Sour vinegar resin, fine resin, and (iv) acid resin. The thickness of the coating film layer is preferably about 5 to 50 Å. When the thickness of the coating film layer is in the range of 5 to 5 Å (4), the adhesion to the coating material can be exhibited, and it is economically advantageous. In the method of forming a metal sheet for coating, a method of laminating a molten resin for forming a film for coating film on a surface of a metal sheet and laminating it, and laminating a film formed in advance (4) is used. The method to the metal plate, etc. The coating material which can be used as the resin coating layer may, for example, be an amino carboxylic acid-based resin, an acrylic resin or a polyamine-based resin, and may be applied by any method such as spraying. A hard coat layer may also be provided on the outermost layer of the resin coating layer. The thickness of the resin coating layer is not particularly limited, and the thickness can be appropriately selected in accordance with the purpose. In particular, in the case of the resin constituting the coating film layer, the resin constituting the coating film layer is selected from the resin constituting the film layer for coating and the resin forming the convex portion as the same material 'on the resin layer a, MXD 6 When the convex portion made of nylon is injection-molded, the coating for the resin coating layer of 099123431 26 201127618 is selected as the grade for MXD6 nylon, whereby the convex portion for injection molding and the coating film layer can be formed. The coating is applied, so that the steps can be simplified. Similarly, in the case where the resin constituting the film layer for coating is selected from the same material as the resin constituting the resin layer b, the polycarbonate layer b is formed of two parts of the resin layer b to be formed by injection and the polycarbonate is selected. (4) The coating material used for the resin coating layer of the grade material can be applied together with the convex portion for injection molding and the coating thin film layer, so that the step can be simplified. Further, when the resin layer a and the resin layer are laminated to form a resin layer, a resin layer having high adhesion to both resin layers can be formed as an adhesive layer between the resin layer a and the resin layer b. . As such an adhesive layer, an adhesive layer composed of a poly-based resin, an epoxy resin, an amino acid curable resin, or the like, and an adhesive layer composed of a polyester resin is preferable. &lt;Thickness of Resin/Metal Composite Laminate&gt; Metal plate and resin layer constituting the resin/metal composite laminate of the present invention (i.e., 'resin layer a, resin layer a and resin layer b), and if necessary The primer layer or the top layer, the other layer is as described above, and the total thickness of the resin/metal composite laminate of the present invention varies depending on the use thereof, and is usually (U to 3.0 faces, particularly om, and as The use of the mobile phone as a frame is required to be thinner, preferably about 0.1 to 1.0 mm. &lt;Manufacturing method of tree shrew/metal composite laminate&gt; The resin/metal composite laminate of the present invention is on a metal plate. At least one side is formed by forming a resin layer a of 099123431 27 201127618 as a main component, or a resin layer a and the above-mentioned resin layer b as a main component of the above-mentioned crystallization index. The resin layer a is formed as a metal plate. In the method of forming a molten resin of a resin for forming a resin layer a, a film is formed by laminating a film on the surface of a metal plate, and a film formed by forming a resin layer a in advance with a resin is laminated to a metal plate. In addition, as a method of forming the resin layer a and the resin layer b on the metal plate, a molten resin which forms a resin for the resin layer a and a resin which forms a resin for the resin layer b are used on the surface of the metal plate. a method of simultaneously forming a film by laminating together; forming a resin layer b by laminating a film of a resin layer b for forming a resin layer b in a film form on a resin layer a of a metal plate on which a resin layer a is formed in advance according to the above method. In the method, a method of forming a resin layer a resin layer a and a resin film forming resin layer b by laminating a metal sheet into a metal sheet is formed. Fig. 3 shows a resin film laminated to a metal sheet to produce the resin/metal of the present invention. A schematic view of the step of laminating the composite material, the metal plate 22 is sandwiched between the pair of rolls 23 and 23 by the rewinding body 21 of the metal sheet, and is sent out in the direction of the arrow, heated by the heating furnace 24, and then sent out from the rewinding body 25 of the resin film. a resin film (a film for forming a resin layer a resin or a resin film for forming a resin layer a and a resin film for forming a resin layer b) 26 is laminated and sandwiched The rollers 27 and 27 are pressed between each other, and then reheated by the reheating furnace 28 to melt-bond the resin film 26 to the metal plate 22 to form a resin/metal composite laminate 29, which is wound up to the rewinding body 30. 099123431 28 201127618 The metal plate may also be pre-formed with a primer layer, or a metal layer formed by the lamination step of the resin film may be used to form a primer layer. The 'Tree Moon's film is used for improving the adhesion to the metal plate. Further, a surface treatment such as a corona discharge treatment may be performed. In the lamination step of the resin film, the reheating condition after the control of the resin film is viscous (the heating temperature and the heating time (linear velocity) of the reheating furnace 28) Then, the crystallization index of the formed resin layer a can be adjusted. #,If the reheating temperature is increased and the reheating time is shortened, the resin layer a' having a small crystallization index is formed by reversely reducing the reheating temperature and/or prolonging the reheating time to form the resin layer a having a large crystallization index. Therefore, by controlling this reheating condition, the resin layer a having a crystallization index of 0.40 to 〇.80 can be formed and the resin/metal composite laminate of the present invention can be obtained. In the present invention, the heating conditions of the resin film for laminating the metal sheet are also different depending on the kind of the resin constituting the resin layer (the resin layer a, or the resin layer &amp; and the resin layer b). The heating temperature of the furnace 24 is 300 to 500 C, and the reheating temperature (temperature of the reheating furnace 28) after the resin film is melted is 250 to 450 ° C, and the reheating time (the laminated material passes through the reheating furnace 28) Time) is preferably about 3 to 10 seconds. [Resin/Metal Composite Injection Molded Body] The resin/metal composite injection molded body of the present invention is synthesized on the resin layer (resin layer a or resin layer b) of the resin/metal composite laminate of the present invention described above. The molten resin of the resin is injection-molded, and the convex portion of 099123431 29 201127618 formed by the synthetic resin is integrally formed. Fig. 2 is a cross-sectional view showing an example of a resin/metal composite injection molded body of the present invention. The resin/metal composite injection molded body 2 is formed by forming a resin layer (resin layer a or resin layer a) on one surface of the metal plate 1A. After the resin/metal composite laminate of the present invention in which the resin layer b) 1B is bent, the convex portion 3 formed of the synthetic resin is integrally molded by injection molding. &lt;Synthetic resin for forming a convex portion&gt; The synthetic resin for forming the convex portion by injection molding is not particularly limited, and examples thereof include a styrene resin such as polystyrene, ABS resin, and MBS resin, and polymethacrylic acid. An acrylic resin such as a methyl ester, a polyester resin, a polyolefin resin, a polyamide resin, a polycarbonate, a polyphenylene oxide, and a mixture of the resins. In particular, in the case where the resin layer on the metal plate is composed only of the above-mentioned resin layer a, it is obtained by using MXD 6 nylon (MXDA) and adipic acid in terms of high strength and excellent mechanical properties. A crystalline thermoplastic resin is preferred. Further, the resin layer on the metal plate is composed of the resin layer a and the resin layer b, and the surface layer is the resin layer b, and the polycarbonate resin or ABS is excellent in compatibility with the resin layer b. A mixture of one or a combination of a resin or a polycarbonate resin and the above resin is suitable, and a polycarbonate resin is particularly preferable. Further, the synthetic resin for forming the convex portion is usually different from the resin of the resin layer of the resin/metal composite laminate. The shape and size of the convex portion formed by injection molding are not particularly limited, and may be appropriately determined according to the purpose thereof. In addition, the reinforcing rib and the boss can be formed as a partition plate, an insulating plate, or a protective wall or a surrounding member of the member. . &lt;Method for Producing Resin/Metal Composite Injection Molding Body&gt; Hereinafter, the use of the tree of the present invention/metal 1 will be described with reference to Figs. 4a to 4e.

