TWI605102B - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
TWI605102B
TWI605102B TW102139146A TW102139146A TWI605102B TW I605102 B TWI605102 B TW I605102B TW 102139146 A TW102139146 A TW 102139146A TW 102139146 A TW102139146 A TW 102139146A TW I605102 B TWI605102 B TW I605102B
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Taiwan
Prior art keywords
phosphate
flame retardant
adhesive
adhesive sheet
mass
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TW102139146A
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Chinese (zh)
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TW201432011A (en
Inventor
Kenji Ohata
Seitaro Yamaguchi
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Lintec Corp
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Publication of TW201432011A publication Critical patent/TW201432011A/en
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Publication of TWI605102B publication Critical patent/TWI605102B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

黏著片 Adhesive film

本發明關於黏著片。更詳細地，關於不使用在焚化時發生有毒氣體的鹵系難燃劑或有發生內分泌攪亂化學物質等之虞的含芳香族之磷酸酯系難燃劑，而具有優異的難燃性、黏著特性及高溫時黏著特性之難燃性黏著片。 The present invention relates to an adhesive sheet. In more detail, it is excellent in flame retardancy and adhesion without using a halogen-based flame retardant which generates a toxic gas during incineration or an aromatic-containing phosphate-based flame retardant which generates an endocrine disrupting chemical or the like. A flame retardant adhesive sheet with characteristics and adhesive properties at high temperatures.

於電子零件相關或電子機器關聯、飛行器、原子能發電所等各式各樣領域中要求難燃性。為了應付此，對彼等領域所使用的構件賦予難燃性，同時於固定此等構件的黏著帶或片，亦要求UL94規格的VTM-0水準高之難燃性。 It is required to be flame retardant in various fields such as electronic component related or electronic machine related, aircraft, and atomic power generation. In order to cope with this, it is required to impart flame retardancy to members used in these fields, and at the same time, to fix the adhesive tape or sheet of such members, the VTM-0 level of UL94 specification is required to be high in flame retardancy.

為了提高黏著帶或片之難燃性，一般對於黏著劑組成物，採用使含有各種難燃劑之方法。作為該難燃劑，一般為溴或氯等之鹵系化合物、或在鹵系化合物中併用氧化銻者等。 In order to improve the flame retardancy of the adhesive tape or sheet, a method of containing various flame retardants is generally employed for the adhesive composition. The flame retardant is generally a halogen compound such as bromine or chlorine, or a halogen oxide compound or the like.

然而，鹵系化合物之難燃劑，由於在燃燒時產生鹵系氣體，而具有對人體或環境有害之問題。 However, the flame retardant of the halogen compound has a problem of being harmful to the human body or the environment because it generates a halogen-based gas during combustion.

因此，為了解決此等問題，專利文獻1中提案一種難燃性黏著帶，其使用摻合磷酸酯系難燃劑與含氮之磷酸鹽化合物系難燃劑作為鹵系化合物以外之難燃劑而成之 黏著劑組成物。 Therefore, in order to solve such problems, Patent Document 1 proposes a flame-retardant adhesive tape which uses a phosphate-based flame retardant and a nitrogen-containing phosphate compound-based flame retardant as a flame retardant other than a halogen compound. Made Adhesive composition.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2006-219564號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-219564

然而，專利文獻1之難燃性黏著帶，由於以含芳香族之磷酸酯系難燃劑作為必要成分，在燃燒時有產生已知為內分泌攪亂化學物質的雙酚A之虞。又，該難燃性黏著帶係有高溫時的黏著特性低之問題。 However, in the flame-retardant adhesive tape of Patent Document 1, since an aromatic phosphate-containing flame retardant is used as an essential component, bisphenol A known as an endocrine disrupting chemical substance is generated during combustion. Further, the flame retardant adhesive tape has a problem that the adhesive property at a high temperature is low.

本發明係在如此的狀況下而完成者，目的在於提供一種黏著片，其係在基材的至少一面上具有包含難燃劑的黏著劑層之黏著片，該黏著劑層不含有鹵系難燃劑及含芳香族之磷系難燃劑作為難燃劑，該黏著片能滿足難燃性(UL94 VTM-0)與黏著特性(8N/25mm以上)、及高溫時(80℃)黏著特性(8N/25mm以上)。 The present invention has been accomplished under such circumstances, and an object thereof is to provide an adhesive sheet having an adhesive sheet having an adhesive layer containing a flame retardant on at least one side of a substrate, the adhesive layer not containing a halogen system A fuel-based and aromatic-containing phosphorus-based flame retardant is used as a flame retardant. The adhesive sheet can satisfy the flame retardancy (UL94 VTM-0) and adhesion characteristics (8N/25mm or more) and high temperature (80°C) adhesion characteristics. (8N/25mm or more).

本發明者們為了達成前述目的，重複專心致力的研究，結果得到下述之知識見解。 In order to achieve the above object, the inventors of the present invention repeated the intensive research and obtained the following knowledge findings.

發現：於基材的至少一面上所設置的黏著劑層係由包含丙烯酸系共聚物(A)、與不具有芳香環之特定的磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)之黏著劑組成物所構成，丙烯酸系共聚物(A)以特定的比例包含含有羧基之單體單元(例如丙烯酸單元等)，更且 相對於丙烯酸系共聚物(A)，前述黏著劑組成物中之難燃劑(B1)及(B2)的合計量在特定之範圍的情況，得到能符合前述目的之黏著片。 It has been found that the adhesive layer provided on at least one side of the substrate is composed of an acrylic copolymer (A), a specific phosphate-based flame retardant (B1) having no aromatic ring, and a nitrogen-containing phosphate. The compound is composed of an adhesive composition of a flame retardant (B2), and the acrylic copolymer (A) contains a carboxyl group-containing monomer unit (for example, an acrylic unit or the like) in a specific ratio, and When the total amount of the flame retardants (B1) and (B2) in the above-mentioned adhesive composition is within a specific range with respect to the acrylic copolymer (A), an adhesive sheet which can meet the above object can be obtained.

本發明係以如此的知識見解為基礎而完成者。 The present invention has been completed on the basis of such knowledge.

即，本發明提供下述[1]~[7]。 That is, the present invention provides the following [1] to [7].

[1]一種黏著片，其係在基材的至少一面上具有黏著劑層之黏著片，其特徵為前述黏著劑層係由包含丙烯酸系共聚物(A)、與下述通式(1)所表示的不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)之黏著劑組成物所構成，丙烯酸系共聚物(A)以15~35質量%的比例包含含有羧基之單體單元作為單體單元，且該黏著劑組成物中，相對於100質量份之丙烯酸系共聚物(A)，不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)的合計量為40~90質量份， [1] An adhesive sheet comprising an adhesive sheet having an adhesive layer on at least one side of a substrate, wherein the adhesive layer is composed of an acrylic copolymer (A) and a general formula (1) The adhesive composition of the phosphate-free flame retardant (B1) having no aromatic ring and the flame retardant (B2) containing a nitrogen-containing phosphate compound, and the acrylic copolymer (A) is 15~ The proportion of 35 mass% includes a monomer unit containing a carboxyl group as a monomer unit, and in the adhesive composition, a phosphate-based flame retardant having no aromatic ring with respect to 100 parts by mass of the acrylic copolymer (A) The total amount of (B1) and the nitrogen-containing phosphate compound-based flame retardant (B2) is 40 to 90 parts by mass.

(式中，R1、R2、R3及R4係各自獨立表示氫、碳數1~12的烷基、或碳數3~12的環烷基；D係表示可具有取代基之碳數1~5的伸烷基或可具有取代基之碳數1~5的伸氧烷基(oxyalkylene)；n係0~3之數值，n為2以上的情況，複數的OR4可各自相同或相異；R1與R2、R2與R3、或R1與R3係可互相鍵結形成環，n為1以上的情況，R1、R2或R3 與一個R4可互相鍵結形成環；此外，該環係可具有取代基)。 (wherein R 1 , R 2 , R 3 and R 4 each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms; and D represents a carbon which may have a substituent An alkylene group having 1 to 5 or an oxyalkylene having 1 to 5 carbon atoms which may have a substituent; n is a value of 0 to 3, and n is 2 or more, and the plural OR 4 may be the same Or different; R 1 and R 2 , R 2 and R 3 , or R 1 and R 3 may be bonded to each other to form a ring, n is 1 or more, and R 1 , R 2 or R 3 and one R 4 may be used. Bonded to each other to form a ring; further, the ring system may have a substituent).

[2]如上述[1]記載之黏著片，其中黏著劑組成物不含有鹵素化合物、銻化合物、及含芳香族之磷酸酯系化合物之任一者。 [2] The adhesive sheet according to the above [1], wherein the adhesive composition does not contain any one of a halogen compound, a hydrazine compound, and an aromatic phosphate-containing compound.

[3]如上述[1]或[2]記載之黏著片，其中不具有芳香環之磷酸酯系難燃劑(B1)為選自磷酸三丁酯、磷酸三己酯、磷酸三環己酯、磷酸參(2-乙基己)酯、磷酸三辛酯、磷酸三癸酯、及縮合磷酸酯之至少一種。 [3] The adhesive sheet according to the above [1] or [2] wherein the phosphate-based flame retardant (B1) having no aromatic ring is selected from the group consisting of tributyl phosphate, trihexyl phosphate, and tricyclohexyl phosphate. At least one of phosphoric acid (2-ethylhexyl) ester, trioctyl phosphate, tridecyl phosphate, and condensed phosphate.

[4]如上述[1]至[3]中任一項記載之黏著片，其中不具有芳香環之磷酸酯系難燃劑(B1)之磷含有率為8~20質量%。 [4] The adhesive sheet according to any one of the above [1] to [3] wherein the phosphorus ester-containing flame retardant (B1) having no aromatic ring has a phosphorus content of 8 to 20% by mass.

