CN103874739A - Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component - Google Patents

Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component Download PDF

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CN103874739A
CN103874739A CN 201280050873 CN201280050873A CN103874739A CN 103874739 A CN103874739 A CN 103874739A CN 201280050873 CN201280050873 CN 201280050873 CN 201280050873 A CN201280050873 A CN 201280050873A CN 103874739 A CN103874739 A CN 103874739A
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thermally conductive
sensitive adhesive
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熊本拓朗
北川明子
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日本瑞翁株式会社
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications
    • C09J2203/30Use of the adhesive tape
    • C09J2203/326Use of the adhesive tape for bonding electronic components such as wafers, chips or semiconductors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2205/00Other features
    • C09J2205/10Other features of adhesive tapes; Production process thereof
    • C09J2205/102Other features of adhesive tapes; Production process thereof additives as essential feature of the adhesive layer, the additive itself being indicated with the corresponding code of C08K
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of acrylic polymer
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/34Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737Organic materials with or without a thermoconductive filler
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

This mixed composition contains 100 parts by mass of a (methyl)acrylate resin composition (A) containing (methyl)acrylate acid ester polymers (A1) and (methyl)acrylate acid ester monomers (alpha1), 90-1200 parts by mass of a thermally conductive filler (B), 0.2-8 parts by mass of polyfunctional monomers (D) having multiple polymerizable unsaturated bonds, and 0.3-5.0 parts by mass of a polyfunctional epoxy compound (E) having 2 to 10000 functional groups and a viscosity at 25 DEG C of 600mPa*s or less. This composition is characterized by performing a polymerization reaction between the (methyl)acrylate acid ester monomers (alpha1) and the polyfunctional monomers (D), and a crosslinking reaction of the (methyl)acrylate acid ester polymers (A1) and/or polymers containing structural units derived from the (methyl)acrylate acid ester monomers (alpha1).

Description

导热性压敏粘接剂组合物、导热性压敏粘接性片状成形体、 The thermally conductive pressure-sensitive adhesive composition, the thermally conductive pressure-sensitive adhesive sheet materials,

它们的制造方法以及电子部件 A manufacturing method thereof and an electronic component

技术领域 FIELD

[0001] 本发明涉及导热性压敏粘接剂组合物、导热性压敏粘接性片状成形体、它们的制造方法、以及具备该导热性压敏粘接剂组合物或者该导热性压敏粘接性片状成形体的电子部件。 [0001] The present invention relates to a thermally conductive pressure-sensitive adhesive composition, the thermally conductive pressure-sensitive adhesive sheet materials, methods of their manufacture, including the thermally conductive and pressure-sensitive adhesive composition or the thermally conductive pressure sensitive adhesive sheet-shaped molded electronic component.

背景技术 Background technique

[0002] 近年来,对于等离子体显示面板(PDP)、集成电路(IC)芯片等这样的电子部件,伴随其高性能化发热量增大。 [0002] In recent years, the plasma display panel such electronic component (PDP), an integrated circuit (IC) chip or the like, which is accompanied by high performance heat increases. 其结果,需要采取由于温度上升而导致的功能障碍的对策。 As a result, it is necessary to take countermeasures dysfunction due to the temperature rise caused. 通常而言,采用将金属制的散热器、散热板、散热片等散热体安装于电子部件等中所具备的发热体上,从而使其散热的方法。 Generally, the use of a metallic heat sink, the heat radiating plate, and heat sinks mounted on the radiator heating element provided in the electronic component and the like, so that it cooling method. 为了有效地进行从发热体向散热体的导热,使用导热性高的片状的构件(导热片)。 For effective thermal conductivity from the heating body to the radiator, the high thermal conductivity of the sheet-like member (heat sheet). 通常而言,在将发热体和散热体进行固定的用途中,需要除了导热性之外还具有压敏粘接性的组合物(以下称为“导热性压敏粘接剂组合物”)、或片状的构件(以下称为“导热性压敏粘接性片状成形体”)。 In general, use of fixed in the heat generator and the radiator, the thermal conductivity is also required in addition to the pressure sensitive adhesive composition (hereinafter referred to as "thermally conductive pressure-sensitive adhesive composition"), or a sheet-like member (hereinafter referred to as "pressure-sensitive adhesive sheet-like thermally conductive molded article").

[0003] 上述导热性压敏粘接剂组合物以及导热性压敏粘接性片状成形体以从发热体向散热体传导热作为目的之一而使用,因而要求能够密合于发热体以及散热体的柔软性。 [0003] The thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet-like thermally conductive molded article as an object of heat conduction from the heating member to the heat transfer medium used, thus requiring the heat generating member capable of adhesion, and the flexibility of the heat sink. 作为涉及柔软性优异的导热性压敏粘接性片状成形体的技术,例如有专利文献I中公开的阻燃性散热片、专利文献2中公开的导热片。 As relates to the flexibility of the thermally conductive pressure-sensitive adhesive sheet-like molded article having excellent techniques, for example, disclosed in Patent Document I fins flame retardant, Patent Document 2 discloses a thermally conductive sheet.

[0004] 现有技术文献专利文献 [0004] PRIOR ART DOCUMENTS Patent Documents

专利文献1:日本特开2006-176640号公报专利文献2:日本特开2010-132856号公报。 Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-176640 Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-132856.

发明内容 SUMMARY

[0005] 发明要解决的问题 [0005] Problems to be solved

为了使用导热性压敏粘接剂组合物或导热性压敏粘接性片状成形体有效地将热从发热体向散热体传导,如上所述,可以考虑提高柔软性从而提高发热体与散热体的密合性。 In order to use the thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive or a thermally conductive sheet materials efficiently heat from the heating member to heat the conductive member, as described above, can be considered to improve the flexibility of the heat generator and the radiator to improve adhesion thereof. 另外,为了使用导热性压敏粘接剂组合物或导热性压敏粘接性片状成形体有效地从发热体向散热体传导热,例如,可以考虑将它们薄薄地成形从而降低厚度方向的热阻。 Further, in order to use the thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive or a thermally conductive sheet materials effectively conduct heat from the heat generating body into the heat sink, for example, they may be considered to reduce the thickness of the thin molded direction thermal resistance.

[0006] 然而,以往的导热性压敏粘接剂组合物或导热性压敏粘接性片状成形体存在以下问题:若薄薄地成形,则难以获得作为制品而要求的拉伸强度。 [0006] However, the presence of conventional thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive or a thermally conductive sheet materials the following question: if the thinly formed, it is difficult to obtain as a product of the tensile strength requirements. 另外,欲调整组成使其具有拉伸强度时,硬度也增加,柔软性受损。 Further, the composition to be adjusted so as to have a tensile strength, hardness increases, the flexibility is impaired. 若变硬,则有可能在与被粘体之间发生空气混入等从而从发热体向散热体的传热效率变差。 When hardened, there may be mixed in with the air between the adherend and the like so as to deteriorate the efficiency of heat transfer from the heating member to the heat sink. 由此,对于以往的技术,使导热性压敏粘接剂组合物或导热性压敏粘接性片状成形体薄薄地成形时,难以兼具柔软性和拉伸强度。 Accordingly, the conventional technology, so that the thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive or a thermally conductive sheet-shaped thin molded into time, difficult to achieve both flexibility and tensile strength.

[0007] 因此,本发明的课题在于,提供即使薄薄地成形也能够具备柔软性和拉伸强度的导热性压敏粘接剂组合物以及导热性压敏粘接性片状成形体、和它们的制造方法、以及具备该导热性压敏粘接剂组合物或该导热性压敏粘接性片状成形体的电子部件。 [0007] Accordingly, an object of the present invention is to provide a thin molding can be even provided with flexibility and tensile strength of the thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet materials, and their the manufacturing method including the thermally conductive and pressure-sensitive adhesive composition or a pressure-sensitive adhesive property of the thermally conductive sheet materials of the electronic component.

[0008] 解决问题的技术手段 [0008] problem-solving techniques

本发明的第I方式为导热性压敏粘接剂组合物(F),其为含有100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、90质量份以上且1200质量份以下的导热性填料(Β)、0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、和0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa-s以下的多官能环氧化合物(E)的混合组合物,其进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应而成。 I first embodiment of the present invention is a thermally conductive pressure-sensitive adhesive composition (F), which is a (meth) acrylate polymer (Al) containing 100 parts by mass, and (meth) acrylate monomers ([alpha] I), (meth) acrylic resin composition ([alpha]), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (Beta), 0.2 parts by mass or more and 8 parts by mass or less having a plurality of polymerizable unsaturated a polyfunctional monomer (D) of the key, and 0.3 parts by mass 5.0 parts by mass or more and having the following functional groups of 2 to 10,000 and having a viscosity at 25 ° C, 600mPa-s or less polyfunctional epoxy compound (E ) mixed composition, which was (meth) acrylate monomer (α I) a polyfunctional monomer and (D) a polymerization reaction, and (meth) acrylate polymer (Al) and / or a source comprising crosslinking the polymer (meth) acrylate monomer of the structural unit (α I) from the reaction.

[0009] 本说明书中“(甲基)丙烯酸”表示“丙烯酸和/或甲基丙烯酸”。 [0009] In the present specification, "(meth) acrylic" means "acrylic and / or methacrylic acid." “导热性填料(B)”是指,通过添加能够提高导热性压敏粘接剂组合物(F)或者之后说明的导热性压敏粘接性片状成形体(G)的导热性的、导热系数在lW/mK以上的填料。 "Thermally conductive filler (B)" refers to, can be improved by adding thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive sheet-like pressure-sensitive adhesive described later molded into a thermal conductivity (G), and the thermal conductivity of the filler in lW / mK or more. “(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应”是指,(甲基)丙烯酸酯单体(α I)与多官能性单体(D)的共聚反应、(甲基)丙烯酸酯单体(α I)的聚合反应、以及多官能性单体(D)的聚合反应中的一种或多种聚合反应。 "(Meth) acrylate monomer (α I) and polymerization reaction of the polyfunctional monomer (D)" refers to, (meth) acrylate monomer (α I) and a polyfunctional monomer (D) copolymerization reaction, the polymerization reaction of (meth) acrylate monomer (α I) of the polymerization reaction, and the polyfunctional monomer (D) in one or more polymerization. “(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应”是指,(甲基)丙烯酸酯聚合物(Al)彼此的交联反应、含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物彼此的交联反应、以及(甲基)丙烯酸酯聚合物(Al)与含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应中的一种或者多种交联反应。 "(Meth) acrylate polymer (Al) and / or derived containing (meth) crosslinking reaction of the polymer structural units of the acrylate monomer (α I)" means, (meth) acrylates polymer (Al) a crosslinking reaction with each other, containing a crosslinking reaction with each other, and (meth) acrylate polymer (Al) derived from a (meth) acrylate structural unit of the polymer monomer (α I) of the (meth) reaction of a crosslinked polymer of an acrylate monomer structural unit (α I) or more in the crosslinking reactions containing derived.

[0010] 本发明的第2方式为导热性压敏粘接性片状成形体(G),其将包含100质量份的含有(甲基)丙烯酸酯聚合物( Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(A)、90质量份以上且1200质量份以下的导热性填料(Β)、0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、和0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa-s以下的多官能环氧化合物 [0010] The second embodiment of the present invention is a thermally conductive pressure-sensitive adhesive sheet-like molded article (G), which comprises 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylic acid ester monomers (α I) of the (meth) acrylic resin composition (a), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (Beta), 0.2 parts by mass or more and 8 parts by mass or less having a plurality polymerizable unsaturated bond of a polyfunctional monomer (D), and 0.3 parts by mass or more and having a 5.0 parts by mass or less of functional groups of 2 or more and 10,000 or less and a viscosity at 25 ° C, a polyfunctional 600mPa-s or less an epoxy compound

(E)的混合组合物成形为片状后,或者在将该混合组合物成形为片状的同时,进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应而成。 After the (E) mixed composition into a sheet, or sheet-like molded simultaneously in the mixed composition, a (meth) acrylate monomer (α I) and the polyfunctional monomer (D), polymerization, and (meth) acrylate polymer (Al) and / or derived containing (meth) crosslinked polymer structural units of the acrylate monomer (α I) from the reaction.