積層材之本發明之樹脂/金屬複合射出成形體之製造方=D 一例，但本發明之樹脂/金屬複合射出成形體之製造方去= 非限定於圖4a至4e所示之方法。 首先，將金屬板！八與樹脂層（樹脂層a、或樹脂層 脂層b)lB積層之本發明的樹脂/金屬複合積層材）（亦可具有 底漆層ic)切斷成適當大小（圖4a)，錄，視需要進行伸拉 深=工、彎曲加工、以及打穿加卫等，賦型成平板狀、剖面 L字型、剖面17字型等所欲之形狀（圖4b、4c)。 +其次’將賦型的樹脂/金屬複合積層材卜配置於射出成形 权具4的腔體内’由射出成形機5，將凸部形成用合成樹脂 之熔嘁祕月曰6朝向樹脂層1B流入並射出成形（圖4d)。其後， 由模具中取出成形體’取得在樹脂/金屬複合積層材i之樹 月曰層1B面形成合成樹脂之凸部3之本發明的樹脂/金屬複合 射出成形體2(圖4e)。 於此射出成形步驟中’本發明之樹脂/金屬複合積層材的 樹脂層a，經由將其結晶化指數作成適當範圍，則可以射出 099123431 31 201127618 之熔融樹脂之熱予以迅速炼融並與射出樹脂相溶化且炫 黏，故經由射出成形所形成的凸部，對於樹脂層a可成為強 固接黏一體化者。 又，樹脂層a上具有樹脂層b之情況，樹脂層b與聚碳酸 酯系樹脂、ABS樹脂、或聚碳酸酯系樹脂與上述樹脂中之1 種或2種以上之混合物的相溶性優異，故經由射出成形所形 成的凸部，對於樹脂層b可強固接黏一體化。更且，經由在 金屬板之間設置加工性佳的樹脂層a，則可提高金屬的加壓 適性。 關於此射出成形條件，亦根據凸部形成用合成樹脂之種類 而異，使用MXD6尼龍（熔點：240〜245°C左右）作為凸部形 成用合成樹脂之情況，以 熔融樹脂溫度：270〜300°C 射出成形模具溫度：100〜160°C 進行射出成形為佳。 又，使用聚碳酸酯（熔點：230〜260°C左右）作為凸部形成 用合成樹脂之情況，以 熔融樹脂溫度：270〜300°C 射出成形模具溫度：60〜120°C 進行射出成形為佳。 如此處理所得之本發明之樹脂/金屬複合射出成形體，視 需要，亦可再於金屬板之形成樹脂層面反側面施行塗佈、鍵 099123431 32 201127618 敷等表面處理。 &lt;用途&gt; 本發明之樹脂/金屬複合積層材可用於作為個人電腦、桌 上型電腦、各種印刷機、各種影印機等〇A機器、電話機^ 電子辭典•字典、音響機n'電視、收音機等電子機器等之 ‘框體（外殼）用、零件用，特別可活用薄型之同時，具有肋材、 鎖住螺絲用凸座等凸部之特徵’適合使用作為行動電話的框 體。 [實施例] 以下列舉實施例、比較例及參考例更加具體說明本發明， 但本發明只要不超出此要旨’不被下列實施例所限定。 [實施例1〜4、比較例1〜3] 在不銹鋼板(SUS 304 1/2H 0.3mm厚）之一面，塗佈雙盼a 型環氧樹脂後，形成厚度1 /zm的底漆層。 其次，以圖3所示之方法，在此不鎸鋼板的形成底漆層面 積層6尼龍薄膜(三菱樹脂(股)製、熔點：22(rc)，取得樹脂 /金屬複合積層材。 積層時於加熱爐24中的加熱溫度為35(TC，於再加熱燐 • 28中的再加熱溫度、冷卻方法、及再加熱時間如表1所示， 使各例所形成之樹脂層的結晶化度變化。另外，所形成之樹 脂層（樹脂層a)的厚度均為25# m。 另外，實施例3及4以實施例1相同條件作成樣品，僅將 099123431 33 201127618 使用之金屬於實施例3變更成鍍鎳不銹鋼（SUS 3〇4 1/2H 0.3mm厚），實施例4變更成鋁合金(A5182 〇.3mm厚）。 [表1] 實施例1 實施例2 _實施例 實施例4 比較例1 比較例2 比較例3 再加熱溫度 CC) 300 300 300 300 300 100 100 冷卻方法 冷卻爐 水冷 冷卻爐 冷卻爐 冷卻盧 冷卻爐 冷卻爐 再加熱時間 (秒） 6 6 6 6 12 6 12 對於所得之樹脂/金屬複合積層材’分別以下列方法調查 樹脂層的結晶化指數，結果示於表2 ° [結晶化指數] 將樹脂/金屬複合積層材’使用Perkin Elmer公司製之示 差掃描型熱量計（DSC)於30〜300°C之溫度範圍中以升溫速 度10°C/分鐘升溫，測定此時之結晶熔解熱量（第1次結晶熔 解熱量Hml)和結晶化發熱量（第1次結晶化發熱量Hcl)，其 後放冷至30°C後’再測定於30〜300°C之溫度範圍中以升溫 速度10°C/分鐘升溫時之結晶熔解熱量（第2次結晶熔解熱量 Ημ)和結晶化發熱量（第2次結晶化發熱量札2)(此值示於表 2) ^由該等值，以下述(I)式算出結晶化指數。 [數3] •(I) 結晶化指數_ lHmil ~ lHcilThe production of the resin/metal composite injection molded body of the present invention of the laminated material is an example of D, but the production of the resin/metal composite injection molded body of the present invention is not limited to the method shown in Figs. 4a to 4e. First, put the metal plate! 8. The resin/metal composite laminate of the present invention (which may also have a primer layer ic) laminated with a resin layer (resin layer a or resin layer lipid layer b) 1B is cut into an appropriate size (Fig. 4a), recorded, If necessary, stretch and draw = work, bending, and punching, etc., and shape it into a flat shape, a cross-section L-shape, a cross-section 17-shape, etc. (Fig. 4b, 4c). + Next, 'the shaped resin/metal composite laminate is placed in the cavity of the injection molding tool 4'. From the injection molding machine 5, the molten resin of the synthetic resin for forming the convex portion 6 is directed toward the resin layer 1B. Inflow and injection molding (Fig. 4d). Then, the resin/metal composite injection molded body 2 of the present invention in which the convex portion 3 of the synthetic resin is formed on the surface of the resin layer of the resin/metal composite laminate i is obtained by taking out the molded body from the mold (Fig. 4e). In the injection molding step, the resin layer a of the resin/metal composite laminate of the present invention can be rapidly smelted and injected with the heat of the molten resin of 099123431 31 201127618 by setting the crystallization index to an appropriate range. Since it is melted and viscous, the convex portion formed by injection molding can be strongly bonded to the resin layer a. Further, when the resin layer b has the resin layer b, the resin layer b is excellent in compatibility with a polycarbonate resin, an ABS resin, or a polycarbonate resin, and one or a mixture of two or more of the above resins. Therefore, the convex portion formed by injection molding can be strongly bonded to the resin layer b. Further, by providing the resin layer a having good workability between the metal plates, the pressurization property of the metal can be improved. The injection molding conditions are also different depending on the type of the synthetic resin for forming the convex portion, and MXD6 nylon (melting point: about 240 to 245 ° C) is used as the synthetic resin for forming the convex portion, and the molten resin temperature is 270 to 300. °C Injection molding temperature: 100 to 160 ° C. Injection molding is preferred. In addition, when polycarbonate (melting point: 230 to 260 ° C) is used as the synthetic resin for forming a convex portion, the temperature of the molten resin is 270 to 300 ° C, and the temperature of the molding die is 60 to 120 ° C. good. The resin/metal composite injection molded body of the present invention thus obtained may be subjected to surface treatment such as coating or keying of a resin layer on the opposite side of the formation of a resin sheet, if necessary, by a coating such as 099123431 32 201127618. &lt;Application&gt; The resin/metal composite laminate of the present invention can be used as a personal computer, a desktop computer, various printing machines, various photocopiers, etc., a machine, a telephone, an electronic dictionary, a dictionary, a sound machine, a television, In the case of an electronic device such as a radio, it is used for a frame or a housing. In particular, it can be used in a thin shape, and has the characteristics of a rib, a projection such as a boss for locking a screw, and is suitable for use as a casing for a mobile phone. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, Comparative Examples and Reference Examples, but the present invention is not limited by the following examples. [Examples 1 to 4, Comparative Examples 1 to 3] A double-prepared a-type epoxy resin was applied to one surface of a stainless steel plate (SUS 304 1/2H 0.3 mm thick) to form a primer layer having a thickness of 1 /zm. Next, in the method shown in Fig. 3, a primer layer area layer 6 of a nylon film (manufactured by Mitsubishi Resin Co., Ltd., melting point: 22 (rc)) was obtained, and a resin/metal composite laminate was obtained. The heating temperature in the heating furnace 24 was 35 (TC, the reheating temperature in the reheating 燐 28, the cooling method, and the reheating time are as shown in Table 1, and the degree of crystallization of the resin layer formed in each example was changed. Further, the thickness of the formed resin layer (resin layer a) was 25 # m. Further, Examples 3 and 4 were sampled under the same conditions as in Example 1, and only the metal used in 099123431 33 201127618 was changed in Example 3. Nickel-plated stainless steel (SUS 3〇4 1/2H 0.3 mm thick), Example 4 was changed to aluminum alloy (A5182 〇.3 mm thick). [Table 1] Example 1 Example 2 - Example Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reheating temperature CC) 300 300 300 300 300 100 100 Cooling method Cooling furnace Water-cooled cooling furnace Cooling furnace Cooling furnace Cooling furnace Reheating time (seconds) 6 6 6 6 12 6 12 Resin/metal composite laminates are adjusted in the following ways The crystallization index of the resin layer is shown in Table 2 ° [Crystalization Index] The resin/metal composite laminate was subjected to a differential scanning calorimeter (DSC) manufactured by Perkin Elmer Co., Ltd. in a temperature range of 30 to 300 °C. The temperature was raised at a temperature increase rate of 10 ° C /min, and the heat of crystal melting (first crystal heat of fusion Hml) and the heat of crystallization (first crystallization heat generation Hcl) were measured, and then cooled to 30 ° C. After the measurement, the heat of crystal melting (the second crystal melting heat Ημ) and the crystallization heat generation (the second crystallization heat generation) at a temperature increase rate of 10 ° C /min in a temperature range of 30 to 300 ° C are measured. 2) (This value is shown in Table 2) ^ From these values, the crystallization index is calculated by the following formula (I) [3] • (I) Crystallization index _ lHmil ~ lHcil

IhJ~~ 其次，將各樹脂/金屬複合積層材配置於射出成形模具 内，射出MXD6尼龍（三菱工程塑料(股）製「Renny」（註冊 099123431 34 201127618 商標)NXG5050、熔點：243¾」之熔融樹脂（樹脂溫度275 C) ’並以模具溫度160。(：進行射出成形，製造於樹脂/金屬 複合積層材之樹脂層面一體成形半徑3 425mm、高度15mm 之圓柱狀凸部的拉伸試驗用樣品。 對於所得之拉伸試驗用樣品，以下列方法進行拉伸試驗， * 結果不於表2。 [拉伸試驗] 將拉伸試驗用樣品之岐狀凸料拉伸速度在 與樹脂/金屬複合積層材相反方向拉伸，測定凸部由樹脂層 斷裂時的強度，並將其視為接勘強度。 接黏強度為8MPa以上視為合格。 [參考例1] 在2根熱幸比間使66尼龍樹脂(東麗公司製「⑽卜n」、 溶點赋）炫融，取得厚度25&quot;m的66尼龍薄膜。 使用此66尼龍薄臈代替6尼龍薄膜，以實施例丄同樣之 手、'只在不鎮鋼板表面形成樹脂層，取得樹脂/金屬複合積層 材。 ’ 使帛此如9/金屬複合積層材同實闕1製造拉伸試驗用 ‘樣品’並同樣進行拉伸試驗，結果示於表2。 [參考例2] 將實施例1所用之不錄鋼板於⑽中加熱，使市售之猜 稀橡膠衣熱壓勒膠帶(Tesatape公司製、軟化點100。〇 099123431 35 201127618 炫黏形成厚度3 8 // m的樹脂層，取得樹脂/金屬複合積層材。 使用此樹脂/金屬複合積層材同實施例1製造拉伸試驗用 樣品，並同樣進行拉伸試驗，結果示於表2。 另外，於表2中，併記各例中射出成形時樹脂(樹脂/金屬 複合積層材之樹脂層的樹脂）對於射出成形模具有（〇）無(X) 發黏。 [表2] 樹 月1 / 金 屬 複 合 積 層 材 之 樹 月I 層 實施 例 1 實施 例 2 實施 例 3 實施 例 4 比較 例 1 比較 例 2 比較 例 3 參考 例 參考 例 2 Hml(J/g) 62.0 58.8 60.7 60.9 59.9 57.6 60.1 Hc(J/g) -14.2 -25.3 -13.2 -15.5 0 0 0 Hn2(J/g) 70.1 68.3 71.1 72.5 69.5 63.1 64.0 Hc2(J/g) 0 0 0 0 0 0 0 結晶化指 數 0.682 0.490 0.668 0.626 0.862 0.913 0.939 / / 熔點(。〇 220 220 220 220 220 220 220 270 100 (軟化 點） 對於模具 有無發黏 〇 〇 〇 〇 〇 〇 〇 〇 X 接黏強度 (MPa) 9.2 9.5 11.3 9.8 5.0 3.8 3.5 4.0 6.5 由上述之結果，若根據形成結晶化指數0.40〜0.80之聚醯 胺系樹脂層作為樹脂層a之本發明的樹脂/金屬複合積層 材，可知經由射出成形，可將MXD 6尼龍所形成之凸部以 高接黏強度一體成形。 另外，參考例1為樹脂層a之熔點，比射出成形之熔融樹 脂的熔點更高，射出成形時因樹脂層a未充分熔融，因此對 36 099123431 201127618 於模具雖無發黏，但凸部的接黏強度低。 參考例2為樹脂層a之熔點（軟化點）比射出成形之熔融樹 月曰的k點更低’凸部的接黏強度雖較比較例1〜3高但不充 分，又，經由樹脂層a之樹脂於模具内流動，具有樹脂發黏 • 的問題。 ' [實施例5〜7] 將聚碳酸酯系樹脂(PC)(黏度平均分子量25000)與聚對苯 二酸丁二g旨（PBT)(苯盼/四氣乙烯=50/50(體積比）溶液中， 3〇°C之固有黏度1.2448)以表3所示之重量比率混合，並供 給至於280°C中加熱的擠壓機，使用此擠壓機於280°C混 練’並將熔融狀態之樹脂組成物由T字模以片狀擠壓，冷 卻固化製作表3所示之厚度及熔點之形成樹脂層b的薄膜。 在作為樹脂層a之6尼龍薄膜(厚度：20//m、熔點：220 °C、結晶化指數：〇.40〜〇·8〇之範圍、三菱樹脂（股）製 「Diamilon」）上’將聚酯系接黏劑和異氰酸酯交聯劑以1〇〇 重里伤· 12.5重置份之比例配合塗佈接黏劑6g/m2，並於乾 燥爐中以60°C加熱30秒鐘乾燥後，以60°C中加熱的螺紋接 • 官軺* ’將形成上述樹脂層b之薄膜積層，於烤爐内以60°C - A化$日，取得積層薄膜。 將雙齡A型環氧樹脂塗佈不銹鋼板(SUS 304、1/2H、 0.3mm厚）的一面，形成厚度的底漆層。 