[5]如上述[1]至[4]中任一項記載之黏著片，其中構成丙烯酸系共聚物(A)之丙烯酸系單體單元之側鏈碳數為7以下。 [5] The adhesive sheet according to any one of the above [1] to [4] wherein the acrylic monomer unit constituting the acrylic copolymer (A) has a side chain carbon number of 7 or less.

[6]如上述[1]至[5]中任一項記載之黏著片，其中黏著劑組成物係以質量比計為1：0.2~1：5的比例包含不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)。 [6] The adhesive sheet according to any one of the above [1] to [5] wherein the adhesive composition is a phosphate ester system having no aromatic ring in a ratio of 1:0.2 to 1:5 by mass ratio. The flame retardant (B1) and the nitrogen-containing phosphate compound are flame retardants (B2).

[7]如上述[1]至[6]中任一項記載之黏著片，其中基材具有符合UL94規格中規定之試驗VTM-0之難燃性。 [7] The adhesive sheet according to any one of [1] to [6] wherein the substrate has a flame retardancy according to the test VTM-0 specified in the UL94 specification.

依照本發明，提供一種黏著片，其係在基材的至少一面上具有含難燃劑的黏著劑層之黏著片，該黏著劑層不含有鹵系難燃劑、含芳香族的磷系難燃劑作為 難燃劑，該黏著片能滿足難燃性(UL94 VTM-0)與黏著特性(8N/25mm以上)、及高溫時(80℃)黏著特性(8N/25mm以上)。 According to the present invention, there is provided an adhesive sheet which is an adhesive sheet having an adhesive layer containing a flame retardant on at least one side of a substrate, the adhesive layer not containing a halogen-based flame retardant, and an aromatic-containing phosphorus system Fuel as a fuel Flame retardant, the adhesive sheet can meet the flame retardancy (UL94 VTM-0) and adhesion characteristics (8N/25mm or more) and high temperature (80 °C) adhesion characteristics (8N/25mm or more).

1a、1b、1c‧‧‧黏著片 1a, 1b, 1c‧‧‧ Adhesive tablets

11‧‧‧基材 11‧‧‧Substrate

12a、12b‧‧‧黏著劑層 12a, 12b‧‧‧Adhesive layer

13a‧‧‧剝離片 13a‧‧‧ peeling film

第1圖係顯示本發明的黏著片之構成的一態樣之截面示意圖。 Fig. 1 is a schematic cross-sectional view showing an aspect of the constitution of the adhesive sheet of the present invention.

[實施發明之形態] [Formation of the Invention]

本發明之黏著片係在基材的至少一面上具有黏著劑層之黏著片，其特徵為前述黏著劑層係由包含丙烯酸系聚合物(A)、與前述通式(1)所表示的不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)之黏著劑組成物所構成。 The adhesive sheet of the present invention is an adhesive sheet having an adhesive layer on at least one side of a substrate, characterized in that the adhesive layer is composed of an acrylic polymer (A) and not represented by the above formula (1). It is composed of a phosphate-based flame retardant (B1) having an aromatic ring and an adhesive composition of a nitrogen-containing phosphate compound-based flame retardant (B2).

本發明之黏著片的構成，只要是在基材的一面或兩面上具有黏著劑層，則沒有特別的限定。 The adhesive sheet of the present invention is not particularly limited as long as it has an adhesive layer on one or both sides of the substrate.

第1圖係顯示本發明之黏著片的構成之一態樣之圖。本發明之黏著片的構成係不限於如第1圖(a)，在基材11的一面上具有黏著劑層12a之黏著片1a，亦可如第1圖(b)，在基材11的一面上所形成的黏著劑層12a之上，更積層有剝離片13a之黏著片1b。 Fig. 1 is a view showing an aspect of the constitution of the adhesive sheet of the present invention. The adhesive sheet of the present invention is not limited to the adhesive sheet 1a having the adhesive layer 12a on one surface of the substrate 11 as shown in Fig. 1(a), and may be as shown in Fig. 1(b) on the substrate 11. On the adhesive layer 12a formed on one side, the adhesive sheet 1b of the release sheet 13a is further laminated.

又，本發明之黏著片也可如第1圖(c)，在基材11的兩面具有黏著劑層12a、12b之黏著片1c，亦可在該黏著劑層12a、12b的各自之上，更積層有剝離片13a、13b之黏著片。再者，於第1圖(c)中，剝離片13a、13b的表示 係省略。 Further, the adhesive sheet of the present invention may have an adhesive sheet 1c having adhesive layers 12a and 12b on both sides of the substrate 11 as shown in Fig. 1(c), or may be on each of the adhesive layers 12a and 12b. The adhesive sheets of the release sheets 13a and 13b are laminated. Furthermore, in the first figure (c), the representation of the release sheets 13a and 13b It is omitted.

[基材] [substrate]

本發明之黏著片中所用的基材，較佳為使用具有符合UL94規格中規定之試驗VTM-0之難燃性者。於本發明中，所謂「符合UL94規格中規定之試驗VTM-0」，係指在保險業實驗室公司(UNDERWRITERS LABORATORIES INC.)發行之塑膠材料的難燃性試驗規格UL94的薄型材料垂直燃燒試驗方法中規定之試驗中，VTM等級被判定為VTM-0者。 The substrate used in the adhesive sheet of the present invention is preferably one which has a flame retardancy which is in compliance with the test VTM-0 specified in the UL94 specification. In the present invention, the "test VTM-0 in accordance with the UL94 specification" refers to the vertical burning test of the thin material of the flame retardant test specification UL94 issued by the plastics laboratory company (UNDERWRITERS LABORATORIES INC.). In the test specified in the method, the VTM level was judged as VTM-0.

作為如此的基材，可使用由以樹脂單體具有難燃性的樹脂所構成之基材、由含有難燃劑的樹脂所構成之基材、將上述樹脂塗布或積層於片上而成之基材、及金屬箔等。於本發明中，較佳為使用樹脂製之基材。 As such a substrate, a substrate composed of a resin having flame retardancy with a resin monomer, a substrate composed of a resin containing a flame retardant, and a base formed by coating or laminating the resin on a sheet can be used. Materials, metal foils, etc. In the present invention, it is preferred to use a substrate made of a resin.

作為以樹脂單體具有難燃性之樹脂，可舉出聚醚醯亞胺樹脂或聚苯醚醯亞胺樹脂等之聚醯亞胺樹脂、聚芳醯胺樹脂、聚苯硫樹脂、聚醚醚酮樹脂等。 Examples of the resin having a flame retardancy in a resin monomer include a polyimide imine resin such as a polyether fluorene imine resin or a polyphenylene quinone imide resin, a polyarsenamide resin, a polyphenylene sulfide resin, and a polyether. Ether ketone resin and the like.

作為由含有難燃劑的樹脂所成之基材中使用的樹脂，除了上述以樹脂單體具有難燃性的樹脂，還可舉出聚碳酸酯樹脂、聚苯乙烯樹脂、聚乙烯樹脂、聚酯樹脂、聚烯烴樹脂、聚胺基甲酸酯樹脂、酚樹脂、尿素樹脂、EVA樹脂、丙烯酸樹脂、丙烯腈丁二烯苯乙烯樹脂(ABS樹脂)、環氧樹脂、聚苯乙烯-聚碳酸酯共混樹脂、聚苯乙烯-ABS共混樹脂、聚醯胺樹脂等。 Examples of the resin used for the substrate made of a resin containing a flame retardant include a polycarbonate resin, a polystyrene resin, a polyethylene resin, and a polyether in addition to the above-mentioned resin having a flame retardancy. Ester resin, polyolefin resin, polyurethane resin, phenol resin, urea resin, EVA resin, acrylic resin, acrylonitrile butadiene styrene resin (ABS resin), epoxy resin, polystyrene-polycarbonate Ester blend resin, polystyrene-ABS blend resin, polyamide resin, and the like.

作為難燃劑，可舉出磷系難燃劑、聚矽氧系化合物、三聚氰胺系化合物、受阻胺系化合物、胍系化合物等 之有機系難燃劑、或銻系化合物、金屬氫氧化物等之無機系難燃劑。上述難燃劑係可單獨或2種以上組合使用。 Examples of the flame retardant include a phosphorus-based flame retardant, a polysulfonium-based compound, a melamine-based compound, a hindered amine-based compound, an anthraquinone-based compound, and the like. An organic flame retardant, or an inorganic flame retardant such as a lanthanoid compound or a metal hydroxide. The above-mentioned flame retardant may be used singly or in combination of two or more kinds.

又，亦可使用將前述以樹脂單體具有難燃性的樹脂或含有難燃劑的樹脂塗布或積層於片上而成之基材。作為該片，例如可舉出片狀的塑膠、含浸紙等之紙、織布、不織布等。 Further, a substrate obtained by coating or laminating a resin having a flame retardancy of a resin monomer or a resin containing a flame retardant on a sheet may be used. Examples of the sheet include a sheet-like plastic, a paper such as impregnated paper, a woven fabric, a non-woven fabric, and the like.

於上述基材之中，從難燃性之觀點而言，較佳為由聚醯亞胺樹脂、聚芳醯胺樹脂、聚苯硫樹脂、聚醚醚酮樹脂所構成之基材，或將此等樹脂塗布於前述片上而成之基材。 Among the above-mentioned substrates, from the viewpoint of flame retardancy, a substrate composed of a polyimide resin, a polyarsenamide resin, a polyphenylene sulfide resin, a polyetheretherketone resin, or the like is preferable. These resins are coated on the substrate to form a substrate.

又，從環境對應之觀點而言，較佳為實質上不含有鹵系難燃劑的基材，更佳為使用實質上完全不含有任何難燃劑之基材。 Further, from the viewpoint of environmental compatibility, a substrate which does not substantially contain a halogen-based flame retardant is preferable, and a substrate which does not substantially contain any flame retardant at all is more preferably used.