[0011] 本发明的第3方式是导热性压敏粘接剂组合物(F)的制造方法,其包含如下工序:制作包含(Α)、(B)、(D)、(E)的混合组合物的工序,所述(Α)、(B)、(D)、(E)为:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(A)、90质量份以上且1200质量份以下的导热性填料(Β)、0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、和0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E);以及、在该混合组合物中,进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应的工序。 [0011] In a third embodiment of the present invention is a method for producing the thermally conductive pressure-sensitive adhesive composition (F), comprising the steps of: making comprising (Α), (B), (D), (E) a mixed step composition, the (Α), (B), (D), (E) as follows: 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomer ( α I) of the (meth) acrylic resin composition (a), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (Beta), 0.2 parts by mass or more and 8 parts by mass or less having a plurality of polymerizable not a polyfunctional monomer (D) an unsaturated bond, and 0.3 parts by mass 5.0 parts by mass or more and having the following functional groups of 2 to 10,000 and having a viscosity at 25 ° C, or less 600mPa s polyfunctional epoxy compound (E ); and, in the mixed composition, a (meth) acrylate monomer (α I) and polyfunctional monomer (D) polymerization, (meth) acrylate polymer (Al) and / containing or derived from a (meth) step of the crosslinking reaction of the polymer structural units of the acrylate monomer (α I) of.

[0012] 本发明的第4方式为导热性压敏粘接性片状成形体(G)的制造方法,其包含如下工序:制作包含(Α)、(B)、(D)、(E)的混合组合物的工序,所述(Α)、(B)、(D)、(E)为:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、90质量份以上且1200质量份以下的导热性填料(Β)、0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、和0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa_s以下的多官能环氧化合物(E);以及、在将该混合组合物成形为片状后,或者在将该混合组合物成形为片状的同时,进行(甲基)丙烯酸酯单体UI)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应的工序。 [0012] In a fourth embodiment of the present invention is a pressure-sensitive adhesive sheet-like thermally conductive molded body manufacturing method (G), comprising the steps of: making comprising (Α), (B), (D), (E) the step of mixing the composition, the (Α), (B), (D), (E) as follows: 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomers (meth) acrylic resin composition of the material (α I) of the ([alpha]), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (Beta), 0.2 parts by mass or more and 8 parts by mass or less having a plurality of polymerization polyfunctional monomers unsaturated bond (D), and 0.3 parts by mass or more and having a functional group of 2 or more and 10000 or less parts by mass or less and 5.0 or less 600mPa_s polyfunctional epoxy compound viscosity at 25 ° C ( E); and, in the mixed composition was molded into a sheet, or the mixed composition was formed into a sheet simultaneously, be (meth) acrylate monomer UI) and a polyfunctional monomer (D ) and / or derived containing (meth) step of the crosslinking reaction of the polymer structural units of the acrylate monomer (α I) of the polymerization reaction, and (meth) acrylate polymer (Al).

[0013] 本发明的第5方式为电子部件,其具备散热体和贴合于该散热体的本发明的第I方式的导热性压敏粘接剂组合物(F)、或者具备散热体和贴合于该散热体的本发明的第2方式的导热性压敏粘接性片状成形体(G)。 [0013] The fifth embodiment of the present invention is an electronic component that includes a heat sink and a heat conductive pressure-sensitive adhesive composition (F) is bonded to a first embodiment I of the present invention the heat sink, or radiator and comprising the pressure-sensitive adhesive sheet-like thermally conductive properties of the second embodiment of the present invention is bonded to the molded radiator (G).

[0014] 发明效果 [0014] Effect of the Invention

根据本发明可以提供即使薄薄地成形也能够具有柔软性和拉伸强度的导热性压敏粘接剂组合物以及导热性压敏粘接性片状成形体、和它们的制造方法、以及具备该导热性压敏粘接剂组合物或者该导热性压敏粘接性片状成形体的电子部件。 According to the present invention can provide even a thin molding can also have a tensile strength and flexibility of the thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet materials, and a manufacturing method thereof, and including the the thermally conductive pressure-sensitive adhesive composition or the thermally conductive pressure-sensitive adhesive sheet-shaped molded electronic component.

具体实施方式 detailed description

[0015] 1.导热性压敏粘接剂组合物(F)、导热性压敏粘接性片状成形体(G) [0015] 1. the thermally conductive pressure-sensitive adhesive composition (F), the thermal conductivity of the pressure sensitive adhesive sheet-like molded article (G)

本发明的导热性压敏粘接剂组合物(F),其在包含如下(Α)、(B)、(D)、(E)的混合组合物中:含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、导热性填料(B)、具有多个聚合性不饱和键的多官能性单体(D)(有时简称为“多官能性单体(D)”)、·和具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E)(有时简称为“多官能环氧化合物(E)”),至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的共聚反应、(甲基)丙烯酸酯单体(α I)的聚合反应、以及多官能性单体(D)的聚合反应中的至少任一种聚合反应、以及(甲基)丙烯酸酯聚合物(Al)彼此的交联反应、含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物彼此的交联反应、以及(甲基)丙烯酸酯聚合物(Al)和含有来源于(甲基)丙烯酸酯单体(α I)的结构单元 The thermally conductive pressure-sensitive adhesive composition (F) of the present invention, which comprises the following (Α), (B), (D), (E) a mixed composition: containing (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition ([alpha]), the thermally conductive filler (B), having a plurality of single polyfunctional polymerizable unsaturated bond body (D) (sometimes referred to as "multifunctional monomer (D)"), ·, and having a viscosity of 2 or more and 10,000 or less and a functional group 600mPa s at 25 ° C or less polyfunctional epoxy compound (E) (sometimes referred to as "polyfunctional epoxy compound (E)"), at least (meth) acrylate monomer (α I) and polyfunctional monomer (D) copolymerization, (meth) acrylate monomers polymerization polymerization member (α I) of a polyfunctional monomer and (D) at least any one of the reaction, and (meth) acrylate polymer (Al) with each other polymerization crosslinking reactions, comprising source in (meth) acrylate structural unit of the polymer monomer (α I) of the cross-linking reaction with each other, and (meth) acrylate polymer (Al) derived containing (meth) acrylate monomer ( α I) of the structural units 的聚合物的交联反应中的至少任一种交联反应而成。 The crosslinking reaction of the polymer at least one selected from the crosslinking reaction.

[0016] 另外,本发明的导热性压敏粘接性片状成形体(G),其将上述混合组合物成形为片状后,或者在将上述混合组合物成形为片状的同时,至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的共聚反应、(甲基)丙烯酸酯单体(α I)的聚合反应、以及多官能性单体 After [0016] Further, the thermally conductive pressure-sensitive adhesive of the present invention, the sheet material (G), which the mixed composition into a sheet, or the mixed composition was molded into a sheet at the same time, at least for (meth) acrylate monomer (α I) and polyfunctional monomer (D) copolymerization, (meth) acrylate monomer (α I) of the polymerization, a polyfunctional monomer, and

(D)的聚合反应中的至少任一种聚合反应、以及(甲基)丙烯酸酯聚合物(Al)彼此的交联反应、含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物彼此的交联反应、以及(甲基)丙烯酸酯聚合物(Al)和含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应中的至少任一种交联反应而成。 (D) polymerization of at least any one reaction, and (meth) acrylate polymer (Al) with each other polymerization crosslinking reactions, comprising from (meta) acrylate monomer (α I) of the polymer cross-linking reaction with each other, and (meth) acrylate polymer (Al) containing units derived from a crosslinking reaction of the polymer (meth) acrylate monomer of the structural unit (α I) in at least any one of a crosslinking reaction from.

[0017] 以下对于构成这样的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的物质进行说明。 [0017] Here constituting such thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of the substance will be described.

[0018] < (甲基)丙烯酸类树脂组合物(A) > [0018] <(meth) acrylic resin composition (A)>

用于本发明的(甲基)丙烯酸类树脂组合物(A)含有(甲基)丙烯酸酯聚合物(Al )、以及(甲基)丙烯酸酯单体(α I)。 Used in the present invention, (meth) acrylic resin composition (A) containing a (meth) acrylate polymer (Al), and (meth) acrylate monomer (α I). 需要说明的是,如上所述,得到导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)时,进行得到产生来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应。 Incidentally, as described above, to give the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive sheet-like pressure-sensitive adhesive property when the molded article (G), for generating obtained from (meth) acrylate polymerization of monomer units of the polymer structure (α I), and (meth) acrylate polymer (Al) and / or derived containing (meth) acrylate monomer (α I) of the structural unit the crosslinking reaction of the polymer. 通过进行该聚合反应和交联反应,含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物与(甲基)丙烯酸酯聚合物(Al)的成分混合和/或一部分键合。 By performing the polymerization reaction and crosslinking reaction, comprising from (meth) acrylate structural unit of the polymer monomer (α I) with (meth) acrylate polymer mixture (Al) of the component and / or a portion of Bond.

[0019] 本发明中,关于丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的用量,相对于(甲基)丙烯酸类树脂组合物(A) 100质量%,优选(甲基)丙烯酸酯聚合物(Al)为5质量%以上且50质量%以下、(甲基)丙烯酸酯单体(α I)为50质量%以上且95质量%以下。 [0019] In the present invention, (meth) acrylic ester polymer The amount of the (Al) and acrylate monomer (α I), the mass 100 relative to the (meth) acrylic resin composition (A)%, preferably (meth) acrylate polymer (Al) 5 mass% or more and 50 mass% or less, (meth) acrylate monomer (α I) is 50 mass% or more and 95 mass% or less. 通过使(甲基)丙烯酸酯单体(α O的含有比率为上述范围,容易成形导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 By reacting (meth) acrylate monomer (α O content ratio within the above range, easy to form the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G).

[0020]((甲基)丙烯酸酯聚合物(Al)) [0020] ((meth) acrylate polymer (of Al))

能够用于本发明的(甲基)丙烯酸酯聚合物(Al)没有特别限定,优选含有形成玻璃化转变温度为-20°C以下的均聚物的(甲基)丙烯酸酯单体的单元(al)、以及具有有机酸基的单体单元(a2)。 Can be used in the present invention, (meth) acrylate polymer (Al) is not particularly limited, but preferably forming unit comprising a glass transition temperature of (meth) acrylate monomers below -20 ° C is a homopolymer of ( al), and a monomer unit (a2) having an organic acid group.

[0021] 赋予上述(甲基)丙烯酸酯单体的单元(al)的(甲基)丙烯酸酯单体(aim)没有特别限定,例如可以列举出丙烯酸乙酯(均聚物的玻璃化转变温度为-24°C)、丙烯酸正丙酯(均聚物的玻璃化转变温度为_37°C)、丙烯酸正丁酯(均聚物的玻璃化转变温度为-54°C)、丙烯酸仲丁酯(均聚物的玻璃化转变温度为-22°C )、丙烯酸正庚酯(均聚物的玻璃化转变温度为_60°C)、丙烯酸正己酯(均聚物的玻璃化转变温度为_61°C)、丙烯酸正辛酯(均聚物的玻璃化转变温度为_65°C)、丙烯酸2-乙基己酯(均聚物的玻璃化转变温度为_50°C)、丙烯酸2-甲氧基乙酯(均聚物的玻璃化转变温度为_50°C)、丙烯酸3-甲氧基丙酯(均聚物的玻璃化转变温度为_75°C)、丙烯酸3-甲氧基丁酯(均聚物的玻璃化转变温度为_56°C)、丙烯酸乙氧基甲酯(均聚物的玻璃化转变温度为_50°C)、甲基丙烯酸正辛酯(均聚物的玻璃化转变 [0021] imparting the above-described (meth) acrylate monomer unit (Al) is (meth) acrylate monomer (AIM) is not particularly limited, and examples include ethyl acrylate (homopolymer has a glass transition temperature to -24 ° C), n-propyl acrylate (homopolymer has a glass transition temperature of _37 ° C), n-butyl acrylate (homopolymer has a glass transition temperature of -54 ° C), sec-butyl acrylate, ester (homopolymer has a glass transition temperature of -22 ° C), n-heptyl acrylate, acrylate (homopolymer has a glass transition temperature of _60 ° C), hexyl acrylate (homopolymer glass transition temperature _61 ° C), n-octyl acrylate (homopolymer has a glass transition temperature of _65 ° C), 2-ethylhexyl acrylate (homopolymer has a glass transition temperature of _50 ° C), acrylic acid 2-methoxyethyl acrylate (homopolymer has a glass transition temperature of _50 ° C), 3-methoxy propyl acrylate (homopolymer has a glass transition temperature of _75 ° C), acrylic acid 3 methoxybutyl acetate (homopolymer has a glass transition temperature of _56 ° C), ethoxy methyl acrylate (homopolymer has a glass transition temperature of _50 ° C), n-octyl methacrylate ( homopolymer has a glass transition 度为_25°C)、甲基丙烯酸正癸酯(均聚物的玻璃化转变温度为_49°C)等。 Degree of _25 ° C), n-decyl methacrylate (homopolymer has a glass transition temperature of _49 ° C) and the like. 其中,优选为丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸2-甲氧基乙酯,更优选为丙烯酸正丁酯、丙烯酸2-乙基己酯,进一步优选为丙烯酸2-乙基己酯。 Among these, n-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, more preferably acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, more preferably hexyl ester.