其—人’將上述積層薄膜，以6尼龍薄膜側為不銹鋼板側， 099123431 37 201127618 與加熱至300°C的不銹鋼板熔黏，取得「樹脂層/接黏劑％ 尼龍/環氧/SUS」構造的樹脂/金屬複合積層材（評估樣品）。 [比較例4] 在不銹鋼板(SUS 304、1/2Η、0.3mm厚）的表面，以棒塗 機塗佈20g/m2矽烷偶合劑1%水溶液，並以u〇t加熱3〇 秒鐘乾燥，其次，於其塗佈面熔黏聚胺基曱酸酯薄膜 (KUrabow公司製商品名「叫25〇」），取得「樹脂層/胺基石夕 烧/SUS」構成的積層材（評估樣品）。 [比較例5] 對預先於170¾加熱的不銹鋼板(sus 3〇4、1/2H、〇 3爪爪 厚）’熔黏厚度50 # m之聚酯系接黏薄膜(Kumb〇w公司製商 口口名「Kuran y3 Gl3」’取得「樹脂層/sus」構成的積層材 (評估樣品;）。 [比較例6] 對預先於not加熱的不錄鋼板(sus 3〇4、丨舰、〇 3議 厚）熔黏厚度30_之聚g旨系接黏薄膜（東亞合成公司製、 商品名「AronmeU PES111EEj再於其上，將厚度13”爪 之聚碳酸醋片材以17(rc積層，取得「職層/接黏薄膜腿」 構成的積層材（評估樣品）。 [評估方法] 況明關於貫施例及比較例4〜6所得樣品之評估方法及評 估結果。 099123431 38 201127618 &lt;與射出成形樹脂的接黏性&gt; 將290 C中加熱溶融的聚碳酸醋樹脂，於評估樣品之樹脂 上射出成$ (射出形狀：半徑3.425mm的圓柱狀）。其次， 於孟直方向進行拉伸試驗(拉伸速度：5mm/min)，測定斷裂 強度。 此時’測定環境試驗後的強度變化。環境試驗係於恆溫槽 中以85 C保持96小時’另一方面於恆溫恆濕槽中以6〇°c 95% RH的環境下保持96小時。 結果示於表3。 [表3] \ 樹脂層之構成 初期值 (MPa) 環境試驗 (95%RHx96h、 單位：MPa) 組成 (重量％) 厚度 (Mm) 熔點 CC) 60 °C 85 °C 實施例5 PC/PBT=60/40 50 200 9.3 8.9 9.6 實施例6 PC/PBT=60/40 30 200 9.1 8.0 8.5 實施例7 PC/PBT=70/30 75 205 10.0 9.5 9.3 比較例4 聚胺基甲酸酯 50 165 8.9 6.6 4.5 比較例5 聚酯 50^ 126 7.4 4.0 3.0 比較例6 PC 130 j 240 5.2 5.0 4.8 實施例5〜7之樣品，於初期接黏及環境試驗後均顯示良好 的接黏性（剝離強度）。相對地，比較例4及5之樣品為初期 接黏良好，但環境試驗後接黏性(剝離強度）大為降低。比較 例6之樣品為初期強度低。 &lt;耐熱性&gt; 將模具溫度設定成80°C、100°c或120°C，並將加熱熔融 099123431 39 201127618 之聚碳酸酯樹脂在評估樣品的樹脂層上射出成形（射出形 狀：半徑3.425mm的圓柱狀）’此時以目視觀察表面及内部 外觀有無變化，並以下列基準評估。 〇：無變化 △:表面有粗糙 X .有剝離 [表4] \ 樹脂層二 t構成 檨品外顧 x\ 組成 (重量％) 厚度 (um) 熔點 CC) 模具溫度 80°C 模具溫度 100°c 模具溫度 120°C 實施例5 PC/PBT=60/40 50 200 ~~δ^ 〇 〇 實施例6 PC/PBT=60/40 30 200 〇 〇 〇 實施例7 PC/PBT=70/30 75 205 〇 〇 〇 比較例4 聚胺基甲酸酯 50 165 --*=«*= --U 〇 Δ X 比較例5 聚酯 50 126 △ △ X 比較例6 PC 130 240 ~~δ^ ------- 〇 〇 實施例5〜7之樣品即使模具溫度為12(rc，於表面及内部 亦未察見外觀變化。相對地，比較例4之樣品於崎雖^ 好’但右於loot：以上，則表面溶解。又，比較例5之樣品 於80 C及1〇〇。(：之兩溫度中表面溶解，發生表面粗輪。又， 比較例6之樣品與實施例5〜7之樣品相同，於薄膜表面及内 部未察見外觀變化。 &lt;埃里克森試驗〉 以圖5a至5c所示之方法進行埃里克森試驗。 首先如圖5a所不般，在樣品31表面加入刻紋32(5mm 門隔）其次，如圖5b所示般，使用JISK6744所規定之埃 099123431 201127618 里克森試驗裝置，並在樣品31的中心部分，將前端為球狀 的衝壓機33押入5mm〜7mm(圖5b中，％為字模，％為壓 料板），如® 5c所錢，觀察樣品31是否發生浮起和些微 裂痕，旅以下列基準評估。結果示於表5。 - 〇：無剝離、及裂痕 * △:稍有裂痕 X :有剝離 [表5]IhJ~~ Next, the resin/metal composite laminate is placed in an injection molding die, and MXD6 nylon (Mitsubishi Engineering Plastics Co., Ltd.) "Renny" (registered 099123431 34 201127618 trademark) NXG5050, melting point: 2433⁄4" molten resin is injected. (Resin temperature: 275 C) 'The mold temperature was 160. (:: Injection molding was carried out, and a sample for tensile test of a cylindrical convex portion having a radius of 3,425 mm and a height of 15 mm was integrally formed on the resin layer of the resin/metal composite laminate. For the obtained tensile test sample, the tensile test was carried out in the following manner, and the results were not shown in Table 2. [Tensile test] The tensile speed of the ridge-like projection of the tensile test sample was laminated with the resin/metal composite layer. The material was stretched in the opposite direction, and the strength at which the convex portion was broken by the resin layer was measured, and this was regarded as the joint strength. The adhesive strength was 8 MPa or more, which was considered to be acceptable. [Reference Example 1] 66 between two heats. Nylon resin ("10"b", "Soluble point" made by Toray Industries Co., Ltd., and made a 66 nylon film with a thickness of 25 &quot; m. Using this 66 nylon thinner instead of 6 nylon film, the same hand, ' only A resin layer is formed on the surface of the steel sheet, and a resin/metal composite laminate is obtained. 'A sample such as a 9/metal composite laminate is produced as a tensile test for a tensile test. The results are shown in the table. 2. [Reference Example 2] The unrecorded steel sheet used in Example 1 was heated in (10) to obtain a commercially available guess rubber garment heat-pressing tape (manufactured by Tesatape Co., Ltd., softening point 100. 〇099123431 35 201127618 A resin/metal composite laminate was obtained from the resin layer of 3: 8 m. The sample for tensile test was produced in the same manner as in Example 1 using this resin/metal composite laminate, and the tensile test was carried out in the same manner. The results are shown in Table 2. In Table 2, the resin (resin of the resin layer of the resin/metal composite laminate) at the time of injection molding in each case was recorded, and there was (〇) no (X) tackiness to the injection molding die. [Table 2] Tree Moon 1 / Metal composite laminate material layer I layer Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reference Example Reference Example 2 Hml (J/g) 62.0 58.8 60.7 60.9 59.9 57.6 60.1 Hc ( J/g) -14.2 -25. 3 -13.2 -15.5 0 0 0 Hn2(J/g) 70.1 68.3 71.1 72.5 69.5 63.1 64.0 Hc2(J/g) 0 0 0 0 0 0 0 Crystallization index 0.682 0.490 0.668 0.626 0.862 0.913 0.939 / / Melting point (. 