作為本發明之黏著片中使用的基材之具體的製品例，可舉出Lumirror ZV10(商品名，在聚對苯二甲酸乙二酯薄膜上塗布有聚醯亞胺樹脂之薄膜，東麗股份有限公司製)、Torelina(商品名，聚苯硫樹脂薄膜，東麗股份有限公司製)、Mictron(商品名，聚芳醯胺樹脂薄膜，東麗股份有限公司製)、Kapton(商品名，聚醯亞胺樹脂薄膜，東麗-杜邦股份有限公司製)、Superio UT(商品名，聚醚醯亞胺系樹脂薄膜，三菱樹脂股份有限公司製)、Daiarami(商品名，含有難燃劑之聚對苯二甲酸乙二酯樹脂薄膜，三菱樹脂股份有限公司製)等。 Specific examples of the substrate used in the adhesive sheet of the present invention include Lumirror ZV10 (trade name, a film coated with a polyimide resin on a polyethylene terephthalate film, Toray Co., Ltd. Co., Ltd.), Torelina (trade name, polyphenylene sulfide resin film, manufactured by Toray Industries, Inc.), Mictron (trade name, polyarsenamide resin film, manufactured by Toray Industries, Inc.), Kapton (trade name, poly醯imino resin film, manufactured by Toray-DuPont Co., Ltd.), Super UT (trade name, polyether phthalimide resin film, manufactured by Mitsubishi Plastics Co., Ltd.), Daiarami (trade name, containing flame retardant) A polyethylene terephthalate resin film, manufactured by Mitsubishi Plastics Co., Ltd., and the like.

又，可舉出LAXRON Polyca SDB-3(商品名，含有難燃劑之聚碳酸酯樹脂薄膜，TOKIWA電氣股份有限公司 製)、Sunloid Barrier(商品名，聚苯醚系樹脂薄膜，住友BAKELITE股份有限公司製)、Sunloid Ecosheet Polyca(商品名，含有非鹵素難燃劑之聚碳酸酯樹脂薄膜，住友BAKELITE股份有限公司製)、Ultem(商品名，聚醚醯亞胺樹脂薄膜，旭硝子股份有限公司製)、Lexan(商品名，聚碳酸酯系樹脂片，旭硝子股份有限公司製)、Valox(商品名，聚對苯二甲酸丁二酯系樹脂薄膜，旭硝子股份有限公司製)、Safety薄膜(商品名，聚乙烯系樹脂薄膜，大井田工業股份有限公司製)等。再者，並非受此等的製品例所限定。 Further, LAXRON Polyca SDB-3 (trade name, polycarbonate resin film containing flame retardant, TOKIWA Electric Co., Ltd.) , Sunloid Barrier (trade name, polyphenylene ether resin film, manufactured by Sumitomo BAKELITE Co., Ltd.), Sunloid Ecosheet Polyca (trade name, polycarbonate resin film containing non-halogen flame retardant, manufactured by Sumitomo BAKELITE Co., Ltd. ), Ultem (trade name, polyether phthalimide resin film, manufactured by Asahi Glass Co., Ltd.), Lexan (trade name, polycarbonate resin sheet, manufactured by Asahi Glass Co., Ltd.), Valox (trade name, poly-p-phenylene) A butadiene succinate resin film, manufactured by Asahi Glass Co., Ltd., and a safety film (trade name, polyethylene resin film, manufactured by Omachi Industrial Co., Ltd.). Furthermore, it is not limited by the product examples of these.

基材之厚度係可按照黏著片的用途來適宜決定，通常為1~100μm，較佳為5~100μm，更佳為10~80μm。 The thickness of the substrate can be appropriately determined depending on the use of the adhesive sheet, and is usually 1 to 100 μm, preferably 5 to 100 μm, more preferably 10 to 80 μm.

[黏著劑層] [Adhesive layer]

本發明之黏著片係在上述基材的至少一面上，具有由包含丙烯酸系聚合物(A)、與前述通式(1)所表示的不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)之黏著劑組成物所構成的黏著劑層。 The adhesive sheet of the present invention has at least one surface of the base material, and has a phosphate-based flame retardant (B1) containing an acrylic polymer (A) and having no aromatic ring represented by the above formula (1). An adhesive layer composed of an adhesive composition of a nitrogen-containing phosphate compound-based flame retardant (B2).

於本發明之黏著片中，從難燃性及黏著力的並存之觀點而言，該黏著劑層的每一面之厚度較佳為5~50μm，更佳為10~40μm。 In the adhesive sheet of the present invention, the thickness of each side of the adhesive layer is preferably from 5 to 50 μm, more preferably from 10 to 40 μm, from the viewpoint of coexistence of flame retardancy and adhesion.

再者，本發明中所謂的「黏著劑層的每一面之厚度」，係表示在基材的一面或兩面上所設置的黏著劑層之各自的厚度(第1圖(a)~(c)的Z1、Z2之各自)。 In the present invention, the "thickness of each side of the adhesive layer" means the thickness of each of the adhesive layers provided on one or both sides of the substrate (Fig. 1 (a) to (c). Each of Z1 and Z2).

<黏著劑組成物> <Adhesive Composition>

本發明所用之構成黏著劑層的黏著劑組成物，包含丙烯酸系共聚物(A)、與通式(1)所表示的不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)，視需要可含有交聯劑、其他的添加劑及有機溶劑等。以下，說明黏著劑組成物中所含有的各成分。 The adhesive composition constituting the adhesive layer used in the present invention comprises an acrylic copolymer (A), a phosphate-based flame retardant (B1) having no aromatic ring represented by the formula (1), and nitrogen-containing The phosphate compound is a flame retardant (B2), and may contain a crosslinking agent, other additives, an organic solvent, etc. as needed. Hereinafter, each component contained in the adhesive composition will be described.

(丙烯酸系共聚物(A)) (acrylic copolymer (A))

本發明所用之丙烯酸系共聚物(A)較佳為包含來自(甲基)丙烯酸烷酯(a1)(以下亦稱為「單體(a1)」)之結構單元(a1)、及來自含羧基之單體(a2)(以下亦稱為「單體(a2)」)之結構單元(a2)之共聚物。再者，從所得之黏著片的難燃性之觀點而言，構成丙烯酸系共聚物(A)之單體(a1)等的丙烯酸系單體單元之側鏈碳數較佳為7以下，更佳為5以下。 The acrylic copolymer (A) used in the present invention preferably contains a structural unit (a1) derived from an alkyl (meth)acrylate (a1) (hereinafter also referred to as "monomer (a1)"), and derived from a carboxyl group. A copolymer of the structural unit (a2) of the monomer (a2) (hereinafter also referred to as "monomer (a2)"). In addition, from the viewpoint of the flame retardancy of the obtained adhesive sheet, the acrylic monomer unit constituting the monomer (a1) of the acrylic copolymer (A) preferably has a side chain carbon number of 7 or less. Good for 5 or less.

又，丙烯酸系共聚物(A)之共聚合形態係沒有特別的限制，可為無規共聚物、嵌段共聚物、接枝共聚物之任一者。 Further, the copolymerization form of the acrylic copolymer (A) is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer.

(單體(a1)) (monomer (a1))

(甲基)丙烯酸烷酯(a1)係丙烯酸系共聚物(A)的主成分單體。單體(a1)之側鏈碳數較佳為7以下，更佳為5以下。此碳數若為7以下，則所得之黏著片的難燃性良好。 The alkyl (meth)acrylate (a1) is a main component monomer of the acrylic copolymer (A). The side chain carbon number of the monomer (a1) is preferably 7 or less, more preferably 5 or less. When the carbon number is 7 or less, the obtained adhesive sheet is excellent in flame retardancy.

作為單體(a1)，例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯等之具有碳數1~10的烷基之(甲基)丙烯酸烷酯。此等單體(a1)係可為單獨或組合2種以上使用。 Examples of the monomer (a1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. An alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms such as hexyl (meth)acrylate or cyclohexyl (meth)acrylate. These monomers (a1) may be used alone or in combination of two or more.

於此等之中，從黏著性能之觀點而言，較佳為(甲基)丙烯酸丁酯，更佳為丙烯酸丁酯。 Among these, from the viewpoint of adhesive properties, butyl (meth)acrylate is preferred, and butyl acrylate is more preferred.

再者，當併用2種以上的單體(a1)時，較佳為至少含有(甲基)丙烯酸丁酯。單體(a1)中的(甲基)丙烯酸丁酯之比例較佳為60~100質量%，更佳為75~100質量%，尤佳為90~100質量%，尤更佳為實質上100質量%。 In addition, when two or more types of monomers (a1) are used in combination, it is preferred to contain at least (butyl) (meth)acrylate. The proportion of the butyl (meth)acrylate in the monomer (a1) is preferably from 60 to 100% by mass, more preferably from 75 to 100% by mass, even more preferably from 90 to 100% by mass, even more preferably substantially 100. quality%.

(單體(a2)) (monomer (a2))

單體(a2)係含羧基的單體，較佳可舉出羧酸。 The monomer (a2) is a carboxyl group-containing monomer, preferably a carboxylic acid.

作為羧酸之合適例，可舉出(甲基)丙烯酸、巴豆酸、富馬酸、馬來酸等，此等之中較佳為(甲基)丙烯酸，更佳為丙烯酸。 Suitable examples of the carboxylic acid include (meth)acrylic acid, crotonic acid, fumaric acid, and maleic acid. Among them, (meth)acrylic acid is preferred, and acrylic acid is more preferred.