[0022] 这些(甲基)丙烯酸酯单体(aim)可以单独使用一种,也可以组合使用两种以上。 [0022] These (meth) acrylate monomer (AIM) can be used alone or in combination of two or more.

[0023](甲基)丙烯酸酯单体(aim)以由其得到的单体单元(al)在(甲基)丙烯酸酯聚合物(Al)中达到优选为80质量%以上且99.9质量%以下、更优选为85质量%以上且99.5质量%以下的量的方式供于聚合。 [0023] (meth) acrylate monomer (AIM) to its monomer units (Al) obtained reaches the (meth) acrylate polymer (Al) is preferably 80 mass% or more and 99.9 mass% or less , more preferably 85% by mass and 99.5% by mass or less in an amount of ways for the polymerization. (甲基)丙烯酸酯单体(aim)的用量在上述范围内时,容易将聚合时的聚合体系的粘度保持在适当的范围。 (Meth) acrylate monomer amount (AIM) in the above range, the viscosity of the polymerization system is easy when the polymerization is kept in an appropriate range.

[0024] 接着,对具有有机酸基的单体单元(a2)进行说明。 [0024] Next, the monomer unit (a2) having an organic group will be described. 赋予具有有机酸基的单体单元(a2)的单体(a2m)没有特别限定,作为其代表性的例子,可以列举出具有羧基、酸酐基、磺酸基等有机酸基的单体。 Imparting monomer having a monomer unit (a2) in an organic acid group (A2M) is not particularly limited, Examples of representative may include a monomer having a carboxyl group, an acid anhydride group, a sulfonic acid group and the like organic acid groups. 另外,除了这些以外,还可以使用含有次磺酸基、亚磺酸基、磷酸基等的单体。 Further, in addition to these, also possible to use monomers containing a sulfenic acid group, a sulfinic acid group, a phosphoric acid group and the like.

[0025] 作为具有羧基的单体的具体例,可以列举出例如丙烯酸、甲基丙烯酸、巴豆酸等α, 烯属不饱和单羧酸;衣康酸、马来酸、富马酸等α,烯属不饱和多元羧酸,以及衣康酸单甲酯、马来酸单丁酯、富马酸单丙酯等α,β_烯属不饱和多元羧酸偏酯等。 [0025] Specific examples of the monomer having a carboxyl group, [alpha] can include acrylic acid, methacrylic acid, crotonic acid, ethylenically unsaturated monocarboxylic acid; itaconic acid, maleic acid, fumaric acid and the like [alpha], ethylenically unsaturated polycarboxylic acid, and itaconic acid, monomethyl maleate, monobutyl maleate, fumarate propyl α, β_ ethylenically unsaturated polycarboxylic acid partial esters and the like. 另外,可以同样地使用马来酸酐、衣康酸酐等具有能够通过水解等而得到羧基的基团的物质。 Further, in the same manner using a substance having a carboxyl group can be obtained by hydrolysis of maleic anhydride, itaconic anhydride.

[0026] 作为具有磺酸基的单体的具体例,可以列举出烯丙基磺酸、甲基烯丙基磺酸、乙烯基磺酸、苯乙烯磺酸、丙烯酰胺-2-甲基丙磺酸等α,不饱和磺酸、以及它们的盐。 [0026] Specific examples of the monomer having a sulfonic acid group, include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido-2-methylpropane acid and the like [alpha], unsaturated sulfonic acids, and salts thereof.

[0027] 作为单体(a2m),上面例示的具有有机酸基的单体之中,更优选为具有羧基的单体,其中,特别优选为具有丙烯酸或者甲基丙烯酸的单体。 [0027] As (A2M) monomers exemplified above having an organic group in a monomer, more preferably a monomer having a carboxyl group, wherein, particularly preferably a methacrylic or acrylic monomer. 这些单体从能够在工业上以廉价容易地获得,与其它单体成分的共聚性也良好、生产性的观点出发是优选的。 These monomers can be readily obtained from low cost on an industrial, and other monomer component copolymerizable also good, productivity viewpoint is preferable. 需要说明的是,单体(a2m)可以单独使用一种,也可以组合使用两种以上。 Incidentally, monomers (A2M) may be used alone or in combination of two or more.

[0028] 具有有机酸基的单体(a2m)以由其得到的单体单元(a2)在(甲基)丙烯酸酯聚合物(Al)中达到优选为0.1质量%以上且20质量%以下、更优选为0.5质量%以上且15质量%以下的量的方式供于聚合。 [0028] The monomer having an organic acid group (A2M) to (a2) reaches the (meth) acrylate polymer (Al) in the monomer units derived therefrom is preferably 0.1 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less in an amount of ways for the polymerization. 具有有机酸基的单体(a2m)的用量在上述范围内时,容易将聚合时的聚合体系的粘度保持在适当的范围。 The amount of the monomer having an organic acid group (A2M) when the above range, the viscosity of the polymerization system is easy when the polymerization is kept in an appropriate range.

[0029] 需要说明的是,具有有机酸基的单体单元(a2)如前所述通过具有有机酸基的单体(a2m)的聚合导入(甲基)丙烯酸酯聚合物(Al)中是简便的,因而优选,也可以在(甲基)丙烯酸酯聚合物(Al)生成后,通过公知的高分子反应导入有机酸基。 [0029] Incidentally, the monomer unit (a2) having an organic group as previously described by a monomer having an organic acid group (A2M) introducing a polymerizable (meth) acrylate polymer (Al) is simple, and therefore preferably, it may be in the (meth) acrylate polymer (Al) generated by known polymer reaction for introducing an organic group.

[0030] 另外,(甲基)丙烯酸酯聚合物(Al)也可以含有由具有有机酸基以外的官能团的单体(a3m)得到的单体单元(a3)。 [0030] Further, (meth) acrylate polymer (Al) may contain a monomer unit from a monomer having a functional group other than the organic acid group (A3m) obtained in (a3). 作为上述有机酸基以外的官能团,可以列举出羟基、氨基、酰胺基、环氧基、巯基等。 As a functional group other than the organic acid group may include a hydroxyl group, an amino group, an amide group, an epoxy group, a mercapto group and the like.

[0031] 作为具有羟基的单体,可以列举出(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸3-羟基丙酷等(甲基)丙稀酸羟基烷基酷等。 [0031] The monomer having a hydroxyl group include (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropoxy cool (meth) acrylic acid hydroxyalkyl cool the like.

[0032] 作为具有氨基的单体,可以列举出(甲基)丙烯酸N,N- 二甲基氨基甲酯、(甲基)丙烯酸N,N- 二甲基氨基乙酯、氨基苯乙烯等。 [0032] As the monomer having an amino group, include (meth) acrylate, N, N- dimethylaminomethyl, (meth) acrylate, N, N- dimethylaminoethyl acrylate, aminostyrene and the like.

[0033] 作为具有酰胺基的单体,可以列举出丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N,N-二甲基丙烯酰胺等α,烯属不饱和羧酸酰胺单体等。 [0033] As the monomer having an amide group may include acrylamide, methacrylamide, N- methylol acrylamide, N- methylol acrylamide, N, N- dimethyl acrylamide α, ethylenically unsaturated carboxylic acid amide monomers.

[0034] 作为具有环氧基的单体,可以列举出(甲基)丙烯酸缩水甘油酯、烯丙基缩水甘油醚等。 [0034] As the monomer having an epoxy group, include (meth) acrylate, allyl glycidyl ether.

[0035] 具有有机酸基以外的官能团的单体(a3m)可以单独使用一种,也可以组合使用两种以上。 [0035] The monomer having a functional group other than the organic acid group (A3m) may be used alone or in combination of two or more.

[0036] 具有这些有机酸基以外的官能团的单体(a3m)优选以由其得到的单体单元(a3)在(甲基)丙烯酸酯聚合物(Al)中达到10质量%以下的量的方式用于聚合。 [0036] The monomer having a functional group other than the organic acid group (A3m) preferably (a3) ​​to reach an amount of 10 mass% or less of the (meth) acrylate polymer (Al) in the monomer units derived therefrom manner used for polymerization. 通过使用10质量%以下的单体(a3m),容易将聚合时的聚合体系的粘度保持在适当的范围。 % Or less of the monomer (A3m) using 10 mass, the viscosity of the polymerization system is easy when the polymerization was kept in an appropriate range.

[0037](甲基)丙烯酸酯聚合物(Al)除了可以含有形成上述玻璃化转变温度为_20°C以下的均聚物的(甲基)丙烯酸酯单体单元(al)、具有有机酸基的单体单元(a2)、以及具有有机酸基以外的官能团的单体单元(a3)以外,还可以含有由能够与上述单体共聚的单体(a4m)得到的单体单元(a4)。 [0037] (meth) acrylate polymer (Al) may contain in addition to forming the glass transition temperature of _20 ° C or less is a homopolymer of a (meth) acrylate monomer units (al), an organic acid having a group other than the monomer units (A2), and a monomer unit (a3) ​​a functional group other than the organic acid group, may also contain monomers copolymerizable with the monomer (A4M) to give monomer units (a4) is .

[0038] 单体(a4m)没有特别限定,作为其具体例,可以列举出上述(甲基)丙烯酸酯单体(aim)以外的(甲基)丙烯酸酯单体、α,β _烯属不饱和多元羧酸全酯、烯基芳香族单体、共轭二烯系单体、非共轭二烯系单体、氰化乙烯基单体、羧酸不饱和醇酯、烯烃系单体等。 [0038] (a4m) monomer is not particularly limited, and specific examples thereof include the above-mentioned (meth) acrylate monomer (AIM) other than the (meth) acrylate monomer, α, β _ ethylenic unsaturation unsaturated polycarboxylic acid full ester, alkenyl aromatic monomers, conjugated diene monomers, non-conjugated diene monomer, vinyl cyanide monomers, unsaturated carboxylic acid esters, olefin monomers .

[0039] 作为上述(甲基)丙烯酸酯单体(aim)以外的(甲基)丙烯酸酯单体的具体例,可以列举出丙烯酸甲酯(均聚物的玻璃化转变温度为10°c)、甲基丙烯酸甲酯(均聚物的玻璃化转变温度为105°C)、甲基丙烯酸乙酯(均聚物的玻璃化转变温度为63°C)、甲基丙烯酸正丙酯(均聚物的玻璃化转变温度为25°C)、甲基丙烯酸正丁酯(均聚物的玻璃化转变温度为20°C)等。 [0039] As the acrylic (meth) acrylate ester monomer Specific examples of the monomer other than the ester (AIM) the (meth) may include methyl acrylate (homopolymer has a glass transition temperature of 10 ° c) , methyl methacrylate (homopolymer has a glass transition temperature of 105 ° C), ethyl methacrylate (homopolymer has a glass transition temperature of 63 ° C), n-propyl methacrylate (homo the glass transition temperature thereof is 25 ° C), n-butyl methacrylate (homopolymer has a glass transition temperature of 20 ° C) and the like.

[0040] 作为α,烯属不饱和多元羧酸全酯的具体例,可以列举出富马酸二甲酯、富马酸二乙酯、马来酸二甲酯、马来酸二乙酯、衣康酸二甲酯等。 [0040] As [alpha], specific examples of ethylenically unsaturated polycarboxylic acid full-ester include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, itaconate and so on.

[0041] 作为烯基芳香族单体的具体例,可以列举出苯乙烯、α -甲基苯乙烯、甲基α -甲基本乙稀、乙烯基甲本、以及二乙烯基本等。 [0041] Specific examples of alkenyl aromatic monomers include styrene, α - methylstyrene, methyl-α - A substantially ethylene, vinyl toluene present, and divinyl substantially equal.

[0042] 作为共轭二烯系单体的具体例,可以列举出1,3_丁二烯、2-甲基-1,3-丁二烯(与异戊二烯同义)、1,3-戊二烯、2,3- 二甲基-1,3- 丁二烯、2-氯-1,3- 丁二烯、环戊二烯等。 [0042] Specific examples of the conjugated diene monomer include 1,3_-butadiene, 2-methyl-1,3-butadiene (isoprene and synonymous), 1, -pentadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, cyclopentadiene.

[0043] 作为非共轭二烯系单体的具体例,可以列举出1,4_己二烯、二环戊二烯、亚乙基降冰片烯等。 [0043] Specific examples of non-conjugated diene monomer may include 1,4_-hexadiene, dicyclopentadiene, ethylidene norbornene and the like. [0044] 作为氰化乙烯基单体的具体例,可以列举出丙烯腈、甲基丙烯腈、α -氯丙烯腈、α -乙基丙烯臆等。 [0044] Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α - chloroacrylonitrile, α - ethyl acrylamide chest and the like.