〇220 220 220 220 220 220 220 270 100 (softening point) For the mold, there is no tackiness. X Adhesive strength (MPa) 9.2 9.5 11.3 9.8 5.0 3.8 3.5 4.0 6.5 From the above results, according to The resin/metal composite laminate of the present invention having a polyamide-based resin layer having a crystallization index of 0.40 to 0.80 as the resin layer a, it is understood that the convex portion formed by the MXD 6 nylon can be integrated with high adhesion strength by injection molding. Forming. Further, Reference Example 1 is a melting point of the resin layer a, which is higher than the melting point of the melt-molded resin, and the resin layer a is not sufficiently melted at the time of injection molding. Therefore, the mold is not sticky to the mold, but the convex portion is not adhered to the 36 099123431 201127618. The bonding strength is low. In Reference Example 2, the melting point (softening point) of the resin layer a was lower than the k-point of the molten tree of the injection molding. The adhesive strength of the convex portion was higher than that of Comparative Examples 1 to 3 but insufficient, and further, via the resin layer. The resin of a flows in the mold and has a problem that the resin is sticky. [Examples 5 to 7] Polycarbonate-based resin (PC) (viscosity average molecular weight: 25,000) and polybutylene terephthalate (PBT) (Benzene/tetraethylene ethylene = 50/50 (volume ratio) The solution has an intrinsic viscosity of 1.2 448 °C at a temperature of 3 °C and is supplied to a presser heated at 280 ° C. The extruder is kneaded at 280 ° C and melted. The resin composition of the state was extruded in a sheet shape by a T-die, and the film of the resin layer b which formed the thickness and the melting point shown in Table 3 was cooled and solidified. On the nylon film (thickness: 20//m, melting point: 220 °C, crystallization index: 〇.40~〇·8〇, and Mitsubishi Resin (Diamilon) made of Mitsubishi Resin) The polyester adhesive and the isocyanate crosslinking agent were mixed with a binder of 6 g/m 2 in a ratio of 1 Torr to 12.5 parts, and dried in a drying oven at 60 ° C for 30 seconds. The film layer of the resin layer b was formed by a threaded connection heated at 60 ° C. The layer of the resin layer b was formed in the oven at 60 ° C - A for a day to obtain a laminated film. A double-aged A-type epoxy resin was coated on one surface of a stainless steel plate (SUS 304, 1/2H, 0.3 mm thick) to form a primer layer having a thickness. The "manufacturer" melts the above-mentioned laminated film on the side of the stainless steel plate of the 6 nylon film side, 099123431 37 201127618 and the stainless steel plate heated to 300 ° C to obtain "resin layer / adhesive % nylon / epoxy / SUS" Constructed resin/metal composite laminate (evaluation sample). [Comparative Example 4] On a surface of a stainless steel plate (SUS 304, 1/2 Η, 0.3 mm thick), a 20 g/m 2 decane coupling agent 1% aqueous solution was applied by a bar coater, and dried by heating at 3 Torr for 3 Torr. Then, a polyacrylic phthalate film (trade name "25 〇" manufactured by KUrabow Co., Ltd.) was obtained on the coated surface of the coated surface, and a laminate (evaluation sample) composed of "resin layer/amine stone kiln/SUS" was obtained. . [Comparative Example 5] A polyester-based adhesive film having a thickness of 50 #m on a stainless steel plate (sus 3〇4, 1/2H, 〇3 claw thickness) heated in advance at 1702⁄4 (Kumb〇w company) The product name "Kuran y3 Gl3" is used to obtain a laminated material (evaluation sample;) of "resin layer/sus". [Comparative example 6] Uncoated steel plate (sus 3〇4, 丨, 〇, which is not heated beforehand) 3 thick) melt-adhesive thickness 30_ polyg is intended to be a sticky film (made by East Asia Synthetic Co., Ltd., trade name "AronmeU PES111EEj and then, thickness 13" clawed polycarbonate sheet with 17 (rc layer, A laminate (evaluation sample) consisting of a "layer/adhesive film leg" was obtained. [Evaluation method] The evaluation methods and evaluation results of the samples obtained in the respective examples and Comparative Examples 4 to 6 are shown. 099123431 38 201127618 &lt; Adhesiveness of Injection Molding Resin&gt; Polycarbonate resin melted and melted in 290 C was injected into the resin of the evaluation sample to form $ (injection shape: a cylindrical shape having a radius of 3.425 mm). Secondly, pulling in the direction of Mengzhi Stretch test (tensile speed: 5mm/min), measure the breaking strength. At this time, 'measurement environment test The change in strength was maintained for 96 hours at 85 C in a constant temperature bath. On the other hand, it was maintained in a constant temperature and humidity chamber at 96 ° C 95% RH for 96 hours. The results are shown in Table 3. [Table 3] \ Initial composition of resin layer (MPa) Environmental test (95% RHx96h, unit: MPa) Composition (% by weight) Thickness (Mm) Melting point CC) 60 °C 85 °C Example 5 PC/PBT=60/ 40 50 200 9.3 8.9 9.6 Example 6 PC/PBT=60/40 30 200 9.1 8.0 8.5 Example 7 PC/PBT=70/30 75 205 10.0 9.5 9.3 Comparative Example 4 Polyurethane 50 165 8.9 6.6 4.5 Comparative Example 5 Polyester 50^ 126 7.4 4.0 3.0 Comparative Example 6 PC 130 j 240 5.2 5.0 4.8 The samples of Examples 5 to 7 showed good adhesion (peel strength) after initial adhesion and environmental tests. The samples of Comparative Examples 4 and 5 were excellent in initial adhesion, but the adhesion (peel strength) was greatly reduced after the environmental test. The sample of Comparative Example 6 had a low initial strength. &lt;Heat resistance&gt; The mold temperature was set. To 80 ° C, 100 ° C or 120 ° C, and heat-melted 099123431 39 201127618 polycarbonate resin in the evaluation of the sample resin The injection molding (injection shape: cylindrical shape of radius 3.425mm) 'at this time was visually observed whether the appearance of the surface and internal changes, and to evaluate the following criteria. 