(單體(a3)) (monomer (a3))

於本發明所用之丙烯酸系共聚物(A)中，在不損害本發明的效果之範圍內，亦可具有來自單體(a1)及(a2)以外之其他單體(a3)的結構單元(a3)。 In the acrylic copolymer (A) used in the present invention, structural units derived from monomers (a3) other than the monomers (a1) and (a2) may be contained within a range not impairing the effects of the present invention ( A3).

作為單體(a3)，例如可舉出具有羥基、胺基等的交聯性官能基之(甲基)丙烯酸酯單體；醋酸乙烯酯、丙酸乙烯酯等之乙烯酯類；乙烯、丙烯、異丁烯等之烯烴類；苯乙烯、甲基苯乙烯、乙烯基甲苯等之芳香族乙烯基單體：丁二烯、異戊二烯等之二烯系單體；(甲基)丙烯腈等之腈系單體等。 Examples of the monomer (a3) include a (meth) acrylate monomer having a crosslinkable functional group such as a hydroxyl group or an amine group; a vinyl ester such as vinyl acetate or vinyl propionate; and ethylene and propylene. An olefin such as isobutylene; an aromatic vinyl monomer such as styrene, methyl styrene or vinyl toluene: a diene monomer such as butadiene or isoprene; (meth)acrylonitrile or the like Nitrile monomer and the like.

此等單體(a3)係可為單獨或組合2種以上使用。 These monomers (a3) may be used alone or in combination of two or more.

本發明所用之丙烯酸系共聚物(A)係以15~35質量%，較佳18~32質量%的比例包含含有羧基之單體單元(a2)作為單體單元。此含量少於15質量%時，所得之 黏著片的高溫時黏著特性不足，另一方面若超過35質量%，則黏著特性不足。 The acrylic copolymer (A) used in the present invention contains a carboxyl group-containing monomer unit (a2) as a monomer unit in a ratio of 15 to 35 mass%, preferably 18 to 32 mass%. When the content is less than 15% by mass, the obtained When the adhesive sheet has a high temperature, the adhesive property is insufficient, and if it exceeds 35% by mass, the adhesive property is insufficient.

丙烯酸系共聚物(A)中所含有的結構單元(a1)與結構單元(a2)之質量比[結構單元(a1)/結構單元(a2)]，從黏著力提高之觀點而言，較佳為85/15~65/35，更佳為82/18~68/32。 The mass ratio of the structural unit (a1) to the structural unit (a2) contained in the acrylic copolymer (A) [structural unit (a1) / structural unit (a2)] is preferably from the viewpoint of improving adhesion. It is 85/15~65/35, more preferably 82/18~68/32.

又，於丙烯酸系共聚物(A)中，亦可具有來自結構單元(a1)及(a2)以外之其他單體(a3)的結構單元(a3)，但此時從難燃性及黏著性能之觀點而言，相對於100質量%之丙烯酸系共聚物(A)的全部結構單元，結構單元(a3)之含量為10質量%以下，更佳為5質量%以下，尤佳為1質量%以下，尤更佳為實質上0質量%。 Further, in the acrylic copolymer (A), the structural unit (a3) derived from the other monomer (a3) other than the structural units (a1) and (a2) may be provided, but at this time, flame retardancy and adhesion properties are obtained. In view of the total structural unit of 100% by mass of the acrylic copolymer (A), the content of the structural unit (a3) is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass. In the following, it is more preferably 0% by mass.

作為丙烯酸系共聚物(A)之重量平均分子量(Mw)，從黏著力提高之觀點而言，較佳為10萬~150萬，更佳為12萬~100萬，尤佳為15萬~70萬，尤更佳為17萬~40萬。Mw若為10萬以上，可提高所形成的黏著劑層之內聚力，得到充分的黏著力。又，Mw若為150萬以下，則黏著劑層的彈性模數不變過高，可抑制黏著力之降低。 The weight average molecular weight (Mw) of the acrylic copolymer (A) is preferably from 100,000 to 1,500,000, more preferably from 120,000 to 1,000,000, and particularly preferably from 150,000 to 70, from the viewpoint of improving adhesion. 10,000, especially better, 170,000 to 400,000. If the Mw is 100,000 or more, the cohesive force of the formed adhesive layer can be improved, and sufficient adhesion can be obtained. Further, when the Mw is 1.5 million or less, the elastic modulus of the adhesive layer is not excessively high, and the decrease in the adhesive force can be suppressed.

再者，於本發明中，重量平均分子量(Mw)之值係以凝膠滲透層析(GPC)法所測定的標準聚苯乙烯換算之值，具體地為根據實施例記載之方法所測定之值。 Further, in the present invention, the value of the weight average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically, a method according to the method described in the examples. value.

(丙烯酸系共聚物(A)之合成方法) (Synthesis method of acrylic copolymer (A))

丙烯酸系共聚物(A)係可藉由在由上述單體成分所成的單體混合物中，按照需要地添加溶劑、聚合引發劑 ，使進行聚合反應而合成。 The acrylic copolymer (A) can be optionally added with a solvent or a polymerization initiator in a monomer mixture composed of the above monomer components. It is synthesized by carrying out a polymerization reaction.

作為所用之溶劑，例如可舉出醋酸乙酯、甲苯等。再者，亦可於溶劑的不存在下使進行聚合反應。 Examples of the solvent to be used include ethyl acetate, toluene, and the like. Further, the polymerization reaction can also be carried out in the absence of a solvent.

作為所添加的聚合引發劑，例如可舉出偶氮雙異丁腈、過氧化苯甲醯等。 Examples of the polymerization initiator to be added include azobisisobutyronitrile and benzammonium peroxide.

相對於100質量份之單體混合物，聚合引發劑之添加量較佳為0.01~1質量份，更佳為0.1~0.5質量份。 The amount of the polymerization initiator added is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, per 100 parts by mass of the monomer mixture.

聚合條件係沒有特別的限定，較佳為以氮氣脫氣後，在50~90℃之溫度，費2~30小時進行聚合。 The polymerization conditions are not particularly limited, and it is preferred to carry out the polymerization at a temperature of 50 to 90 ° C for 2 to 30 hours after deaeration with nitrogen.

<(A)成分以外之樹脂成分> <Resin component other than (A) component>

本發明所用之黏著劑組成物，於(A)成分之含量滿足上述範圍之範圍內，亦可含有(A)成分以外之樹脂成分。 The adhesive composition used in the present invention may contain a resin component other than the component (A) in a range in which the content of the component (A) satisfies the above range.

作為(A)成分以外之樹脂成分，例如可舉出胺基甲酸酯樹脂、丙烯酸胺基甲酸酯樹脂、胺基甲酸酯聚酯樹脂、丁基橡膠等。 Examples of the resin component other than the component (A) include a urethane resin, an urethane urethane resin, a urethane polyester resin, and a butyl rubber.

(交聯劑) (crosslinking agent)

本發明所用之黏著劑組成物視需要亦可含有交聯劑。於丙烯酸系共聚物(A)中，由於包含含有羧基之單體單元作為交聯點，可藉由交聯劑來交聯。藉此，所得之黏著劑層的黏著特性成為更良好。 The adhesive composition used in the present invention may further contain a crosslinking agent as needed. In the acrylic copolymer (A), since a monomer unit containing a carboxyl group is contained as a crosslinking point, it can be crosslinked by a crosslinking agent. Thereby, the adhesive property of the obtained adhesive layer becomes more favorable.

作為交聯劑，從反應性之觀點而言，較佳為使用異氰酸酯系交聯劑。 As the crosslinking agent, an isocyanate crosslinking agent is preferably used from the viewpoint of reactivity.

作為異氰酸酯系交聯劑，例如可舉出甲苯二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、苯二甲基二異氰酸酯、氫化苯二甲基二異氰酸酯、二苯基甲 烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、四甲基苯二甲基二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯、聚亞甲基聚苯基異氰酸酯等之聚異氰酸酯化合物；及此等聚異氰酸酯化合物與三羥甲基丙烷等之多元醇化合物的加成物；此等聚異氰酸酯化合物的縮二脲體或異三聚氰酸酯體；更且此等聚異氰酸酯化合物與眾所周知的聚醚多元醇或聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等之加成物等。 Examples of the isocyanate crosslinking agent include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, hydrogenated dimethyl diisocyanate, and diphenylmethyl. Polyisocyanate compounds such as alkyl diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl dimethyl diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate; and the like An adduct of a polyisocyanate compound with a polyol compound such as trimethylolpropane; a biuret or isomeric cyanate of such a polyisocyanate compound; and such a polyisocyanate compound and a well-known polyether An adduct of a polyol or a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, or the like.

於此等異氰酸酯系交聯劑之中，作為黏著劑的物性之觀點而言，較佳為選自4,4’-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯及此等之改性體的1種以上，特佳為2,4-甲苯二異氰酸酯之改性體。 Among these isocyanate-based crosslinking agents, from the viewpoint of physical properties of the adhesive, it is preferably selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 2,6-. Toluene diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, and one or more of these modified bodies, particularly preferably 2,4-toluene A modified body of isocyanate.

此異氰酸酯系交聯劑，相對於100質量份之該丙烯酸系共聚物(A)，較佳為以0.01~10質量份的比例使用。 The isocyanate crosslinking agent is preferably used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the acrylic copolymer (A).

(不具有芳香環之磷酸酯系難燃劑(B1)) (phosphate-free flame retardant (B1) without aromatic ring)

本發明所用之黏著劑組成物包含前述丙烯酸系共聚物(A)，和不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)。 The adhesive composition used in the present invention comprises the above-mentioned acrylic copolymer (A), a phosphate-based flame retardant (B1) having no aromatic ring, and a nitrogen-containing phosphate compound-based flame retardant (B2).

不具有芳香環之磷酸酯系難燃劑(B1)係具有下述通式(1)所表示的結構。 The phosphate-based flame retardant (B1) having no aromatic ring has a structure represented by the following formula (1).