[0045] 作为羧酸不饱和醇酯单体的具体例,可以列举出醋酸乙烯酯等。 [0045] Specific examples of the unsaturated carboxylic acid ester monomer include vinyl acetate and the like.

[0046] 作为烯烃系单体的具体例,可以列举出乙烯、丙烯、丁烯、戊烯等。 [0046] Specific examples of the olefin monomers include ethylene, propylene, butene, pentene and the like.

[0047] 单体(a4m)可以单独使用一种,也可以组合使用两种以上。 [0047] (a4m) monomers may be used alone or may be used in combination of two or more.

[0048] 单体(a4m)以由其得到的单体单元(a4)的量在(甲基)丙烯酸酯聚合物(Al)中达到优选为10质量%以下、更优选为5质量%以下的量的方式供于聚合。 [0048] (a4m) monomer in an amount of monomeric units derived therefrom (a4) reaches 10 mass% is preferably in the (meth) acrylate polymer (Al), and more preferably 5 mass% or less way for the amount of the polymerization.

[0049](甲基)丙烯酸酯聚合物(Al)特别优选通过将上述形成玻璃化转变温度为_20°C以下的均聚物的(甲基)丙烯酸酯单体(aim)、具有有机酸基的单体(a2m)、根据需要使用的含有有机酸基以外的官能团的单体(a3m)、以及根据需要使用的能够与这些单体共聚的单体(a4m)进行共聚从而得到。 [0049] particularly preferably by (meth) acrylate polymer (Al) is formed above the glass transition temperature of _20 ° C or less homopolymer (meth) acrylate monomer (aim), an organic acid having a group-containing monomer (a2m), (a3m), and obtained by copolymerizing such a monomer according to a functional group other than the organic acid group-containing monomer according to need (A4M) copolymerizable with these monomers to be used.

[0050] 得到(甲基)丙烯酸酯聚合物(Al)时的聚合方法没有特别限定,可以是溶液聚合、乳液聚合、悬浮聚合、本体聚合等的任一种,也可以这些以外的方法。 When the polymerization process [0050] The obtained (meth) acrylate polymer (Al) is not particularly limited, and may be solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization of any one of these methods may also be outside. 但是,在这些聚合方法之中优选为溶液聚合,其中更优选使用醋酸乙酯、乳酸乙酯等羧酸酯、或苯、甲苯、二甲苯等芳香族溶剂作为聚合溶剂的溶液聚合。 However, among these polymerization methods, solution polymerization is preferred, which is more preferably used ethyl acetate, ethyl lactate and the like carboxylic acid ester, or benzene, toluene, xylene and the like aromatic solvents as a polymerization solvent, solution polymerization. 聚合时,单体可以分批添加到聚合反应容器中,优选将总量一下子添加。 When the polymerization, monomers may be added batchwise to a polymerization reaction vessel, it is preferable to add a total once. 聚合引发的方法没有特别限定,作为聚合引发剂,优选为热聚合引发剂。 The method of the polymerization initiator is not particularly limited, as a polymerization initiator, preferably a thermal polymerization initiator. 该热聚合引发剂没有特别限定,例如可以使用过氧化物聚合引发剂、偶氮化合物聚合引发剂。 The thermal polymerization initiator is not particularly limited, for example using a peroxide polymerization initiator, an azo compound polymerization initiator.

[0051] 作为过氧化物聚合引发剂,除了叔丁基过氧化氢这样的过氧化氢、过氧化苯甲酰、过氧化环己酮这样的过氧化物以外,还可以列举出过硫酸钾、过硫酸钠、过硫酸铵等过硫酸盐等。 [0051] As a polymerization initiator, a peroxide, in addition to t-butyl hydrogen peroxide such as hydrogen peroxide, benzoyl peroxide, such peroxides cyclohexanone peroxide, may also include potassium persulfate, sodium persulfate, ammonium persulfate and the like. 这些过氧化物可以与还原剂适当组合以氧化还原系催化剂的形式使用。 These peroxides can be suitably used in combination with a reducing agent as a redox catalyst.

[0052] 作为偶氮化合物聚合引发剂,可以列举出2,2' -偶氮双异丁腈、2,2' -偶氮双(2,4-二甲基戊腈)、2,2' -偶氮双(2-甲基丁腈)等。 [0052] The azo compound as a polymerization initiator include 2,2 '- azobisisobutyronitrile, 2,2' - azobis (2,4-dimethylvaleronitrile), 2,2 ' - azobis (2-methylbutyronitrile) and the like.

[0053] 聚合引发剂的用量没有特别限定,优选相对于单体100质量份为0.01质量份以上且50质量份以下的范围。 [0053] The polymerization initiator used is not particularly limited with respect to 100 parts by mass of the monomer in the range of 0.01 parts by mass or more and 50 parts by mass or less.

[0054] 这些单体的其它聚合条件(聚合温度、压力、搅拌条件等)没有特别制限。 [0054] Other polymerizable monomers such conditions (polymerization temperature, pressure, stirring conditions and the like) is not particularly restricted.

[0055] 聚合反应结束后根据需要将所得到的聚合物从聚合介质中分离。 After the separation [0055] The polymerization reaction is required a polymer obtained from the polymerization medium. 分离的方法没有特别限定。 The separation method is not particularly limited. 例如,溶液聚合的情况下,可以将聚合溶液置于减压下,馏去聚合溶剂,从而得到(甲基)丙烯酸酯聚合物(Al)。 For example, the case of solution polymerization, the polymerization solution was placed under reduced pressure, the polymerization solvent was distilled off, thereby obtaining (meth) acrylate polymer (Al).

[0056](甲基)丙烯酸酯聚合物(Al)的重均分子量(Mw)通过凝胶渗透色谱法(GPC法)进行测定,优选以标准聚苯乙烯换算计在10万以上且100万以下的范围,更优选在20万以上且50万以下的范围。 [0056] (meth) acrylate polymer (Al), weight average molecular weight (Mw) measured by gel permeation chromatography (GPC method), preferably in terms of standard polystyrene of 100,000 or more and 1,000,000 or less range, more preferably 200,000 or more and 500,000 or less. (甲基)丙烯酸酯聚合物(Al)的重均分子量可以通过调整聚合时使用的聚合引发剂的量、链转移剂的量来进行控制。 The (meth) acrylate polymer (Al) average molecular weight of the amount of the polymerization initiator, the amount of chain transfer agent by adjusting the polymerization initiator used to control.

[0057]((甲基)丙烯酸酯单体混合物(α I)) [0057] ((meth) acrylate monomer mixture (α I))

(甲基)丙烯酸酯单体(α I)只要是含有(甲基)丙烯酸酯单体的单体就没有特别限定,优选含有形成玻璃化转变温度为-20°C以下的均聚物的(甲基)丙烯酸酯单体(a5m)。 (Meth) acrylate monomer (α I) as long as the monomer is (meth) acrylate monomer containing not particularly limited, but preferably is formed of a glass transition temperature below -20 ° C homopolymer ( meth) acrylate monomer (a5m).

[0058] 作为形成玻璃化转变温度为-20°C以下的均聚物的(甲基)丙烯酸酯单体(a5m)的例子,可以列举出与用于(甲基)丙烯酸酯聚合物(Al)的合成的(甲基)丙烯酸酯单体(aim)相同的(甲基)丙烯酸酯单体。 [0058] As the transition is an example of forming a glass transition temperature below -20 ° C is a homopolymer of (meth) acrylate monomer (A5m) may be used include a (meth) acrylate polymer (Al ) synthesis of (meth) same as (meth) acrylate monomer acrylate monomer (aim). (甲基)丙烯酸酯单体(a5m)可以单独使用一种,也可以组合使用两种以上。 (Meth) acrylate monomer (A5m) may be used alone or in combination of two or more.

[0059](甲基)丙烯酸酯单体(α I)中的(甲基)丙烯酸酯单体(a5m)的比率优选为50质量%以上且100质量%以下,更优选为75质量%以上且100质量%以下。 [0059] The ratio of the (meth) acrylate monomers (meth) acrylate monomer (α I) of (A5m) is preferably 50 mass% or more and 100 mass% or less, more preferably 75 mass% or more and 100% by mass. 通过使(甲基)丙烯酸酯单体(α I)中的(甲基)丙烯酸酯单体(a5m)的比率为上述范围,容易获得压敏粘接性、柔软性优异的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 By reacting (meth) acrylate monomer (α I) of the (meth) acrylic acid ester monomer ratio (A5m) within the above range, the pressure-sensitive adhesive easily obtained, the flexibility of the pressure-sensitive adhesive having excellent thermal conductivity cement composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G).

[0060] 另外,(甲基)丙烯酸酯单体(α I)可以是(甲基)丙烯酸酯单体(a5m)和能够与其共聚的单体的混合物。 [0060] Further, (meth) acrylate monomer (α I) may be a (meth) acrylate monomer (A5m) and a mixture of a monomer copolymerizable therewith.

[0061](甲基)丙烯酸酯单体(α I)可以是形成玻璃化转变温度为-20°C以下的均聚物的(甲基)丙烯酸酯单体(a5m)、和能够与这些共聚的具有有机酸基的单体(a6m)的混合物。 [0061] (meth) acrylate monomer (α I) may be formed (meth) acrylate monomer (A5m) homopolymer has a glass transition temperature of below -20 ° C, and can be copolymerized with these the mixture of monomers having an organic acid group (A6M) a.

·[0062] 作为上述单体(a6m)的例子,可以列举出与作为用于(甲基)丙烯酸酯聚合物(Al)的合成的单体(a2m)而例示出的单体相同的具有有机酸基的单体。 * [0062] Examples of the monomer (A6M) examples include the synthesis of a monomer as a (meth) acrylate polymer (Al), (A2M) to the same embodiment shown with an organic monomer monomeric acid group. 单体(a6m)可以单独使用一种,也可以组合使用两种以上。 Monomer (A6M) may be used alone or in combination of two or more.

[0063](甲基)丙烯酸酯单体(α I)中的单体(a6m)的比率优选为30质量%以下,更优选为10质量%以下。 [0063] The ratio of the (meth) acrylate monomer (α I) of the monomer (A6M) is preferably 30% by mass or less, more preferably 10 mass% or less. 通过使(甲基)丙烯酸酯单体(α I)中的单体(a6m)的比率为上述范围,容易得到压敏粘接性、柔软性优异的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 By reacting (meth) acrylate monomer (α I) of the monomer (A6M) ratio of the above-described range, the pressure-sensitive adhesive easily obtained, flexibility, excellent thermal and pressure-sensitive adhesive composition (F ) and the thermal conductivity of the pressure-sensitive adhesive sheet-like molded article (G).

[0064](甲基)丙烯酸酯单体(α I)除了可以是(甲基)丙烯酸酯单体(a5m)和能够根据希望进行共聚的具有有机酸基的单体(a6m)的混合物以外,也可以是它们和能够与它们进行共聚的单体(a7m)的混合物。 [0064] (meth) acrylate, in addition to a (meth) acrylate monomer (A5m) and can be a mixture of a monomer having an organic group (A6M) copolymerizable monomer other than as desired (α I), It may be a mixture thereof, and monomer (A7M) can be copolymerized with them.

[0065] 作为上述单体(a7m)的例子,可以列举出与作为用于(甲基)丙烯酸酯聚合物(Al)的合成的单体(a3m)、和单体(a4m)而例示出的单体相同的单体。 [0065] Examples of the monomer (A7M) examples include the synthesis of a monomer as a (meth) acrylate polymer (Al), (A3m), and monomer (A4M) and the embodiment shown in the same monomer. 单体(a7m)可以单独使用一种,也可以组合使用两种以上。 Monomer (A7M) may be used alone or in combination of two or more.

[0066](甲基)丙烯酸酯单体(α I)中的单体(a7m)的比率优选为20质量%以下,更优选为15质量%以下。 [0066] The ratio of the (meth) acrylate monomer (α I) of the monomer (A7M) is preferably 20 mass% or less, more preferably 15 mass% or less.