〇: No change △: The surface is rough X. There is peeling [Table 4] \ Resin layer 2 t constitutes product exterior x\ Composition (% by weight) Thickness (um) Melting point CC) Mold temperature 80 °C Mold temperature 100 ° c Mold temperature 120 ° C Example 5 PC / PBT = 60 / 40 50 200 ~ ~ δ ^ 〇〇 Example 6 PC / PBT = 60 / 40 30 200 〇〇〇 Example 7 PC / PBT = 70 / 30 75 205 〇〇〇Comparative Example 4 Polyurethane 50 165 --*=«*= --U 〇Δ X Comparative Example 5 Polyester 50 126 △ △ X Comparative Example 6 PC 130 240 ~~δ^ -- ----- The samples of Examples 5 to 7 showed no change in appearance on the surface and inside even if the mold temperature was 12 (rc). In contrast, the sample of Comparative Example 4 was good in Yaki but was right Loot: Above, the surface was dissolved. Further, the sample of Comparative Example 5 was at 80 C and 1 〇〇. (The surface was dissolved at two temperatures, and the surface coarse wheel occurred. Further, the sample of Comparative Example 6 and Examples 5 to 7 The samples were the same and no change in appearance was observed on the surface and inside of the film. <Eriksson test> The Erickson test was carried out in the manner shown in Figures 5a to 5c. First, as shown in Figure 5a, in sample 31 table The engraving 32 (5 mm door spacer) is added, and as shown in Fig. 5b, the Rickson test apparatus of EISK9121, 2011, 276, 718, which is defined by JIS K6744, is used, and in the center portion of the sample 31, the punch 33 of the front end is pushed in. 5mm~7mm (in Figure 5b, % is the font, % is the pressure plate), such as the money of 5c, observe whether the sample 31 floats and some micro-cracks, and the brigade is evaluated on the following basis. The results are shown in Table 5. - 〇 : No peeling, and cracks * △: Slight cracks X: Stripping [Table 5]

關於實施例5〜7及比較例4之樣品，即使押出距離為 7mm，亦不會在樣品發生浮起和些微裂痕 相對地’比較例5之樣品’於5mm已觀察到剝離，比較 例6之樣品於5mm及7mm押出均在薄膜發生許多裂痕。 [實施例8] 對鋁合金板(A5182H18 0.3inm厚），將實施例6同樣之積 層薄膜以同樣之方法積層’取得樣品。將模且溫产設定於 12(TC之加熱熔融的聚碳酸酯樹脂，在評估樣品之薄膜上成 形（射出形狀：半徑3.425mm之圓柱狀）。 099123431 41 201127618 [實施例9] 對實施例8同樣之樣品將聚碳酸酯樹脂射出成形後，於加 熱至90t之磷酸50質量％及硝酸5質量％之水溶液中浸潰 30秒鐘，並以1〇質量％硫酸水溶液進行去粗糙處理後，對 樣品加以電極’並於調整至2〇°C之20質量％硫酸水溶液中 浸潰，以電流密度150A/m2進行通電’於金屬表面取得12 的防蝕鋁膜。接著，以有機染料著色成紅色，於95。(： 之溫水中浸潰2分鐘進行封孔處理。 [實施例10] 對實施例8同樣之樣品將聚碳酸酯樹脂射出成形後，於加 熱至55t之氫氧化鈉15質量％水溶液中浸潰180秒鐘，並 以10質量％硫酸水溶液進行去粗糙處理後，對樣品加以電 極，並於調整至20°C之20質量％硫酸水溶液中浸潰，以電 流密度150A/m2進行通電，於金屬表面取得I2“m的防名虫 鋁膜。接著，以有機染料著色成金色’於95¾之溫水中浸 潰2分鐘進行封孔處理。 將實施例8〜10所得之樣品’於垂直方向進行拉伸試驗(拉 伸速度5mm/min)，將斷裂強度測定作為射出接黏強度。結 果示於表6。 099123431 42 201127618 [表6] 防蝕鋁厚度 (β m) 著色 射出接黏強度 (MPa) 實施例8 無 無 10.4 實施例9 12 紅 9.6 實施例10 12 金 9.9 由表6在射出成形後進行防蝕鋁處理之情況（實施例9及 10)中，亦取得與未進行防蝕鋁處理之情況（實施例8)同等之 接黏力，且射出接黏強度的降低為容許範圍。 雖然使用特定之態樣詳細說明本發明，但業者知曉在不脫 離本發明之意圖和範圍可作出各種變更。 另外，本申請為根據2010年2月4日申請之日本專利申 請（特願2010-023143)，其全體經由引用而被援用。 【圖式簡單說明】 圖1係示出本發明之樹脂/金屬複合積層材之實施形態之 一例的剖面圖。 圖2係示出本發明之樹脂/金屬複合射出成形體之實施形 態之一例的剖面圖。 圖3係示出本發明之樹脂/金屬複合積層材之製造步驟之 一例的示意圖。 圖4係示出本發明之樹脂/金屬複合射出成形體之製造步 驟之一例的剖面圖。 圖5為埃里克森試驗方法的說明圖。 圖6係示出習知框體的剖面圖。 099123431 43 201127618 【主要元件符號說明】 1、la、lb 樹脂/金屬複合積層材 ΙΑ 金屬板 IB 樹脂層（樹脂層a、或樹脂層a與樹脂層b的 積層樹脂層） 1C 底漆層 2 樹脂/金屬複合射出成形體 3 凸部 4 射出成形模具 5 射出成形機 6 溶融樹脂 11 框體 11a 本體部 lib 凸部 12 框體 12a 框體本體 12b 凸部 21 金屬板的回捲體 22 金屬板 23 輥 24 加熱爐 25 樹脂薄膜的回捲體 099123431 44 201127618 26 27 28 29 30 &lt; 31 32 33 34 35 樹脂薄膜 輥 再加熱爐 樹脂/金屬複合積層材 回捲體 樣品 刻紋 衝壓機 字模 壓料板 099123431 45With respect to the samples of Examples 5 to 7 and Comparative Example 4, even if the extrusion distance was 7 mm, the sample did not float and some micro-cracks were opposite. The sample of Comparative Example 5 had observed peeling at 5 mm, Comparative Example 6 The samples were cracked at 5 mm and 7 mm, and many cracks occurred in the film. [Example 8] An aluminum alloy sheet (A5182H18 0.3 inm thick) was laminated in the same manner as in the same manner as in Example 6 to obtain a sample. The mold and the temperature-producing were set to 12 (TC-heat-melted polycarbonate resin, and formed on the film of the evaluation sample (injection shape: cylindrical shape having a radius of 3.425 mm). 