(式中，R1、R2、R3及R4係各自獨立表示氫、碳數1~12的烷基、或碳數3~12的環烷基；D係表示可具有取代基之碳數1~5的伸烷基或可具有取代基之碳數1~5的伸氧烷基；n係0~3之數值，n為2以上的情況，複數的OR4可各自相同或相異；R1與R2、R2與R3、或R1與R3係可互相鍵結形成環，n為1以上的情況，R1、R2或R3與一個R4可互相鍵結形成環；此外，該環係可具有取代基)。 (wherein R 1 , R 2 , R 3 and R 4 each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms; and D represents a carbon which may have a substituent a number of 1 to 5 alkylene groups or an alkylene group having 1 to 5 carbon atoms which may have a substituent; n is a value of 0 to 3, and n is 2 or more, and the plural OR 4 may be the same or different ; R 1 and R 2 , R 2 and R 3 , or R 1 and R 3 may be bonded to each other to form a ring, and n is 1 or more, and R 1 , R 2 or R 3 may be bonded to one R 4 ; The ring is formed; in addition, the ring system may have a substituent).

通式(1)中，作為R1、R2、R3及R4所表示的碳數1~12的烷基之具體例，可舉出甲基、乙基、丙基、異丙基、各種的丁基、戊基、己基、庚基、辛基、2-乙基己基、壬基、癸基、十一基、十二基等。於此等之中，較佳為碳數2~10的烷基，更佳為碳數4~8的烷基。 In the general formula (1), specific examples of the alkyl group having 1 to 12 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include a methyl group, an ethyl group, a propyl group and an isopropyl group. Various butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, undecyl, dodecyl and the like. Among these, an alkyl group having 2 to 10 carbon atoms is preferred, and an alkyl group having 4 to 8 carbon atoms is more preferred.

又，作為R1、R2、R3及R4所表示的碳數3~12的環烷基之具體例，可舉出環丙基、環丁基、環戊基、環己基、環辛基、環壬基、環癸基、環十二基等。於此等之中，較佳為碳數5~8的環烷基，更佳為碳數5~6的環烷基。 Further, specific examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Base, cyclodecyl, cyclodecyl, cyclododeyl and the like. Among these, a cycloalkyl group having 5 to 8 carbon atoms is preferred, and a cycloalkyl group having 5 to 6 carbon atoms is more preferred.

另外，於通式(1)中，R1與R2係可互相鍵結形成環，R2與R3、R1與R3亦同樣。n為1以上的情況，R1與1個R4可互相鍵結形成環，R2與1個R4、R3與1個R4亦同樣。 Further, in the formula (1), R 1 and R 2 may be bonded to each other to form a ring, and R 2 and R 3 , and R 1 and R 3 are also the same. When n is 1 or more, R 1 and 1 R 4 may be bonded to each other to form a ring, and R 2 and 1 R 4 and R 3 may be the same as 1 R 4 .

該環係環員碳數較佳為3~6。又，該環亦可具有1個以上的取代基，作為該取代基，可舉出碳數1~4的烷基或烷氧基等。 The ring ring member carbon number is preferably from 3 to 6. In addition, the ring may have one or more substituents, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and the like.

作為不具有芳香環之磷酸酯系難燃劑(B1)，較宜使用選自磷酸三丁酯(TBP)、磷酸三己酯、磷酸三環己酯、磷酸參(2-乙基己)酯(TOP)、磷酸三辛酯、磷酸三癸酯及縮合磷酸酯之至少一種。再者，於本發明中，所謂的縮合磷酸酯，就是指前述通式(1)中n為1~3之化合物或其混合物。 As a phosphate-based flame retardant (B1) having no aromatic ring, it is preferred to use a selected one selected from the group consisting of tributyl phosphate (TBP), trihexyl phosphate, tricyclohexyl phosphate, and bis(2-ethylhexyl) phosphate. (TOP), at least one of trioctyl phosphate, tridecyl phosphate, and condensed phosphate. Further, in the present invention, the term "condensed phosphate ester" means a compound of the above formula (1) wherein n is 1 to 3 or a mixture thereof.

於此等之中，磷含有率更佳為8~20質量%。此磷含有率若為8質量%以上，則難燃性良好，另一方面若為20質量%以下，則黏著性良好。 Among these, the phosphorus content is more preferably 8 to 20% by mass. When the phosphorus content is 8% by mass or more, the flame retardancy is good, and when the content is 20% by mass or less, the adhesiveness is good.

作為不具有芳香環之磷酸酯系難燃劑(B1)的市售品例，可舉出由大八化學工業股份有限公司所市售的磷酸三丁酯(TBP)、磷酸參(2-乙基己)酯(TOP)，及由大八化學工業股份有限公司所市售的非鹵素縮合磷酸酯之DAIGUARD 880等。此等不具有芳香環之磷酸酯系難燃劑(B1)係可為單獨1種或組合2種以上使用。 As a commercial example of the phosphate-based flame retardant (B1) which does not have an aromatic ring, tributyl phosphate (TBP) and phosphoric acid (2-B) which are commercially available from Daiba Chemical Industry Co., Ltd. are mentioned. Ethyl ester (TOP), and DAIGUARD 880, which is a non-halogen condensed phosphate commercially available from Daiba Chemical Industry Co., Ltd. These phosphate-based flame retardants (B1) which do not have an aromatic ring may be used alone or in combination of two or more.

(含氮之磷酸鹽化合物系難燃劑(B2)) (Nitrogen-containing phosphate compound is a flame retardant (B2))

含氮之磷酸鹽化合物系難燃劑(B2)係與前述不具有芳香環之磷酸酯系難燃劑(B1)組合使用。 The nitrogen-containing phosphate compound-based flame retardant (B2) is used in combination with the aforementioned phosphate-based flame retardant (B1) having no aromatic ring.

含氮之磷酸鹽化合物系難燃劑(B2)係沒有特別的限定，可舉出聚磷酸銨、磷酸三聚氰胺、磷酸二三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、磷酸酯醯胺、磷酸胍等。此等含氮之磷酸鹽化合物係可為單獨1種或組合 2種以上使用。 The nitrogen-containing phosphate compound-based flame retardant (B2) is not particularly limited, and examples thereof include ammonium polyphosphate, melamine phosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, phosphine decylamine, and cesium phosphate. These nitrogen-containing phosphate compounds may be used alone or in combination Two or more types are used.

作為含氮之磷酸鹽化合物系難燃劑(B2)的市售品例，可舉出由ADEKA股份有限公司所市售之Adekastab FP-2200等。 As a commercial example of the nitrogen-containing phosphate compound-based flame retardant (B2), Adekastab FP-2200, which is commercially available from ADEKA Co., Ltd., and the like, may be mentioned.

於本發明之黏著片中，在構成黏著劑層的黏著劑組成物中，相對於100質量份之丙烯酸系共聚物(A)，不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)的合計量為40~90質量份，較佳為50~85質量份。該合計量少於40質量份時，難燃性不足，超過90質量份時，黏著特性降低。 In the adhesive sheet of the present invention, the phosphate-based flame retardant (B1) having no aromatic ring is contained in the adhesive composition constituting the adhesive layer with respect to 100 parts by mass of the acrylic copolymer (A). The total amount of the nitrogen phosphate compound-based flame retardant (B2) is 40 to 90 parts by mass, preferably 50 to 85 parts by mass. When the total amount is less than 40 parts by mass, the flame retardancy is insufficient, and when it exceeds 90 parts by mass, the adhesive properties are lowered.

於本發明中，從難燃性及黏著性能之觀點而言，前述黏著劑組成物較佳為以質量比計1：0.2~1：5，更佳1：0.5~1：2的比例，包含不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)。 In the present invention, the adhesive composition is preferably in a ratio of 1:0.2 to 1:5, more preferably 1:0.5 to 1:2, in terms of flame retardancy and adhesion performance. A phosphate-based flame retardant (B1) having no aromatic ring and a flame retardant (B2) containing a nitrogen-containing phosphate compound.

再者，該黏著劑組成物較佳為不含有鹵素化合物、銻化合物及含芳香族之磷酸酯系化合物之任一者。 Further, the adhesive composition preferably contains no halogen compound, an antimony compound or an aromatic phosphate-containing compound.

(其他成分) (other ingredients)

於該黏著劑組成物中，在不損害本發明的效果之範圍內，可摻合其他成分。作為其他成分，例如可舉出紫外線吸收劑、抗氧化劑、防腐劑、防黴劑、可塑劑、消泡劑及潤濕性調整劑等。 In the adhesive composition, other components may be blended insofar as the effects of the present invention are not impaired. Examples of other components include an ultraviolet absorber, an antioxidant, a preservative, an antifungal agent, a plasticizer, an antifoaming agent, and a wettability adjuster.

[剝離片] [Peeling sheet]

本發明之黏著片例如像第1圖(b)中所示，亦可在黏著劑層之上積層剝離片。 For example, as shown in Fig. 1(b), the adhesive sheet of the present invention may have a release sheet laminated on the adhesive layer.

作為本發明之黏著片中使用之剝離片，並沒有特別的限制，從操作容易性之觀點而言，較佳為在片基材上塗布有剝離劑之剝離片。剝離片係可為在片基材的兩面上塗布有剝離劑之經剝離處理者，也可為在片基材的僅單面上塗布有剝離劑之經剝離處理者。 The release sheet used in the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and from the viewpoint of ease of handling, a release sheet coated with a release agent on a sheet substrate is preferred. The release sheet may be a release treatment in which a release agent is applied to both surfaces of the sheet substrate, or may be a release treatment in which a release agent is applied to only one side of the sheet substrate.