[0067]〈聚合引发剂〉 [0067] <Polymerization Initiator>

获得导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)时,聚合(甲基)丙烯酸酯单体(α I)和后述的多官能性单体(D)。 Upon obtaining the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G), polymeric (meth) acrylate monomer (α I) described later polyfunctional monomer (D). 为了促进该聚合,优选使用聚合引发剂。 To facilitate this polymerization, preferably using a polymerization initiator. 作为该聚合引发剂,可以列举出光聚合引发剂、偶氮系热聚合引发剂、有机过氧化物热聚合引发剂等。 Examples of the polymerization initiator include a photopolymerization initiator, an azo-based thermal polymerization initiator, an organic peroxide thermal polymerization initiators. 从赋予所得到的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)优异的粘接性等观点出发,优选使用有机过氧化物热聚合引发剂。 From the thermally conductive pressure-sensitive adhesive composition (F) obtained by imparting pressure-sensitive adhesiveness and thermal conductivity the sheet material (G) and the like having excellent adhesiveness viewpoint, preferably an organic peroxide thermal polymerization initiators agents.

[0068] 作为光聚合引发剂,可以使用公知的各种光聚合引发剂。 [0068] As the photopolymerization initiator, it may be used various known photopolymerization initiators. 其中,优选为酰基氧化膦系化合物。 Among these, acylphosphine oxide-based compound. 作为优选的光聚合引发剂的酰基氧化膦系化合物可以列举出双(2,4,6-三甲基 Acylphosphine oxide-based compound as a preferable initiator may include a photopolymerization bis (2,4,6-trimethyl

苯甲酰)苯基氧化膦、2,4,6-三甲基苯甲酰二苯基氧化膦等。 Benzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

[0069] 作为偶氮系热聚合引发剂,可以列举出2,2' -偶氮双异丁腈、2,2' -偶氮双(2,4-二甲基戊腈)、2,2' -偶氮双(2-甲基丁腈)等。 [0069] Examples of azo-based thermal polymerization initiators include 2,2 '- azobisisobutyronitrile, 2,2' - azobis (2,4-dimethylvaleronitrile), 2,2 '- azobis (2-methylbutyronitrile) and the like.

[0070] 作为有机过氧化物热聚合引发剂,可以列举出叔丁基过氧化氢这样的过氧化氢、过氧化苯甲酰、过氧化环己酮、1,6-双(叔丁基过氧化羰基氧基)己烷、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己酮这样的过氧化物等。 [0070] As the organic peroxide thermal polymerization initiators include t-butyl hydroperoxide such as hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxy oxidation carbonyloxy) hexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexanone peroxide such. 其中,优选在热分解时不会放出成为臭气原因的挥发性物质的引发剂。 Among them, thermal decomposition does not emit volatiles to become the initiator causes odor. 另外,有机过氧化物热聚合引发剂之中,优选I分钟半衰期温度为100°C以上且170°C以下的引发剂。 Further, among the thermal polymerization initiator an organic peroxide, preferably I minute half-life temperature of at least 100 ° C and 170 ° C or less initiator.

[0071] 相对于(甲基)丙烯酸类树脂组合物(A)IOO质量份,上述聚合引发剂的用量优选为0.01质量份以上且10质量份以下,更优选为0.1质量份以上且5质量份以下,进一步优选为0.3质量份以上且2质量份以下。 [0071] with respect to the (meth) acrylic resin composition (A) IOO parts by mass of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.3 parts by mass or more and 2 parts by mass or less. 通过使聚合引发剂的用量为上述范围,容易使(甲基)丙烯酸酯单体混合物(α I)的聚合转化率为适当的范围,容易防止导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)中残留单体臭。 When the polymerization initiator used in the above range, easily (meth) acrylate monomer mixture (α I) in a suitable polymerization conversion rate range, easy to prevent the thermally conductive pressure-sensitive adhesive composition (F) and thermally conductive pressure-sensitive adhesive sheet-like molded article (G) smell of residual monomers. 需要说明的是,(甲基)丙烯酸酯单体(α I)的聚合转化率优选为95质量%以上。 Incidentally, the polymerization conversion ratio (meth) acrylate monomer (α I) is preferably 95% by mass. (甲基)丙烯酸酯单体(α I)的聚合转化率为95质量%以上时,容易防止导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)中残留单体臭。 (Meth) acrylate monomer or higher (α I) polymerization conversion was 95% by mass, it is easy to prevent the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet materials ( G) the residual monomer odor. 另外,通过使聚合引发剂的用量为上述范围,容易防止由于添加聚合引发剂而过度地引发聚合反应的进行,其结果导热性压敏粘接性片状成形体(G)不会成为平滑的片状,引起材料破坏的情况。 Further, by making the amount of the polymerization initiator within the above range, can be easily prevented by the addition of a polymerization initiator to initiate the polymerization reaction excessively proceeds, the thermally conductive pressure-sensitive adhesive as a result of the sheet material (G) does not become smooth a sheet material causing the case of damage.

[0072] <多官能性单体(D) > 本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用多官能性单体(D)。 [0072] <polyfunctional monomer (D)> thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) a polyfunctional monomer using (D). 作为多官能性单体(D),使用能够与(甲基)丙烯酸酯单体(α I)中含有的单体进行共聚的单体。 Examples of the polyfunctional monomer (D), a monomer capable of copolymerizing with the (meth) acrylate monomer monomer (α I) contained. 另外,多官能性单体(D)优选具有多个聚合性不饱和键,在末端具有该不饱和键。 Further, the polyfunctional monomer (D) preferably has a plurality of polymerizable unsaturated bonds, having at the end of the unsaturated bond. 通过使用这样的多官能性单体(D),在共聚物中导入分子内和/或分子间交联,能够提高导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的作为压敏粘接剂的凝集力。 By using such a polyfunctional monomer (D), introduced into the intramolecular and / or intermolecular crosslinking in the copolymer, can improve the thermal conductivity of the pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive the sheet material (G) is used as the pressure-sensitive adhesive cohesion.

[0073] 通常在自由基热聚合等聚合时,即使不使用多官能性单体,一定程度的交联反应也进行。 [0073] Usually in the radical polymerization like polymerization heat, without using the polyfunctional monomer, a certain degree of crosslinking reaction is also carried out. 其中,可以认为根据本发明,通过组合使用多官能性单体(D)以及后面详述的多官能环氧化合物(Ε),在导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)内均匀地形成交联结构,维持柔软性,同时提高拉伸强度。 Wherein, according to the present invention may be considered, by using a combination of a polyfunctional monomer (D) and described later in detail polyfunctional epoxy compound (Epsilon), the thermally conductive pressure-sensitive adhesive composition (F) and thermal conductivity pressure sensitive adhesive sheet materials uniform (G) crosslinked structure, the flexibility is maintained, while improving the tensile strength.

[0074] 作为多官能性单体(D),可以使用例如1,6_己二醇二(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,12-癸二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能性(甲基)丙烯酸酯、2,4-双(三氯甲基)-6-对甲氧基苯乙烯-5-三嗪等取代三嗪、以及4-丙烯酰氧基二苯甲酮这样的单烯属不饱和芳香族酮等。 [0074] Examples of the polyfunctional monomer (D), may be used, for example, 1,6_ hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, 1,12 decanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth ) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyfunctional dipentaerythritol hexa (meth) acrylate, (meth) acrylate, 2,4-bis (trichloromethyl) -6-p-methoxystyrene -5- triazine substituted triazine, and 4- acryloxy benzophenone such monoethylenically unsaturated aromatic ketone. 其中,优选为季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯。 Among these, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate. 多官能性单体(D)可以单独使用一种,也可以组合使用两种以上。 A polyfunctional monomer (D) may be used alone or in combination of two or more.

[0075] 相对于100质量份(甲基)丙烯酸类树脂组合物(A),本发明的导热性压敏粘接剂组合物(F)或者导热性压敏粘接性片状成形体(G)中使用的多官能性单体(D)的量为0.2质量份以上且8质量份以下,优选为0.5质量份以上且2质量份以下。 [0075] with respect to 100 parts by mass of (meth) acrylic resin composition (A), the thermally conductive pressure-sensitive adhesive composition (F) according to the present invention, the thermally conductive pressure-sensitive adhesive or a sheet-like molded article (G amount of the polyfunctional monomer (D)) is used in 0.2 parts by mass or more and 8 parts by mass or less, preferably 0.5 parts by mass or more and 2 parts by mass or less. 通过使多官能性单体(D)的用量为上述范围,容易使导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)兼具作为压敏粘接剂的柔软性和拉伸强度。 By polyfunctional monomer (D) is used in an amount within the above range, easily thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of both pressure-sensitive softness and tensile strength of the adhesive.

[0076] <导热性填料(B) > [0076] <thermally conductive filler (B)>

本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用导热性填料(B)。 The thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article using the (G) of the thermally conductive filler (B). 导热性填料(B)是通过添加能够提高导热性压敏粘接剂组合物(F)、导热性压敏粘接性片状成形体(G)的导热性、导热系数为lW/m K以上的填料。 Thermally conductive filler (B) can be improved by adding thermally conductive pressure-sensitive adhesive composition (F.), The thermally conductive pressure-sensitive adhesive sheet-like molded article (G), thermal conductivity, thermal conductivity of lW / m K or more filler.

[0077] 导热性填料(B)可以使用公知的导热性填料。 [0077] The thermally conductive filler (B) may be a publicly-known thermally conductive filler. 作为导热性填料(B)的具体例,可以列举出氢氧化铝、氢氧化镓、氢氧化铟、氢氧化镁、氢氧化钙、氢氧化锶、氢氧化钡、硼酸锌水合物、高岭土、铝酸钙水合物、碳酸钙、碳酸铝、片钠铝石、氧化铝(氧化铝)、氧化镁、氧化锌、氮化硼、氮化铝、二氧化硅等。 As the thermally conductive filler (B) Specific examples may include aluminum hydroxide, gallium, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, zinc borate hydrate, kaolin, aluminum hydrate, calcium carbonate, aluminum carbonate, dawsonite, aluminum oxide (alumina), magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silica and the like. 这些之中,碳酸钙、氢氧化铝以及氧化铝,由于容易获得、化学性也稳定、且能够大量配合而优选,更优选为氢氧化铝以及氧化铝。 Among these, calcium carbonate, aluminum hydroxide and aluminum, because it is easy to obtain, but also chemically stable, and capable of a large amount is preferable, more preferably alumina, and aluminum hydroxide. 导热性填料(B)可以单独使用一种,也可以组合使用两种以上。 Thermally conductive filler (B) may be used alone or in combination of two or more.

[0078] 导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用的导热性填料(B)的量相对于(甲基)丙烯酸类树脂组合物(A) 100质量份为90质量份以上且1200质量份以下,优选为100质量份以上且1000质量份以下,更优选为200质量份以上且900质量份以下。 [0078] The amount of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of the thermally conductive filler (B) used in the (meth) acrylic resin parts of composition (A) 100 parts by mass of 90 mass or more and 1200 parts by mass or less, preferably 100 parts by mass or more and 1000 parts by mass or less, more preferably 200 parts by mass or more and 900 parts by mass or less. 导热性填料(B)的含量超过上述范围时,成为导热性压敏粘接剂组合物 When the content of the thermally conductive filler (B) exceeds the above range, the thermal conductivity becomes sensitive adhesive composition

(F)以及导热性压敏粘接性片状成形体(G)的原材料的混合组合物的粘度过度地增大,有可能难以成形导热性压敏粘接剂组合物(E)以及导热性压敏粘接性片状成形体(F),或者即使能够成形,导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的硬度增大,形状追随性(对被粘体的密合性)降低。 (F) and the viscosity of the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of the starting material mixture composition increases excessively, it may difficult to form the thermally conductive pressure-sensitive adhesive composition (E) and thermal conductivity the pressure-sensitive adhesive of the sheet material (F), or even can be molded, thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of increased hardness, shape following property (adhesion to the adherend) decreases. 另一方面,导热性填料(B)的含量不足上述范围时,有可能通过使用导热性填料(B),提高导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)的导热性的效果不充分。 On the other hand, when the content is less than the above range thermally conductive filler (B), it is possible by using a thermally conductive filler (B), to improve the thermal conductivity of the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet thermal conductivity molded bodies (G) thermal conductivity effect is insufficient.