099123431 41 201127618 [Example 9] Example 8 In the same sample, after the polycarbonate resin was injection molded, it was immersed in an aqueous solution heated to 90 t of phosphoric acid 50% by mass and 5% by mass of nitric acid for 30 seconds, and then subjected to roughening treatment with a 1% by mass aqueous sulfuric acid solution. The sample was subjected to electrode 'and impregnated in a 20% by mass aqueous sulfuric acid solution adjusted to 2 ° C, and energized at a current density of 150 A/m 2 'to obtain an alumite film of 12 on the metal surface. Then, the organic dye was colored red. (95: The sealing treatment was carried out by immersing in warm water for 2 minutes. [Example 10] After the polycarbonate resin was injection-molded in the same sample as in Example 8, the 15% by mass aqueous solution of sodium hydroxide heated to 55 t was used. After being immersed for 180 seconds, and subjected to roughening treatment with a 10% by mass aqueous sulfuric acid solution, the sample was subjected to an electrode and immersed in a 20% by mass sulfuric acid aqueous solution adjusted to 20 ° C to have a current density of 150 A/m 2 . After energization, I2 "m anti-fame aluminum film was obtained on the metal surface. Then, the organic dye was colored into gold" and immersed in warm water of 953⁄4 for 2 minutes to carry out sealing treatment. The samples obtained in Examples 8 to 10' The tensile test was carried out in the vertical direction (tensile speed: 5 mm/min), and the breaking strength was measured as the injection bonding strength. The results are shown in Table 6. 099123431 42 201127618 [Table 6] Aluminized thickness (β m) Coloring and bonding Strength (MPa) Example 8 None 10.4 Example 9 12 Red 9.6 Example 10 12 Gold 9.9 From the case of the aluminide treatment after the injection molding in Table 6 (Examples 9 and 10), the corrosion resistance was also obtained and not In the case of aluminum treatment (Example 8), the adhesion is equivalent, and the decrease in the bond strength is within the allowable range. While the invention will be described in detail using specific aspects, it is understood that the invention may be made without departing from the scope and scope of the invention. In addition, the present application is incorporated by reference in its entirety to Japanese Patent Application Serial No. 2010-023143 filed on Jan. Fig. 2 is a cross-sectional view showing an example of an embodiment of the resin/metal composite injection molded article of the present invention. Fig. 3 is a view showing the resin of the present invention. Fig. 4 is a cross-sectional view showing an example of a manufacturing procedure of the resin/metal composite injection molded body of the present invention. Fig. 5 is an explanatory view of the Eriksson test method. 6 is a cross-sectional view showing a conventional frame. 099123431 43 201127618 [Description of main components] 1. la, lb resin/metal composite laminate ΙΑ metal plate IB resin layer (resin layer a, or resin layer a and resin layer) 1 laminated layer 2 resin/metal composite injection molded body 3 convex portion 4 injection molding die 5 injection molding machine 6 molten resin 11 frame 11a main body portion lib convex portion 12 frame 12a frame body 12b convex Part 21 Rewinding body of metal plate 22 Metal plate 23 Roller 24 Heating furnace 25 Rewinding body of resin film 099123431 44 201127618 26 27 28 29 30 &lt; 31 32 33 34 35 Resin Reheating furnace rolls resin film / metal composite laminated sheet wrapping body glyph sample Engraving machine press nip plate 09912343145

Claims (1)

201127618 七、申請專利範圍： 1.種樹月曰/金屬複合積層材，其係具有金屬板、和積層 «金屬板的至少—面之以聚醯胺系樹脂作為主成分之樹 脂層者’其特徵為， 下述式（I)所算出之上述樹脂層a的結晶化指數為 0.40〜0.80 ; [數1] 結晶化指數ω Hm2| …U (上述(I)式中，HmI、He]分別係以示差掃描型熱量計(DSC) 將該樹脂層a於30〜_ec之溫度範圍中以升溫速度1(rc/ 刀4里升m時所測疋的結晶溶解熱量（第1次結晶熔解熱量）、 結晶化發熱量（第1次、结晶化發熱量），HmZ為其後放冷至3〇 C後，再將該樹脂層a於30〜300。〇之溫度範圍中以升溫速 度1 〇 °C /分鐘升溫時所測定的結晶熔解熱量（第2次結晶熔解 熱量)）。 2·如申請專利範圍第1項之樹脂/金屬複合積層材，其中， 上述樹脂層a所含之聚醯胺系樹脂為6尼龍。 3.如申請專利範圍第1或2項之樹脂/金屬複合積層材， 其中，上述樹脂層a的厚度為5〜100//m，上述金屬板的厚 度為 0.03〜3.0mm。 4·如申請專利範圍第1至3項中任一項之樹脂/金屬複合 099123431 46 201127618 系；^其中，在上述樹脂層3上，進—步具有以聚碳酸醋 卜 '知與聚s旨系樹脂之混合樹脂作為主成分的第2樹脂層 =申請專利朗第4項之樹脂/金屬複合積層材，其中， 述树月曰層b所含之聚碳酸醋系樹脂與聚酉旨系樹脂之混合 為t碳酸S旨系樹脂··聚If、樹脂=20 : 80〜70 : 30。 盆6.如申請專利範圍第4或5項之樹脂/金屬複合積層材， =中，上述樹脂層b所含之聚_系樹脂為聚對苯二酸丁二 士申η月專利fe圍第4至6項中任-項之樹脂/金屬複合 積層材，其係使用於模内（in_mould)成形。 8. 如申請專利範圍第i至3項中任—項之樹脂/金屬複合 積層材，其係用以在上述樹脂層a上經由射出成形而將合成 樹脂所形成之凸部予以一體形成的樹脂/金屬複合積層材。 9. 如申請專·㈣4至7射任—項之_/金屬複合 積層材，其伽以在上述樹脂層b上經由射出成形而將合成 樹脂所形成之凸部予以一體形成的樹脂/金屬複合積層材。 10·如申請專利範圍第8或9項之樹脂/金屬複合制材， 其中，構成上述樹脂層a、上述樹脂層b、或上述樹脂層a 及樹脂層b的樹脂魅，係較構成上述凸部之合成樹脂的曰炫 點更低10〜60。〇 谷 11_如申請專利範圍第10項之樹脂/金屬複合積層材，1 099123431 47 201127618 中’構成上述凸部之合成樹脂為MXD 6尼龍。 12. 如申請專利範圍第1〇項之樹脂/金屬複合積層材，其 中，構成上述凸部之合成樹脂為聚碳酸酯系樹脂。 13. 如申請專利範圍第丨至12項中任一項之樹脂/金屬複 合積層材，其中，上述金屬板之形成有上述樹脂層a或上述 樹脂層a及樹脂層b的面之反側面，係經防钱|g(alumite&gt; 工處理。 14.如申請專利範圍第i至13項中任—項之樹脂/金屬複 合積層材’其中’在上述金屬板之形成有上述樹脂層a或上 述樹脂層a及樹脂層b的面之反側面，依序具有塗佈用薄膜 層和樹脂塗佈層。 15,一種樹脂/金屬複合射出成形體，其特徵為，在申請專 利範圍第1至14項巾任—項之龍/金屬複合積層材之樹脂 層a或樹脂層b上’將合成麟之㈣樹料崎出成形， 藉此使該合成樹脂所構成之凸部一體成形。 16.—種〇A機器用或電子機 申請專利範圍第15項之樹脂/金屬複合射出成形體。 17.如申請專利範圍第16項之〇A機器用或電子機器用之 框體’其係為行動電話之框體。 18·-種樹脂/金屬複合積層材之製造方法，細以製造申 凊專利範圍第1至14射任-項之翻/金屬複合積層材之 方法’其特徵為具有將樹脂薄膜_至上述金屬板的積層步 099123431 48 201127618 驟。 19.一種樹脂/金屬複合射出成形體之製造方法，係製造申 請專利範圍第15項之樹脂/金屬複合射出成形體之方法，其 特徵為具有：在配置上述樹脂/金屬複合積層材之射出成形 - 模具内，將上述熔融樹脂射出並且將上述凸部予以一體成形 * 的步驟。 