作為剝離片所使用之片基材，例如可舉出玻璃紙、塗布紙、流延塗布紙等之紙基材；於此等紙基材上積層有聚乙烯等的熱塑性樹脂的積層紙；或聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等之聚酯薄膜；聚丙烯或聚乙烯等之聚烯烴薄膜等的塑膠薄膜等。 Examples of the sheet base material used for the release sheet include a paper base material such as cellophane, coated paper, and cast coated paper; and a laminated paper in which a thermoplastic resin such as polyethylene is laminated on the paper base material; or A polyester film such as ethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate; a plastic film such as a polyolefin film such as polypropylene or polyethylene.

作為剝離劑，例如可舉出烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等之橡膠系彈性體、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂、聚矽氧系樹脂等。 Examples of the release agent include a rubber-based elastomer such as an olefin resin, an isoprene resin, and a butadiene resin, a long-chain alkyl resin, an alkyd resin, a fluorine resin, and a polyoxyl Resin or the like.

剝離片之厚度係沒有特別的限制，通常為20~200μm，較佳為25~150μm。 The thickness of the release sheet is not particularly limited and is usually 20 to 200 μm, preferably 25 to 150 μm.

剝離片中之由剝離劑所構成的層之乾燥後的厚度係沒有特別的限定，但以溶液狀態塗布剝離劑時，較佳為0.01~2.0μm，更佳為0.03~1.0μm。使用塑膠薄膜作為剝離片的片基材時，該塑膠薄膜之厚度較佳為3~50μm，更佳為5~40μm。 The thickness of the layer formed of the release agent in the release sheet is not particularly limited. However, when the release agent is applied in a solution state, it is preferably 0.01 to 2.0 μm, more preferably 0.03 to 1.0 μm. When a plastic film is used as the sheet substrate of the release sheet, the thickness of the plastic film is preferably from 3 to 50 μm, more preferably from 5 to 40 μm.

[黏著片之製造方法] [Method of manufacturing adhesive sheet]

本發明之黏著片之製造方法係沒有特別的限定。 The method for producing the adhesive sheet of the present invention is not particularly limited.

作為第1圖(a)中所示的黏著片1a之製造方法，可舉出在基材11上塗布前述黏著劑組成物及使乾燥而形成黏 著劑層12a之製造方法，或在剝離片上塗布前述黏著劑組成物及使乾燥而成為黏著劑層12a，貼合該黏著劑層12a與基材11，一旦得到黏著片1b後，去除剝離片而製造之方法等。 As a method of producing the adhesive sheet 1a shown in Fig. 1(a), the above-described adhesive composition is applied onto the substrate 11 and dried to form a sticky layer. In the method for producing the coating layer 12a, the adhesive composition is applied onto the release sheet, and dried to form the adhesive layer 12a, and the adhesive layer 12a and the substrate 11 are bonded together. Once the adhesive sheet 1b is obtained, the release sheet is removed. And the method of manufacturing, etc.

又，作為第1圖(b)中所示的黏著片1b之製造方法，可舉出於製造上述黏著片1a後，在黏著劑層12a上積層剝離片13之製造方法，或在剝離片上塗布黏著劑組成物及使乾燥而成為黏著劑層12a，貼合該黏著劑層12a與基材11而製造之方法等。 Moreover, as a method of manufacturing the adhesive sheet 1b shown in Fig. 1(b), a method of manufacturing the release sheet 13 on the adhesive layer 12a after the production of the above-mentioned pressure-sensitive adhesive sheet 1a, or coating on the release sheet may be mentioned. The adhesive composition and a method of drying the adhesive layer 12a, bonding the adhesive layer 12a and the substrate 11, and the like.

作為第1圖(c)中所示的黏著片1c之製造方法，可舉出在基材11的一面上，塗布前述黏著劑組成物及使乾燥而形成黏著劑層12a後，在基材11的另一面上，同樣地形成黏著劑層12b之製造方法，或準備2片在剝離片上設有黏著劑層之片，貼合該片的黏著劑層與基材，一旦得到黏著片1b後，去除剝離片而製造之方法等。 The method for producing the adhesive sheet 1c shown in Fig. 1(c) includes the application of the above-described adhesive composition on one surface of the substrate 11 and drying to form the adhesive layer 12a. On the other side, a method of manufacturing the adhesive layer 12b is formed in the same manner, or two sheets having an adhesive layer on the release sheet are prepared, and the adhesive layer and the substrate of the sheet are bonded, and once the adhesive sheet 1b is obtained, A method of manufacturing a release sheet or the like.

於塗布黏著劑組成物之際，為了在基材上容易地形成厚度薄的黏著劑層，較佳為用有機溶劑稀釋該黏著劑組成物，調製適當的固體成分濃度之塗布液，將此塗布。 When the adhesive composition is applied, in order to easily form a thin adhesive layer on the substrate, it is preferred to dilute the adhesive composition with an organic solvent to prepare a coating liquid having an appropriate solid concentration, and apply the coating. .

作為所用之有機溶劑，可舉出甲苯、醋酸乙酯、甲基乙基酮等。 Examples of the organic solvent to be used include toluene, ethyl acetate, and methyl ethyl ketone.

於基材上或剝離片上形成黏著劑層之方法係沒有特別的限制，例如可舉出藉由眾所周知的塗布方法來形成摻合有上述有機溶劑之塗布液之方法。 The method of forming the pressure-sensitive adhesive layer on the substrate or on the release sheet is not particularly limited, and examples thereof include a method of forming a coating liquid in which the organic solvent is blended by a well-known coating method.

作為塗布方法，例如可舉出旋轉塗布法、噴灑塗布 法、棒塗布法、刮刀塗布法(knife coating)、輥塗布法、輥刀塗布法、刀塗布法(blade coating)、模具塗布法、凹版塗布法等之眾所周知的方法。 Examples of the coating method include spin coating and spray coating. A well-known method such as a method, a bar coating method, a knife coating method, a roll coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

又，於防止溶劑或低沸點成分之殘留，同時在已摻合交聯劑之情況，為了使交聯(反應)進行而展現黏著性，於塗布在基材或剝離片後，較佳為進行加熱處理。 Further, in order to prevent the solvent or the low-boiling component from remaining, and in the case where the crosslinking agent has been blended, in order to carry out the crosslinking (reaction), the adhesion is exhibited, and after application to the substrate or the release sheet, it is preferably carried out. Heat treatment.

[黏著片之物性] [The physical properties of the adhesive sheet]

如以上所製作的本發明之黏著片，係在以下的實施例記載之測定方法中，常溫(23℃、50%RH(相對濕度))的黏著力為8N/25mm以上，高溫(80℃)時黏著力為8N/25mm以上及難燃性以UL94規格計為VTM-0，可充分滿足常溫黏著力、高溫(80℃)黏著力及難燃性之全部。 The adhesive sheet of the present invention produced as described above is in the measurement method described in the following examples, and the adhesive force at normal temperature (23° C., 50% RH (relative humidity)) is 8 N/25 mm or more, and high temperature (80° C.). When the adhesion is 8N/25mm or more and the flame retardancy is VTM-0 according to the UL94 specification, it can fully satisfy the room temperature adhesion, high temperature (80 °C) adhesion and flame retardancy.

[實施例] [Examples]

其次，藉由實施例來更詳細說明本發明，惟本發明完全不受此等之例所限定。 The invention is described in more detail by way of examples, but the invention is not limited by the examples.

以下實施例之記載中所示的重量平均分子量(Mw)係使用東曹股份有限公司製「HLC-8020」，於下述之條件下測定，以標準聚苯乙烯換算所求得之值。 The weight average molecular weight (Mw) shown in the following examples was measured using the standard polystyrene conversion under the following conditions using "HLC-8020" manufactured by Tosoh Corporation.

(測定條件) (measurement conditions)

管柱：「TSK gel GMHXL(×2)」「TSK gel G2000HXL」(皆東曹股份有限公司製) Column: "TSK gel GMHXL (×2)" "TSK gel G2000HXL" (made by Tosoh Co., Ltd.)

管柱溫度：40℃ Column temperature: 40 ° C

展開溶劑：四氫呋喃 Developing solvent: tetrahydrofuran

流速：1.0mL/分鐘 Flow rate: 1.0 mL/min

檢測器：示差折射計 Detector: differential refractometer

又，實施例所得之黏著片的常溫黏著力試驗、高溫(80℃)時黏著力試驗及難燃性評價係藉由以下所示之方法進行。 Further, the room temperature adhesion test of the adhesive sheet obtained in the examples, the adhesion test at high temperature (80 ° C), and the evaluation of flame retardancy were carried out by the methods shown below.

(1)常溫黏著力試驗 (1) Normal temperature adhesion test

將剝離片剝離，於23℃、50%RH環境下，將經切割成25mm×300mm的上述黏著片之試驗片貼附於被附體(SUS304鋼板)，而作為黏著力試驗用樣品。根據JIS Z0237，藉由180°拉剝法，以300mm/分鐘的拉伸速度，測定貼附24小時後之黏著力。 The release sheet was peeled off, and the test piece of the above-mentioned adhesive sheet cut into 25 mm × 300 mm was attached to the attached body (SUS304 steel plate) under the environment of 23 ° C and 50% RH, and used as a sample for adhesion test. According to JIS Z0237, the adhesion after 24 hours of attachment was measured by a 180° peeling method at a stretching speed of 300 mm/min.

(2)高溫(80℃)時黏著力試驗 (2) Adhesion test at high temperature (80 ° C)

將剝離片剝離，於23℃、50%RH環境下，將經切割成25mm×300mm的上述黏著片之試驗片貼附於被附體(SUS304鋼板)，而作為黏著力試驗用樣品。將樣品在23℃、50%RH環境下1日調濕後，置入80℃的恆溫槽中1小時。然後，於80℃環境下，藉由180°拉剝法，以300mm/分鐘的拉伸速度，測定黏著力。 The release sheet was peeled off, and the test piece of the above-mentioned adhesive sheet cut into 25 mm × 300 mm was attached to the attached body (SUS304 steel plate) under the environment of 23 ° C and 50% RH, and used as a sample for adhesion test. The sample was conditioned at 23 ° C and 50% RH for 1 day, and then placed in a thermostat at 80 ° C for 1 hour. Then, the adhesion was measured at a stretching speed of 300 mm/min by a 180° peeling method at 80 °C.