[0079] 另外,导热性填料(B)的BET比表面积优选为1.0m2/g以上且10m2/g以下,更优选为1.0m2/g以上且5.0m2/g以下,进一步优选为1.0m2/g以上且3.0m2/g以下。 [0079] Further, the thermally conductive filler (B) is preferably a BET specific surface area of ​​1.0m2 / g or more and 10m2 / g or less, more preferably 1.0m2 / g or more and 5.0m2 / g or less, more preferably 1.0m2 / g and not more than 3.0m2 / g or less. 通过使导热性填料(B)的BET比表面积在上述范围,抑制成为导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)的原材料的混合组合物的粘度过度地增大,同时容易使导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)兼具拉伸强度和柔软性。 By thermally conductive filler (B) has a BET surface area in the above range, suppress the thermally conductive pressure-sensitive adhesive composition (F) and a pressure-sensitive adhesive sheet-like thermal conductivity to the mixed composition ratio of the raw material compact (G), the viscosity was excessively increased while easily thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of both the tensile strength and flexibility. 其中,作为导热性填料(B),可以组合使用BET比表面积在上述范围的导热性填料(BI)、和BET比表面积低于1.0m2/g的导热性填料(B2)。 Wherein, as the thermally conductive filler (B), it can be used in combination BET specific surface area in the range of the above-described thermally conductive filler (the BI), and a BET specific surface area is less than 1.0m2 / g of the thermally conductive filler (B2). 对于此时的BET比表面积在上述范围的导热性填料(BI)与根据希望所使用的BET比表面积低于1.0m2/g的导热性填料(B2)的量比,质量比(导热性填料(BI):导热性填料(B2))优选为(100:0)~(20:80),更优选为(80:20)~(30:70)。 For this case the BET specific surface area in the range of the above-described thermally conductive filler (BI) and the specific surface area of ​​less than 1.0m2 / g according to BET is desired to use thermally conductive filler (B2) the ratio, mass ratio of (thermally conductive filler ( the BI): the thermally conductive filler (B2)) is preferably (100: 0) to (20:80), more preferably (80:20) - (30:70). 由此,通过像这样组合使用BET比表面积不同的导热性填料(B),能够抑制上述混合组合物的粘度过度增大,同时能够在该混合组合物中大量地配合导热性填料(B)。 Thus, by using a different BET specific surface area of ​​the thermally conductive filler (B) such as a combination, it is possible to suppress the viscosity of the mixture composition is excessively increased, while being able to fit a large amount of thermally conductive filler in the mixture composition (B). 需要说明的是,本发明中“BET比表面积”是指通过以下方法计量出的值。 It should be noted that the present invention, "a BET specific surface area" refers to the measurement value by the following method. 首先,将氮和氦的混合气体导入到BET比表面积测定装置内,将放有试样(BET比表面积的测定对象物)的试样单元浸溃在液体氮中,使氮气吸附于试样表面。 First, a mixed gas of nitrogen and helium is introduced into the BET specific surface area measuring apparatus, the sample placed a sample cell (BET specific surface area of ​​the object to be measured) is impregnated in liquid nitrogen, nitrogen gas adsorbed to the sample surface . 达到吸附平衡后,将试样单元放入水浴中加热至常温,使试样上附着的氮脱附。 After the adsorption equilibrium, the sample cell is heated in a water bath to room temperature, nitrogen desorption adhering to the sample. 氮气吸附、脱附时通过试样单元前后的气体的混合比变化,因而以氮和氦的混合比恒定的气体为对照,通过导热度检测器(TCD)检测该变化,求出氮气的吸附量和脱附量。 Nitrogen adsorption, desorption by mixed gas ratio is changed before and after the sample cell, thereby to mix nitrogen and helium gas is constant ratio control, detects the change by a thermal conductivity detector (the TCD), the amount of nitrogen adsorbed is obtained and desorption amount. 测定前将单位量的氮气导入装置内进行标定,预先求出与通过TCD检测出的值对应的表面积的值,从而求出该试样的表面积。 Prior to assay the unit amount of nitrogen gas introduced into the apparatus is calibrated value corresponding to the value previously determined by the surface area of ​​the TCD detected, thereby obtaining the surface area of ​​the sample. 另外,通过将表面积除以该试样的质量,能够求出BET比表面积。 Further, by dividing the mass of the sample surface area, BET specific surface area can be obtained.

[0080] <多官能环氧化合物(E) > [0080] <polyfunctional epoxy compound (E)>

本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用多官能环氧化合物(E)。 The thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) using a polyfunctional epoxy compound (E). 多官能环氧化合物(E)能够与(甲基)丙烯酸酯聚合物(Al)中的有机酸基反应形成交联结构。 Polyfunctional epoxy compound (E) capable of forming a crosslinked structure (meth) acrylate polymer (Al) in the reaction with organic acid groups. 另外,同样地(甲基)丙烯酸酯单体(α I)含有具有有机酸基的单体的情况下,由于能够与该有机酸基反应,能够在含有来源于(甲基)丙烯酸酯单体(α O的结构单元的聚合物中形成交联结构。 Further, in the same manner (meth) acrylate monomer containing (α I) a case where a monomer having an organic acid group, since the group capable of reacting with the organic acid, can be derived containing (meth) acrylate monomer a structural unit (α O crosslinked structure is formed.

[0081] 多官能环氧化合物(E)的25°C下的粘度为600mPa s以下,优选为500mPa s以下,更优选为400mPa_s以下。 Viscosity [0081] The polyfunctional epoxy compound (E) of 600mPa s at 25 ° C or less, preferably 500mPa s or less, more preferably less 400mPa_s. 可以认为多官能环氧化合物的粘度过高时,在成为导热性压敏粘接剂组合物以及导热性压敏粘接性片状成形体的原材料的混合组合物中难以均匀地分散多官能环氧化合物,基于多官能环氧化合物的上述交联结构难以均匀地形成。 Can be considered mixed composition viscosity polyfunctional epoxy compound is too high, becoming the thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet-like thermally conductive molded material which is difficult to uniformly dispersing polyfunctional epoxy oxygen compounds, it is difficult to form a uniform crosslinked structure based on the above-described polyfunctional epoxy compound. 其结果,可以认为通过在导热性压敏粘接剂组合物以及导热性压敏粘接性片状成形体内局部性地形成弱的部分,拉伸强度降低。 As a result, it is considered a weak portion formed by thermally conductive pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet-like thermally conductive body formed locally, reduction in tensile strength. 需要说明的是,多官能环氧化合物(E)的粘度可以与下述磷酸酯(C)同样地操作进行测定。 Incidentally, the viscosity of the polyfunctional epoxy compound (E) can be measured with the following phosphate ester (C) in the same manner.

[0082] 根据本发明,可以认为通过如上所述使用粘度一定程度低的多官能环氧化合物 [0082] According to the present invention, it is considered a low viscosity as mentioned above by using a polyfunctional epoxy compound to some extent

(E),上述多官能性单体(D)和·多官能环氧化合物(E)在成为导热性压敏粘接剂组合物(F)和导热性压敏粘接性片状成形体(G)的原材料的混合组合物内均匀地分散,在导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)内容易均匀地形成交联结构。 (E), the polyfunctional monomer (D) and - polyfunctional epoxy compound (E) in the thermally conductive pressure-sensitive adhesive became composition (F) and the thermally conductive pressure-sensitive adhesive sheet materials ( uniformly dispersed within the raw material mixed composition G), and thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) content is easy to uniformly crosslinked structure. 其结果,可以获得维持柔软性的同时提高拉伸强度的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 As a result, it can be obtained while maintaining flexibility of the thermally conductive pressure-sensitive adhesive composition (F) to improve the tensile strength and the thermal conductivity of the pressure-sensitive adhesive sheet-like molded article (G).

[0083] 本发明中使用的多官能环氧化合物(E)具有2以上且10000以下的官能团(环氧基),官能团的个数优选为2以上且1000以下,更优选为2以上10以下。 [0083] The present invention is used in the polyfunctional epoxy compound (E) having 2 or more and 10,000 or less of a functional group (epoxy group), the number of functional groups is preferably 2 or more and 1000 or less, more preferably 2 or more and 10 or less. 通过使多官能环氧化合物(E)的官能团的个数在上述范围,容易使导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)兼具拉伸强度和柔软性。 By making the number of the polyfunctional epoxy compound (E) a functional group in the above range, easily thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) has both tensile strength and flexibility.

[0084] 作为用于本发明的多官能环氧化合物(E)的具体例,可以列举出间苯二酚二缩水甘油基醚、乙二醇二缩水甘油基醚、1,6-己二醇二缩水甘油基醚、新戊二醇二缩水甘油基醚、氢化双酚A 二缩水甘油基醚、甘油聚缩水甘油基醚、三羟甲基丙烷三缩水甘油基醚、季戊四醇二缩水甘油基醚、季戊四醇三缩水甘油基醚、季戊四醇四缩水甘油基醚、二甘油四缩水甘油基醚、聚甘油聚缩水甘油基醚、山梨糖醇聚缩水甘油基醚等。 [0084] Examples of the polyfunctional epoxy compound (E) used in the present invention. Specific examples include resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether , pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol tetraglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like. 其中,季戊四醇四缩水甘油基醚即使少量也能够有效地形成交联结构,因而优选。 Wherein, pentaerythritol tetraglycidyl ether, even a small amount can be efficiently crosslinked structure, which is preferable. 多官能环氧化合物(E)可以单独使用I种,也可以组合使用2种以上。 Polyfunctional epoxy compound (E) may be used alone, Type I may be used in combination of two or more kinds.

[0085] 相对于(甲基)丙烯酸类树脂组合物(A) 100质量份,本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用的多官能环氧化合物(E)的量为0.3质量份以上且5.0质量份以下,优选为0.4质量份以上且4.0质量份以下,更优选为0.5质量份以上且3.0质量份以下。 [0085] 100 parts by mass of the (meth) acrylic resin composition (A), the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G amount of the polyfunctional epoxy compound (E)) is used is 0.3 parts by mass or more and 5.0 parts by mass or less, preferably 0.4 parts by mass or more and 4.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less. 通过使多官能环氧化合物(E)的用量为上述范围,容易使导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)兼具拉伸强度和柔软性。 By reacting a polyfunctional epoxy compound (E) is used in an amount within the above range, easily thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) has both a tensile strength and softness.

[0086]〈磷酸酯(C)> [0086] <phosphoric ester (C)>

本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中优选使用磷酸酯(C)。 The thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like formed body (G) preferably used phosphoric acid ester (C). 通过使用磷酸酯(C),容易赋予导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)优异的阻燃性。 By using phosphate (C), easy to impart the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) is excellent in flame retardancy. 另外,大量地使用磷酸酯(C)时,形成导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)前的混合组合物的操作性恶化,通过组合使用磷酸酯(C)和上述导热性填料(BI),能够抑制磷酸酯(C)的用量,抑制导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)燃烧时的滴落提高阻燃性,混合组合物的操作性也提高。 Further, when a large amount of phosphoric ester (C), forming the thermally conductive pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like thermal conductivity to deteriorate workability of the mixed composition before molding (G), phosphate ester (C) and said thermally conductive filler (BI) by a combination, can suppress the amount of phosphate (C), the inhibition of the thermally conductive pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like thermally conductive molded dripping during burning (G) to improve the flame resistance, workability of the mixed composition is also improved.

[0087] 磷酸酯(C)优选25°C下的粘度为3000mPa·s以上。 [0087] viscosity phosphate ester (C) at 25 ° C preferably 3000mPa · s or more. 通过使磷酸酯(C)的粘度在上述范围,容易防止导热性压敏粘接剂组合物(F)或者导热性压敏粘接性片状成形体(G)的成形性变差。 By phosphate (C) in the above viscosity range, it is easy to prevent the thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) is deteriorated moldability. 需要说明的是,本发明中磷酸酯的“粘度”是指通过以下说明的方法测定的粘度。 It should be noted that the present invention, the phosphate "viscosity" refers to viscosity measured by the method described below.

[0088](磷酸酯的粘度测定方法) [0088] (viscosity measuring method phosphate)

磷酸酯的粘度测定使用B型粘度计(东京计器株式会社制)按照以下所示的步骤进行。 Viscosity was measured using a phosphate B-type viscometer (Tokyo Keiki Co., Ltd.) according to the procedure described below.

(1)在常温的环境下计量300ml磷酸酯,放入500ml的容器中。 (1) 300ml phosphate measurement environment at room temperature, placed in 500ml containers.

(2)从搅拌用转子N0.1、2、3、4、5、6、7中选择任一个安装于粘度计。 (2) from any selected N0.1,2,3,4,5,6,7 stirred with a rotor mounted on the viscometer.

(3)将放有磷酸酯的容器放在粘度计上,将转子沉没于该容器内的缩合磷酸酯中。 (3) will be placed on the container phosphate viscometer, rotor submerged in the condensed phosphate within the vessel. 此时,以作为转子标记的凹处整好到达磷酸酯的液态界面的方式沉下转子。 In this case, the rotor as marked depression good way to reach the whole liquid interface phosphate sink rotor.

(4)转速从20、10、4、2中选择。 (4) selected from the 20,10,4,2 speed.

(5)按下搅拌开关,读取I分钟后的数值。 (5) pressed stirred switch reads the value of I min.