099123431 49201127618 VII. Scope of application for patents: 1. Planting tree raft/metal composite laminate, which has a metal plate and a resin layer of at least the surface of the metal plate with a polyamide resin as its main component. The crystallization index of the resin layer a calculated by the following formula (I) is 0.40 to 0.80; [Number 1] crystallization index ω Hm2| ... U (HmI, He in the above formula (I), respectively The resin layer a is heated at a temperature increase rate of 1 in the temperature range of 30 _ ec by a differential scanning calorimeter (DSC) (rc/the heat of crystallization of the ruthenium measured when the knives are 4 liters in increments of m (the first crystallization heat of fusion) ), crystallization heat generation (first time, crystallization heat generation), after HmZ is cooled to 3 〇C, and then the resin layer a is in the range of 30 to 300. The temperature rise rate is 1 〇 The resin/metal composite laminate according to the first aspect of the invention, wherein the resin layer a is contained in the resin layer a. The amine resin is 6 nylon. 3. Resin/metal composite layer as claimed in claim 1 or 2. The resin layer a has a thickness of 5 to 100/m, and the metal plate has a thickness of 0.03 to 3.0 mm. 4. The resin/metal composite 099123431 of any one of claims 1 to 3. In the above-mentioned resin layer 3, the second resin layer having a mixed resin of a polycarbonate and a polystyrene resin as a main component is further advanced. /Metal composite laminate, wherein the mixture of the polycarbonate resin contained in the tree sap layer b and the poly fluorene resin is t-carbonic acid S-based resin············ 30. Pot 6. For the resin/metal composite laminate according to item 4 or 5 of the patent application, =, the poly-type resin contained in the above resin layer b is polybutylene terephthalate A resin/metal composite laminate according to any one of items 4 to 6 which is used for in-mould formation. 8. Resin/metal composite laminate according to any of items i to 3 of the patent application. a material for applying a convex portion formed of a synthetic resin to the resin layer a via injection molding A resin/metal composite laminate formed by a body. 9. If the metal composite laminate of the application (4) 4 to 7 is used, it is formed by forming a synthetic resin on the resin layer b by injection molding. A resin/metal composite material in which the convex portion is integrally formed. The resin/metal composite material according to claim 8 or 9, wherein the resin layer a, the resin layer b, or the resin layer a is formed. The resin charm of the resin layer b is 10 to 60 lower than that of the synthetic resin constituting the convex portion. 〇 谷 11_ The resin/metal composite laminate according to item 10 of the patent application, 1 099123431 47 201127618 The synthetic resin constituting the above convex portion is MXD 6 nylon. 12. The resin/metal composite laminate according to the first aspect of the invention, wherein the synthetic resin constituting the convex portion is a polycarbonate resin. The resin/metal composite laminate according to any one of the preceding claims, wherein the metal plate is formed with the resin layer a or the opposite side of the surface of the resin layer a and the resin layer b, A resin/metal composite laminate according to any one of the items ir to 13 of the patent application, wherein the resin layer a or the above is formed on the metal sheet The reverse side surface of the surface of the resin layer a and the resin layer b has a coating film layer and a resin coating layer in this order. 15. A resin/metal composite injection molding body characterized in that it is in the range of claims 1 to 14 On the resin layer a or the resin layer b of the dragon/metal composite laminate of the towel, the synthetic (4) tree material is formed into a shape, whereby the convex portion formed of the synthetic resin is integrally formed. The resin/metal composite injection molded body of the patent application range 15 of the 〇A machine or the electronic machine. 17. The frame of the machine or electronic machine of the 〇A of the scope of claim 16 is a mobile phone The frame. 18·- kinds of resin / metal composite product The manufacturing method of the material, the method of manufacturing the flip/metal composite laminate of the first to the fourth of the application of the patent range of the invention, which is characterized by having a laminate film of the resin film _ to the above metal plate, 099123431 48 201127618. A method for producing a resin/metal composite injection molded article, which is a method for producing a resin/metal composite injection molded article according to claim 15 which is characterized in that: the injection molding of the resin/metal composite laminate is disposed - a step of ejecting the molten resin and integrally molding the convex portion in the mold. 099123431 49
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