(3)難燃性評價 (3) Flame retardancy evaluation

將所製作的黏著片之剝離片剝離，進行保險業實驗室公司發行的塑膠材料之難燃性試驗規格UL94的薄型材料垂直燃燒試驗方法中規定之試驗，判定VTM等級。評價所用的黏著片之樣品尺寸為50mm×200mm，以黏著劑層成為外側，進行試驗。 The release sheet of the produced adhesive sheet was peeled off, and the test specified in the vertical flame test method for the flame retardancy test of the plastic material issued by the Insurance Laboratory Co., Ltd. UL94 was carried out, and the VTM grade was determined. The sample size of the adhesive sheet used for the evaluation was 50 mm × 200 mm, and the test was performed with the adhesive layer being the outer side.

再者，VTM等級的判定基準係如下述。 Furthermore, the criterion for determining the VTM level is as follows.

VTM-0：樣品之燃燒時間為10秒以內，而且不因燃燒物或落下物而引起脫脂棉的著火，更且沒有看見至標 線(自樣品下端起125mm之位置)為止之燃燒。 VTM-0: The burning time of the sample is within 10 seconds, and the cotton wool does not catch fire due to burning or falling objects, and there is no visible to the standard. The burning of the wire (125 mm from the lower end of the sample).

VTM-1：樣品之燃燒時間為30秒以內，而且不因燃燒物或落下物而引起脫脂棉的著火，更且沒有看見至標線為止之燃燒。 VTM-1: The burning time of the sample is within 30 seconds, and the cotton wool does not catch fire due to burning or falling objects, and the burning to the marking line is not seen.

VTM-2：樣品之燃燒時間為30秒以內，而且沒有看見至標線為止之燃燒。 VTM-2: The burning time of the sample was within 30 seconds, and no burning was observed until the marking.

將符合VTM-0者當作合格，將其以外當作不合格。 Those who meet the VTM-0 are deemed to be qualified, and the others are deemed to be unqualified.

於本難燃性評價中，進行4次試驗，計數符合條件最嚴格的VTM-0之次數。例如，於表1之難燃性評價中，「3/4」之記載係表示進行4次試驗之中，符合VTM-0之次數為3次者。 In the evaluation of the flame retardancy, four tests were carried out, and the number of times the most stringent VTM-0 was counted was counted. For example, in the evaluation of the flame retardancy in Table 1, the description of "3/4" indicates that the number of times of VTM-0 is three times among the four tests.

製造例1 Manufacturing example 1

(丙烯酸系共聚物溶液1之調製) (Modulation of Acrylic Copolymer Solution 1)

將作為單體成分之80質量份的丙烯酸丁酯及20質量份的丙烯酸、作為溶劑之200質量份的醋酸乙酯、作為聚合引發劑之0.2質量份的偶氮雙異丁腈加入反應器中及混合。以氮氣進行4小時脫氣，徐徐升溫至60℃為止後，邊攪拌24小時邊進行聚合反應，得到含有重量平均分子量為60萬之丙烯酸系共聚物1的醋酸乙酯溶液(固體成分濃度33質量%)。 80 parts by mass of butyl acrylate and 20 parts by mass of acrylic acid as a monomer component, 200 parts by mass of ethyl acetate as a solvent, and 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator are charged into the reactor. And mixing. After degassing for 4 hours under nitrogen gas, and gradually raising the temperature to 60 ° C, the polymerization reaction was carried out while stirring for 24 hours to obtain an ethyl acetate solution containing an acrylic copolymer 1 having a weight average molecular weight of 600,000 (solid content concentration 33 mass). %).

製造例2 Manufacturing Example 2

(丙烯酸系共聚物溶液2之調製) (Modulation of Acrylic Copolymer Solution 2)

除了使用75質量份的丙烯酸丁酯及25質量份的丙烯酸作為單體成分以外，與製造例1同樣地進行聚合反應，得到含有重量平均分子量為60萬之丙烯酸系共聚物2的 醋酸乙酯溶液(固體成分濃度33質量%)。 A polymerization reaction was carried out in the same manner as in Production Example 1 except that 75 parts by mass of butyl acrylate and 25 parts by mass of acrylic acid were used as the monomer component, thereby obtaining an acrylic copolymer 2 having a weight average molecular weight of 600,000. Ethyl acetate solution (solid content concentration: 33% by mass).

製造例3 Manufacturing Example 3

(丙烯酸系共聚物溶液3之調製) (Modulation of Acrylic Copolymer Solution 3)

除了使用70質量份的丙烯酸丁酯及30質量份的丙烯酸作為單體成分以外，與製造例1同樣地進行聚合反應，得到含有重量平均分子量為60萬之丙烯酸系共聚物3的醋酸乙酯溶液(固體成分濃度33質量%)。 A polymerization reaction was carried out in the same manner as in Production Example 1 except that 70 parts by mass of butyl acrylate and 30 parts by mass of acrylic acid were used as the monomer component, thereby obtaining an ethyl acetate solution containing the acrylic copolymer 3 having a weight average molecular weight of 600,000. (solid content concentration: 33% by mass).

製造例4 Manufacturing Example 4

(丙烯酸系共聚物溶液4之調製) (Modulation of Acrylic Copolymer Solution 4)

除了使用90質量份的丙烯酸丁酯及10質量份的丙烯酸作為單體成分以外，與製造例1同樣地進行聚合反應，得到含有重量平均分子量為65萬之丙烯酸系共聚物4的醋酸乙酯溶液(固體成分濃度33質量%)。 A polymerization reaction was carried out in the same manner as in Production Example 1 except that 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were used as the monomer component, thereby obtaining an ethyl acetate solution containing the acrylic copolymer 4 having a weight average molecular weight of 650,000. (solid content concentration: 33% by mass).

實施例1 Example 1

(黏著片之製作) (production of adhesive sheets)

以固體成分濃度成為10質量%之方式，用醋酸乙酯稀釋100質量份(固體成分)的製造例1所得之含有丙烯酸系共聚物1的醋酸乙酯溶液、2.2質量份(固體成分)作為交聯劑的異氰酸酯系交聯劑(日本聚胺基甲酸酯股份有限公司製，商品名「Coronate L」，三羥甲基丙烷改性甲苯二異氰酸酯之醋酸乙酯溶液(固體成分75質量%))、40質量份作為磷酸酯系難燃劑的磷酸參(2-乙基己)酯(大八化學工業股份有限公司製，商品名「TOP」)、及30質量份的含氮之磷酸鹽系難燃劑(ADEKA股份有限公司製，商品名「Adekastab FP-2200」)之混合物，而調製黏著劑組成 物之溶液。 100 parts by mass (solid content) of the ethyl acetate solution containing the acrylic copolymer 1 obtained in Production Example 1 and 2.2 parts by mass (solid content) were diluted with ethyl acetate to have a solid content of 10% by mass. Isocyanate-based crosslinking agent (manufactured by Japan Polyurethane Co., Ltd., trade name "Coronate L", ethyl acetate solution of trimethylolpropane-modified toluene diisocyanate (solid content: 75 mass%) 40 parts by mass of phosphoric acid phosphatide (2-ethylhexyl) ester (manufactured by Daiba Chemical Industry Co., Ltd., trade name "TOP"), and 30 parts by mass of nitrogen-containing phosphate A mixture of a flame retardant (made by ADEKA Co., Ltd., trade name "Adekastab FP-2200"), and a modified adhesive composition a solution of the substance.

將此溶液塗布在剝離片之經聚矽氧處理的38μm聚酯薄膜(LINTEC股份有限公司製，商品名「SP-PET381031」)上，而使乾燥後的黏著劑層之厚度成為20μm，於100℃乾燥1分鐘後，轉印至基材之在兩面上塗布有聚醯亞胺樹脂的聚對苯二甲酸乙二酯(PET)薄膜(東麗股份有限公司製，商品名「Lumirror ZV30 #40」，厚度：47μm，符合UL94規格中規定之試驗VTM-0)，於23℃、50%RH環境下進行7日風乾，而製作黏著片。 This solution was applied to a polyfluorene-treated 38 μm polyester film (manufactured by LINTEC Co., Ltd., trade name "SP-PET381031"), and the thickness of the dried adhesive layer was 20 μm at 100 After drying at ° C for 1 minute, a polyethylene terephthalate (PET) film coated with a polyimide resin on both surfaces was transferred to a substrate (manufactured by Toray Industries, Inc., trade name "Lumirror ZV30 #40 The thickness: 47 μm, in accordance with the test VTM-0 specified in the UL94 specification, was air-dried at 23 ° C, 50% RH for 7 days to prepare an adhesive sheet.

再者，黏著片的各層之厚度以及總厚度，係使用TECLOCK股份有限公司製之恆壓厚度測定機PG-02J來測定。 Further, the thickness and total thickness of each layer of the adhesive sheet were measured using a constant pressure thickness measuring machine PG-02J manufactured by TECLOCK Co., Ltd.

實施例2~7及比較例1~10 Examples 2 to 7 and Comparative Examples 1 to 10

除了將黏著劑組成變更為如表1之記載以外，用與實施例1同樣之方法來製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the composition of the adhesive was changed to the one shown in Table 1.

表2中顯示實施例1~7及比較例1~10所得之黏著片的常溫黏著力、高溫(80℃)時黏著力及難燃性評價結果。 Table 2 shows the results of evaluation of the room temperature adhesion of the adhesive sheets obtained in Examples 1 to 7 and Comparative Examples 1 to 10, the adhesion at high temperature (80 ° C), and the flame retardancy.