(6)读取的数值乘以系数A而得到的值为粘度[mPa·S]。 (6) A coefficient value read is multiplied by a value obtained by viscosity [mPa · S].

[0089] 需要说明的是,系数A如下述表1中所示,由选择的转子N0.和转速决定。 [0089] Incidentally, the coefficient A as shown in the following Table 1, by the selection of rotor N0. And speed decisions.

[0090] [表1] [0090] [Table 1]

Figure CN103874739AD00141

[0091] 另外,磷酸酯(C)优选在大气压下的15°C以上且100°C以下的温度区域中一直为液体。 [0091] Further, phosphoric ester (C) is preferably at least 15 ° C at atmospheric pressure and at a temperature in the region below 100 ° C has been liquid. 磷酸酯(C)混合时若为液体,则操作性良好,容易成形导热性压敏粘接剂组合物(F)或者导热性压敏粘接性片状成形体(G)。 Phosphoric ester (C) is mixed, if liquid, good operability, easy to form the thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive pressure-sensitive adhesive sheet-like molded article (G). 成形含有磷酸酯(C)的导热性压敏粘接剂组合物 Forming a phosphate containing (C) a thermally conductive pressure-sensitive adhesive composition

(F)或者导热性压敏粘接性片状成形体(G)时,优选在15°C以上且100°C以下的环境中,将构成导热性压敏粘接剂组合物(F)或者导热性压敏粘接性片状成形体(G)的各物质进行混合。 (F) or pressure-sensitive adhesive sheet-like thermally conductive molded article when (G), preferably above 15 ° C and below 100 ° C environment, constituting the thermally conductive pressure-sensitive adhesive composition (F) or thermally conductive pressure-sensitive adhesive sheet-like molded article (G) of each substance were mixed. 通过使混合时的温度在上述范围,为(甲基)丙烯酸类树脂组合物(A)的玻璃化转变温度以上,容易防止(甲基)丙烯酸类树脂组合物(A)中含有的单体等的挥发或者聚合反应开始,因而能够使环境性和操作性良好。 When the temperature of mixing the above range, the glass of (meth) acrylic resin composition (A) a transition temperature, the monomer is easy to prevent the (meth) acrylic resin composition (A) and the like contained in evaporation or polymerization reaction got started, it is possible to make the environment and good operability.

[0092] 本发明中的磷酸酯(C)还可以使用缩合磷酸酯或非缩合磷酸酯。 In [0092] phosphate ester of the present invention (C) may also be used condensed phosphate or condensed phosphate. 这里所述“缩合磷酸酯”是指,I分子内存在多个磷酸酯部位的缩合磷酸酯,“非缩合磷酸酯”是指,I分子内仅存在I个磷酸酯部位的酯。 Here the "condensed phosphate" refers to a molecule in a condensed phosphate I phosphate plurality of sites, "non condensed phosphate" refers to the presence of only the I phosphate ester portion within I molecules. 以下列出满足到此为止说明的条件的磷酸酯(C)的具体例。 The following lists the conditions described far phosphate ester (C) satisfy the specific examples.

[0093] 作为缩合磷酸酯的具体例,可以列举出1,3-亚苯基双(二苯基磷酸酯)、双酚A双(二苯基磷酸酯)、间苯二酚双(二苯基磷酸酯)等芳香族缩合磷酸酯;聚氧基亚烷基双二氯烷基磷酸酯等含卤素系缩合磷酸酯;非芳香族非卤素系缩合磷酸酯;等。 [0093] Specific examples of the condensed phosphoric acid ester include 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate group) and aromatic condensed phosphate; polyoxyalkylene alkyl phosphate bis-dichloro halogen-containing condensed phosphoric acid ester-based; non-halogen non-aromatic condensed phosphoric acid ester; and the like. 这些之中,芳香族缩合磷酸酯由于比重比较小、没有有害物质(卤素等)的放出危险、也容易获得等,而优选,更优选为1,3-亚苯基双(二苯基磷酸酯)、双酚A双(二苯基磷酸酯)。 Among these, the aromatic condensed phosphate due to the small specific gravity, there is no danger of emission of harmful substances (such as halogen), and the like can be easily obtained, and preferably, and more preferably 1,3-phenylene bis (diphenyl phosphate ), bisphenol A bis (diphenyl phosphate). [0094] 作为非缩合磷酸酯的具体例,可以列举出磷酸三苯基酯、磷酸三甲苯基酯、磷酸三(二甲苯基)酯、磷酸甲苯基二苯基酯、磷酸甲苯基-2,6-二甲苯基酯、磷酸2-乙基己基二苯基酯等芳香族磷酸酯;三(β -氯丙基)磷酸酯、磷酸三(二氯丙基)酯、磷酸三(三溴新戊基)酯等含卤素系磷酸酯;等。 [0094] Specific examples of the non-condensed phosphoric acid ester include triphenyl phosphate, tricresyl phosphate, tris (dimethylphenyl) phosphate, cresyl diphenyl phosphate, toluene-2, 6- xylyl phosphate, 2-ethylhexyl diphenyl phosphate and the like aromatic; three (β - chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl pentyl) phosphate ester containing halogen-based; the like. 这些之中,芳香族磷酸酯由于不产生有害物质(卤素等)等而优选。 Among these, the aromatic phosphoric acid ester is not generated harmful substances (halogens, etc.) and the like preferably.

[0095] 磷酸酯(C)可以单独使用一种,也可以组合使用两种以上。 [0095] The phosphoric ester (C) may be used alone or in combination of two or more.

[0096] 本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中使用磷酸酯(C)的情况下,相对于(甲基)丙烯酸类树脂组合物(A) 100质量份,其量优选为45质量份以上且190质量份以下,更优选为55质量份以上且150质量份以下,进一步优选为70质量份以上且120质量份以下。 The case where [0096] the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) in phosphate ester (C) with respect to (meth) 100 parts by mass of the acrylic resin composition (A), the amount thereof is preferably 45 parts by mass or more and 190 parts by mass or less, more preferably 55 parts by mass or more and 150 parts by mass or less, more preferably 70 parts by mass or more and 120 parts by mass the following. 通过使磷酸酯(C)的含量在上述范围,容易提高导热性压敏粘接剂组合物(F)或导热性压敏粘接性片状成形体(G)的阻燃性。 By phosphate (C) content in the above range, the flame retardancy is easily improved thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) is.

[0097]〈其它添加剂〉 [0097] <Other Additives>

在本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)中除了上述物质以外,还可以在不妨碍通过配合上述物质而产生的上述效果的范围内添加公知的各种添加剂。 In the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) in addition to the above substances may also be without prejudice to the above-described materials by blending the above-described generated adding the effects of the various known additives. 作为公知的添加剂,可以列举出发泡剂(包括发泡助剂);上述导热性填料(B)以外的金属的氢氧化物、金属盐水合物等阻燃性导热无机化合物;玻璃纤维;膨胀化石墨粉、PITCH系碳纤维等上述导热性填料(B)以外的导热性无机化合物;外部交联剂;炭黑、二氧化钛等颜料;粘土等其它充填材料;富勒烯、碳纳米管等纳米粒子;多酚系、氢醌系、受阻胺系等抗氧化剂;丙烯酸系聚合物粒子、微粒二氧化硅、氧化镁等增稠剂;等。 Examples of the known additive include a foaming agent (including foaming aid); metal hydroxides other than the above-described thermally conductive filler (B), the thermally conductive metal hydrate inorganic flame retardant compound; glass fibers; the expanded thermally conductive inorganic compound other than graphite, the PITCH-based carbon fiber of the thermally conductive filler (B); external crosslinking agent; carbon black, titanium dioxide and other pigments; clay and other filling materials; fullerenes, carbon nanotubes and other nanoparticles; polyphenol-based, hydroquinone-based, hindered amine-based antioxidant and the like; acrylic polymer particles, particulate silica, magnesia thickener; and the like.

[0098] 2.制造方法 [0098] 2. A method for producing

本发明的导热性压敏粘接剂组合物(F)能够如下获得:将到此为止说明了的各物质进行混合制作混合组合物后,至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应,从而获得。 The thermally conductive pressure-sensitive adhesive composition (F) according to the present invention can be obtained as follows: After each of the substances so far described are mixed to prepare a mixed composition, at least (meth) acrylate monomer (α I) and polyfunctional monomer (D) polymerization, and (meth) acrylate polymer (Al) and / or a (meth) acrylate monomer (α I) of the polymer structural units derived from cross-linking reaction, to thereby obtain.

[0099] 即,本发明的导热性压敏粘接剂组合物(F)的制造方法包括如下工序:制作包含含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、导热性填料(B)、多官能性单体(D)和多官能环氧化合物(E)的混合组合物的工序;以及在该混合组合物中至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应。 [0099] That is, the method for producing the thermally conductive pressure-sensitive adhesive composition of the invention is (F) comprises the steps of: making comprising comprising (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition ([alpha]), the thermally conductive filler (B), polyfunctional monomer (D) and the polyfunctional epoxy compound (E) is a mixed composition; and at least (meth) acrylate monomer (α I) a polyfunctional monomer and (D) a polymerization reaction, and (meth) acrylate polymer (Al) and / or a mixture containing sources of the composition polymer (meth) acrylate monomer of the structural unit (α I) of the crosslinking reaction. 需要说明的是,其它能够使用的物质、各物质的优选的含有比率等如上所述,这里省略详细的说明。 Incidentally, other materials can be used, preferably each substance content ratio, etc. As described above, the detailed description thereof is omitted herein.

[0100] 本发明的导热性压敏粘接剂组合物(F)的制造方法中,在进行上述聚合和交联反应时,优选进行加热。 [0100] The method for producing the thermally conductive pressure-sensitive adhesive composition of the present invention, (F), in carrying out the polymerization and crosslinking reaction is preferably heated. 该加热可以使用例如热风、电加热器、红外线等。 The hot-air heating may be used, for example, an electric heater, infrared rays. 此时的加热温度优选为聚合引发剂效率良好地分解、(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合推进的温度。 The heating temperature is preferably a polymerization initiator with good decomposition efficiency, polymeric (meth) acrylate monomer (α I) and the polyfunctional monomer (D) is propelled temperature. 温度范围根据所使用的聚合引发剂的种类而不同,优选为100°C以上且200°C以下,更优选为130°C以上且180°C以下。 The temperature range of the kind used in the polymerization initiator, but is preferably not less than 100 ° C and below 200 ° C, more preferably 130 ° C and 180 ° C or less.

[0101] 本发明的导热性压敏粘接性片状成形体(G)能够如下获得:将到此为止说明的各物质混合,制作混合组合物,将该混合组合物成形为片状后,或者在将该混合组合物成形为片状的同时,至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应,从而获得。 [0101] The thermally conductive pressure-sensitive adhesive of the present invention, the sheet material (G) can be obtained as follows: each material will be explained so far mixed to prepare mixed composition, the mixed composition was molded into a sheet, or molding the mixed composition into a sheet while at least (meth) acrylate monomer (α I) a polyfunctional monomer and (D) a polymerization reaction, and (meth) acrylate polymer (Al) and / or crosslinking reaction of the polymer of (meth) acrylate monomer structural units (α I) containing from to obtain.

[0102] 即,本发明的导热性压敏粘接性片状成形体(G)的制造方法包含如下工序:制作包含含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(A)、导热性填料(B )、多官能性单体(D )和多官能环氧化合物(E )的混合组合物的工序;以及将该混合组合物成形为片状后,或者在将该混合组合物成形为片状的同时,至少进行(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合反应、以及(甲基)丙烯酸酯聚合物(Al)和/或含有来源于(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应的工序。 [0102] That is, the method for producing the thermally conductive pressure-sensitive adhesive of the present invention, the sheet material (G), comprising the steps of: making comprising comprising (meth) acrylate polymer (Al) and (meth) acrylate step monomer (α I) of the (meth) acrylic resin composition (a), the thermally conductive filler (B), polyfunctional monomer (D) and the polyfunctional epoxy compound (E) a mixed composition of ; and after forming the mixed composition into a sheet, or molded in the mixed composition into a sheet while at least (meth) acrylate monomer (α I) and polyfunctional monomer (D) polymerization, and (meth) acrylate polymer (Al) and / derived containing (meth) step of the crosslinking reaction or a polymer structural units acrylic acid ester monomer (α I) of. 需要说明的是,其它能够使用的物质、各物质的优选含有比率等如上所述,这里省略详细说明。 Incidentally, other materials can be used, preferably the content ratio of each material, etc. As described above, the detailed description thereof will be omitted here.