表1中的主劑(丙烯酸系共聚物)、交聯劑、難燃劑之詳細係如以下。 The details of the main component (acrylic copolymer), the crosslinking agent, and the flame retardant in Table 1 are as follows.

BA：丙烯酸丁酯 BA: butyl acrylate

AAc：丙烯酸 AAc: Acrylic

交聯劑：異氰酸酯系交聯劑(日本聚胺基甲酸酯股份有限公司製，商品名「Coronate L」，三羥甲基丙烷改性甲苯二異氰酸酯之醋酸乙酯溶液(固體成分75質量%)) Crosslinking agent: isocyanate-based crosslinking agent (manufactured by Japan Polyurethane Co., Ltd., trade name "Coronate L", trimethylolpropane-modified toluene diisocyanate ethyl acetate solution (solid content: 75% by mass) ))

難燃劑(B1)：不具有芳香環之磷酸酯系難燃劑 Flame Retardant (B1): Phosphate-based flame retardant without aromatic ring

‧TOP：磷酸參(2-乙基己)酯(大八化學工業股份有限公司製，TOP) ‧TOP: Phosphate (2-ethylhexyl) ester (made by Daiba Chemical Industry Co., Ltd., TOP)

‧TBP：磷酸三丁酯(大八化學工業股份有限公司製，TBP) ‧TBP: Tributyl phosphate (Duba Chemical Industry Co., Ltd., TBP)

‧DAIGUARD 880(大八化學工業股份有限公司製，非含有芳香環之縮合磷酸酯系難燃劑) ‧DAIGUARD 880 (made by Daiba Chemical Industry Co., Ltd., condensed phosphate ester-free flame retardant containing no aromatic ring)

(B1)以外之磷酸酯系難燃劑 Phosphate-based flame retardant other than (B1)

‧BDP：雙酚A磷酸雙二苯酯(大八化學工業股份有限公司製，CR-741) ‧BDP: bisphenol A bis-diphenyl phosphate (made by Daiba Chemical Industry Co., Ltd., CR-741)

難燃劑(B2)：含氮之磷酸鹽化合物系難燃劑(ADEKA股份有限公司製，Adekastab FP-2200) Flame Retardant (B2): Nitrogen-containing phosphate compound is a flame retardant (Adekastab FP-2200, manufactured by ADEKA Co., Ltd.)

[產業上之可利用性] [Industrial availability]

依照本發明，可提供不使用在焚化時發生有毒之含鹵系氣體的鹵系難燃劑與被指出對人體有不良影響之氧化銻，以及有產生被指出為內分泌攪亂化學物質的雙酚A等之虞的含芳香族之磷酸酯系難燃劑，且具有優異的難燃性與黏著特性以及高溫時黏著特性之難燃性黏著片。 According to the present invention, it is possible to provide a halogen-based flame retardant which does not use a toxic halogen-containing gas during incineration, a cerium oxide which is indicated to have an adverse effect on the human body, and a bisphenol A which is produced as an endocrine disrupting chemical substance. A flame retardant adhesive sheet containing an aromatic phosphate-based flame retardant and having excellent flame retardancy and adhesion properties and adhesive properties at high temperatures.

1a、1b、1c‧‧‧黏著片 1a, 1b, 1c‧‧‧ Adhesive tablets

11‧‧‧基材 11‧‧‧Substrate

12a、12b‧‧‧黏著劑層 12a, 12b‧‧‧Adhesive layer

13a‧‧‧剝離片 13a‧‧‧ peeling film

Claims (7)

一種黏著片，其係在基材的至少一面上具有黏著劑層之黏著片，其特徵為該黏著劑層係由包含丙烯酸系共聚物(A)、與下述通式(1)所表示的不具有芳香環之磷酸酯系難燃劑(B1)、與含氮之磷酸鹽化合物系難燃劑(B2)之黏著劑組成物所構成，丙烯酸系共聚物(A)係包含來自(甲基)丙烯酸烷酯的構成單元(a1)、以及來自選自包含(甲基)丙烯酸、巴豆酸、富馬酸及馬來酸之群組中之一種以上的含有羧基之單體的構成單元(a2)作為單體單元之共聚物，丙烯酸系共聚物(A)以15~35質量%的比例包含構成單元(a2)，丙烯酸系共聚物(A)中的構成單元(a1)與構成單元(a2)的質量比為85/15~65/35，含氮之磷酸鹽化合物系難燃劑(B2)係選自包含聚磷酸銨、磷酸三聚氰胺、磷酸二三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺及磷酸胍之群組中的一種以上，且該黏著劑組成物中，相對於100質量份之丙烯酸系共聚物(A)，不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)的合計量為40~90質量份， (式中，R1、R2、R3及R4係各自獨立表示氫、碳數4~12的烷基、或碳數3~12的環烷基；D係表示可具有取代基之碳數1~5的伸烷基或可具有取代基之碳數1~5的伸氧烷基(oxyalkylene)；n係0~3之數值，n為2以上 的情況，複數的OR4可各自相同或相異；R1與R2、R2與R3、或R1與R3係可互相鍵結形成環，n為1以上的情況，R1、R2、或R3與一個R4可互相鍵結形成環；此外，該環係可具有取代基；惟，R1、R2、R3及R4不全部為氫)。 An adhesive sheet comprising an adhesive sheet having an adhesive layer on at least one side of a substrate, characterized in that the adhesive layer is composed of an acrylic copolymer (A) and represented by the following formula (1) The phosphate-based flame retardant (B1) which does not have an aromatic ring, and the adhesive composition of the nitrogen-containing phosphate compound-based flame retardant (B2), and the acrylic copolymer (A) contains (meth) a constituent unit (a1) of an alkyl acrylate, and a constituent unit derived from a carboxyl group-containing monomer selected from the group consisting of (meth)acrylic acid, crotonic acid, fumaric acid, and maleic acid (a2) In the copolymer of the monomer unit, the acrylic copolymer (A) contains the constituent unit (a2) in a ratio of 15 to 35% by mass, and the constituent unit (a1) and the constituent unit (a2) in the acrylic copolymer (A). The mass ratio is 85/15~65/35, and the nitrogen-containing phosphate compound flame retardant (B2) is selected from the group consisting of ammonium polyphosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate and phosphoric acid. One or more of the group of cockroaches, and the adhesive composition is relative to 100 parts by mass Acid-based copolymer (A), having no phosphate-based flame retardant (B1) with a nitrogen-containing aromatic ring of the total amount of the phosphate compound-based flame retardant (B2) is 40 to 90 parts by mass, (wherein R 1 , R 2 , R 3 and R 4 each independently represent hydrogen, an alkyl group having 4 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms; and D represents a carbon which may have a substituent An alkylene group having 1 to 5 or an oxyalkylene having 1 to 5 carbon atoms which may have a substituent; n is a value of 0 to 3, and n is 2 or more, and the plural OR 4 may be the same Or different; R 1 and R 2 , R 2 and R 3 , or R 1 and R 3 may be bonded to each other to form a ring, n is 1 or more, R 1 , R 2 , or R 3 and one R 4 The rings may be bonded to each other to form a ring; in addition, the ring system may have a substituent; however, R 1 , R 2 , R 3 and R 4 are not all hydrogen). 如請求項1之黏著片，其中黏著劑組成物不含有鹵素化合物、銻化合物、及含芳香族之磷酸酯系化合物之任一者。 The adhesive sheet of claim 1, wherein the adhesive composition does not contain any one of a halogen compound, a hydrazine compound, and an aromatic phosphate-containing compound. 如請求項1或2之黏著片，其中不具有芳香環之磷酸酯系難燃劑(B1)為選自磷酸三丁酯、磷酸三己酯、磷酸三環己酯、磷酸參(2-乙基己)酯、磷酸三辛酯、磷酸三癸酯、及縮合磷酸酯之至少一種。 The adhesive sheet of claim 1 or 2, wherein the phosphate-based flame retardant (B1) having no aromatic ring is selected from the group consisting of tributyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, and phosphoric acid (2-B) At least one of a hexyl ester, a trioctyl phosphate, a tridecyl phosphate, and a condensed phosphate. 如請求項1或2之黏著片，其中不具有芳香環之磷酸酯系難燃劑(B1)之磷含有率為8~20質量%。 The adhesive sheet of claim 1 or 2, wherein the phosphate-containing flame retardant (B1) having no aromatic ring has a phosphorus content of 8 to 20% by mass. 如請求項1或2之黏著片，其中構成丙烯酸系共聚物(A)之來自(甲基)丙烯酸烷酯的構成單元(a1)之側鏈碳數為7以下。 The adhesive sheet of claim 1 or 2, wherein the constituent unit (a1) derived from the alkyl (meth)acrylate constituting the acrylic copolymer (A) has a side chain carbon number of 7 or less. 如請求項1或2之黏著片，其中黏著劑組成物係以質量比計為1：0.2~1：5的比例包含不具有芳香環之磷酸酯系難燃劑(B1)與含氮之磷酸鹽化合物系難燃劑(B2)。 The adhesive sheet of claim 1 or 2, wherein the adhesive composition comprises a phosphate-based flame retardant (B1) having no aromatic ring and a nitrogen-containing phosphoric acid in a ratio of 1:0.2 to 1:5 by mass ratio. The salt compound is a flame retardant (B2). 如請求項1或2之黏著片，其中基材具有符合UL94規格中規定之試驗VTM-0之難燃性。 The adhesive sheet of claim 1 or 2, wherein the substrate has a flame retardancy in accordance with the test VTM-0 specified in the UL94 specification.
TW102139146A 2012-10-29 2013-10-29 Adhesive sheet TWI605102B (en)

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