[0103] 本发明的导热性压敏粘接性片状成形体(G)的制造方法中,进行上述聚合和交联反应时,优选进行加热。 When [0103] The method for producing the thermally conductive pressure-sensitive adhesive of the present invention, the sheet material (G), the above-described polymerization and crosslinking reaction is preferably heated. 该加热可以使用例如热风、电加热器、红外线等。 The hot-air heating may be used, for example, an electric heater, infrared rays. 此时的加热温度优选为聚合引发剂有效地分解、(甲基)丙烯酸酯单体(α I)和多官能性单体(D)的聚合推进的温度。 The heating temperature is preferably effective to decompose the polymerization initiator, polymerizable (meth) acrylate monomer (α I) and the polyfunctional monomer (D) is propelled temperature. 温度范围根据所使用的聚合引发剂的种类而不同,优选为100°C以上200°C以下,更优选为130°C以上180°C以下。 The temperature range of the kind used in the polymerization initiator, but is preferably not less than 100 ° C 200 ° C or less, more preferably 130 ° C 180 ° C or less.

[0104] 将上述混合组合物成形为片状的方法没有特别限定。 [0104] The above mixture composition into a sheet molding method is not particularly limited. 作为合适的方法,可以列举出例如将混合组合物涂布于经过脱模处理的聚酯膜等脱模膜上的流延法(々' ^卜法),将混合组合物夹持于两张根据需要经过了脱模处理的脱模膜之间并使其通过辊之间的方法,以及使用挤出机挤出混合组合物时使其通过模控制厚度的方法等。 As a suitable method, for example, include a mixed composition was coated on a release polyester film after release treatment film casting method (々 '^ BU method), the mixed composition was sandwiched between two the need to go through between the release film and allowed to release treatment by the process of molding the like so as to control the thickness of the mixed composition is extruded between the rollers by the process, and the use of an extruder. [0105] 本发明的导热性压敏粘接性片状成形体(G)即使比以往的导热性压敏粘接性片状成形体更薄地成形也能够具备优异的柔软性和拉伸强度。 [0105] The thermally conductive pressure-sensitive adhesive of the present invention, the sheet material (G) than a conventional molded article, even if the thermal conductive sheet-like pressure-sensitive adhesive property can be formed thinner have excellent flexibility and tensile strength. 另外,通过使导热性压敏粘接性片状成形体(G)的厚度薄,能够降低导热性压敏粘接性片状成形体(G)的厚度方向的热阻。 Further, by making the thermal conductivity of the pressure sensitive adhesive sheet-like molded article (G) in thickness, can reduce the thermal resistance of the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) in the thickness direction. 导热性压敏粘接性片状成形体(G)的厚度可以例如为0.05mm以上且3.0mm以下,优选为0.1mm以上,优选为1.0mm以下,更优选为0.5mm以下。 The thickness of the thermally conductive pressure-sensitive adhesive of the sheet material (G) may, for example, 0.05mm or more and 3.0mm or less, preferably 0.1mm or more, preferably 1.0mm or less, more preferably 0.5mm or less. 通过使导热性压敏粘接性片状成形体(G)在上述下限以上,容易防止在将该导热性压敏粘接性片状成形体(G)贴附于发热体和散热体时卷入空气,结果能够防止热阻的增加,使对被粘体的贴附工序中的操作性良好。 By thermally conductive pressure-sensitive adhesive sheet-like molded article (G) than the above lower limit, molded easily prevented (G) in the thermally conductive sheet-like pressure-sensitive adhesive property when the volume is attached to the heating element and a radiator into the air, the result is possible to prevent increase in thermal resistance, so that a good step of attaching the adherend operability.

[0106] 另外,导热性压敏粘接性片状成形体(G)能够在基材的单面或者两面成形。 [0106] Further, the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) can be formed on both surfaces or on one surface of the substrate. 构成该基材的材料没有特别限定。 The material constituting the substrate is not particularly limited. 作为该基材的具体例,可以列举出铝、铜、不锈钢、铍铜等导热性优异的金属、以及合金的箔状物、导热性有机硅等由其自身导热性优异的聚合物形成的片状物、含有导热性添加物而成的导热性塑料膜、各种无纺布、玻璃布、蜂窝结构体等。 Specific examples of the substrate include a substrate excellent in thermal conductivity by itself polymer formed of aluminum, copper, stainless steel, beryllium copper or the like having excellent thermal conductivity metal, and alloy foils, heat-conductive silicone, etc. which was thermally conductive thermal conductivity containing an additive made of a plastic film, non-woven, glass cloth, and the like of the honeycomb structure. 作为塑料膜,可以使用聚酰亚胺、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚四氟乙烯、聚醚酮、聚醚砜、聚甲基戊烯、聚醚酰亚胺、聚砜、聚苯硫醚、聚酰胺酰亚胺、聚酯酰亚胺、芳香族聚酰胺等耐热性聚合物的膜。 As the plastic film, a polyimide, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polytetrafluoroethylene, polyether ketone, polyether sulfone, polymethylpentene, poly heat-resistant polymer film ether, polysulfone, polyphenylene sulfide, polyamideimide, polyester imide, aromatic polyamide and the like.

[0107] 3.使用例 [0107] 3. Example

本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)可以用作电子部件的一部分。 The thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) may be used as part of the electronic component. 此时,能够在散热体这样的在基材上直接成形而作为电子部件的一部分提供。 In this case, the radiator on a substrate such as a part directly formed to provide an electronic component. 作为该电子部件的具体例,可以列举出具有电致发光元件(EL)、发光二极管(LED)光源的设备中的发热部周围的部件、汽车等的功率器件周围的部件、燃料电池、太阳能电池、电池、手机、掌上电脑(PDA)、笔记本电脑、液晶、表面传导型电子发射元件显示器(SED)、等离子体显示面板(PDP)、或者集成电路(IC)等具有发热部的设备或部件。 Specific examples of the electronic component may include a peripheral electroluminescence elements (the EL), around the light emitting diode (LED) light source device of the heat generating unit member, such as an automobile power device components, fuel cells, solar cells , batteries, mobile phones, PDAs (PDA), notebook computers, liquid crystal, a surface-conduction electron-emitter display (SED), plasma display panel (PDP), or an integrated circuit (IC) device or the like member having a heat generating portion.

[0108] 需要说明的是,作为本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)用于电子设备的方法,以用于LED光源的情况作为例子时,可以例示以下这样的使用方法。 [0108] Incidentally, as the thermally conductive pressure-sensitive adhesive composition (F) of the present invention and a method of thermally conductive pressure-sensitive adhesive sheet-like molded article (G) for an electronic device, for LED a light source as an example, the following can be exemplified such use. 即有直接贴附于LED光源;夹持于LED光源与散热材料(散热器、风扇、拍尔帖元件、热管、石墨片材等)之间;贴附于与LED光源连接的散热材料(散热器、风扇、珀尔帖元件、热管、石墨片材等);作为包围LED光源的筐体使用;贴附于包围LED光源的筐体;埋于LED光源与筐体的间隙;等方法。 That is directly attached to the LED light source; sandwiched between the LED light source and the heat radiation material (heat sinks, fans, Peltier elements beat, heat pipe, the graphite sheet, etc.); a heat dissipating material is attached to the LED light source is connected (heat , fans, Peltier elements, a heat pipe, the graphite sheet, etc.); as a housing surrounding the LED light source; attached to the housing surrounding the LED light source; LED light source and the gap is buried in the housing body; like. 另外,作为具备本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的LED光源的用途例,可以列举出透射型的具有液晶面板的显示装置的背光源装置(电视、手机、PC、笔记本PC、PDA等);车辆用灯具;工业用照明;商业用照明;一般住宅用照明;等。 Further, use of the LED light source embodiment of the present invention includes a thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) may include a transmission type liquid crystal panel having backlight unit of a display device (TV, mobile, PC, notebook PC, PDA, etc.); vehicle lighting; industrial lighting; commercial lighting; general residential lighting; and so on.

[0109] 另外,作为本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的除LED光源以外的使用例,可以列举出以下这样的用途。 [0109] Further, as the thermally conductive pressure-sensitive adhesive composition (F) of the present invention and the sheet-like thermally conductive pressure-sensitive adhesive to use LED light sources other than the embodiment article (G) may include the following manner the use of. 即PDP面板;IC发热部;冷阴极管(CCFL);有机EL光源;无机EL光源;高亮度发光LED光源;高亮度发光有机EL光源;高亮度发光无机EL光源;CPU ;MPU ;半导体元件;等中也可以使用本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 I.e. PDP panel; the IC heat generating portion; cold cathode tube (the CCFL); organic EL light source; an inorganic EL light source; high-brightness LED light source; high-brightness light-emitting organic EL light source; high luminance of the inorganic EL light source; CPU; MPU; semiconductor element; and the like may also be used in the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G).

[0110] 进一步地,本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)的使用方法不限定于上述形态,也可以贴附于到此为止例示出的以外的装置的筐体等使用。 [0110] Further, the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) is not limited to the use of form, may be attached to housing means other than the embodiment shown so far is used. 例如,也可以在汽车等所具备的装置中使用。 For example, the apparatus may be used in the automobile or the like provided. 即,可以列举出贴附于汽车所具备的装置的筐体的内部;贴附于汽车所具备的筐体的外侧;将位于汽车所具备的筐体的内部的发热部(汽车导航系统/燃料电池/热交换器)与该筐体连接;贴附于与位于汽车所具备的筐体的内部的发热部(汽车导航系统/燃料电池/热交换器)连接的散热板;等。 I.e., it may include means attached to the interior of the car is provided in the housing; attached to the outside of automobile is provided in the housing; the housing is located in the interior of cars included in the heat generating portion (car navigation system / fuel battery / heat exchanger) connected to the housing; the heat generating portion is attached to the inside of the heat dissipation plate housing body (car navigation system / fuel cell / heat exchanger) located connected to the car included; and the like.

[0111] 需要说明的是,除了汽车以外,也可以通过同样的方法使用本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)。 [0111] Incidentally, in addition to the car, may be molded (G) using a thermally conductive pressure-sensitive adhesive composition (F) of the present invention and the sheet-like thermally conductive pressure-sensitive adhesive property by the same method. 作为其对象,可以列举出例如电脑;住宅;电视机;手机;自动贩卖机;冰箱;太阳能电池;表面传导型电子发射元件显示器(SED);有机EL显示器;无机EL显示器;有机EL照明;无机EL照明;有机EL显示器;笔记本电脑;PDA ;燃料电池;半导体装置;电饭煲;洗衣机;洗涤干燥机;光半导体元件与荧光体组合而成的光半导体装置;各种功率器件;游戏机;电容器;等。 As a target, for example, it may include a computer; Residence; TV; phone; vending machine; refrigerator; solar cell; surface-conduction electron-emitter display (SED); organic EL display; an inorganic EL display; organic EL illumination; Inorganic EL lighting; organic EL display; laptop; a PDA; fuel cell; semiconductor device; cooker; washing machine; washing and drying machine; an optical semiconductor device of an optical semiconductor element and the phosphor are combined; various power devices; gaming machine; a capacitor; Wait.

[0112] 进一步地,本发明的导热性压敏粘接剂组合物(F)以及导热性压敏粘接性片状成形体(G)不仅能用于上述使用方法,还能够根据用途通过其它方法使用。 [0112] Further, the thermally conductive pressure-sensitive adhesive composition (F) and the thermal conductivity of the present invention, the pressure-sensitive adhesive sheet-like molded article (G) not only for the above-described method of use is also possible according to the use by another method. 可以列举出例如用于使地毯、暖垫等热均匀化;用作LED光源/热源的密封剂;用作太阳能电池单元的密封剂;用作太阳能电池的背板;用于太阳能电池的背板与屋顶之间;用于自动贩卖机内部的隔热层的内侧;在有机EL照明的筐体内部与干燥剂、吸湿剂一起使用;在有机EL照明的筐体内部的导热层以及其上与干燥剂、吸湿剂一起使用;在有机EL照明的筐体内部的导热层、散热层、以及它们之上与干燥剂、吸湿剂一起使用;在有机EL照明的筐体内部的导热层、环氧系的散热层、以及其上与干燥剂、吸湿剂一起使用;对于用于使人、动物降温的装置、衣类、毛巾、片材等冷却构件,在与身体的相反侧使用;用于在电子照片复印机、电子照片打印机等图像形成装置中搭载的固定装置的加压构件;用作在电子照片复印机、电子照片打印机等图像形成装置中搭载 May include for example, carpets, mats and other warm thermal homogenization; back sheet for a solar cell; LED as a light source / heat sealing agent; as a sealant of the solar battery cell; as a solar cell back sheet and between the roof; inside a vending machine inside the heat-insulating layer; used with the organic EL illumination casing interior with a desiccant, moisture absorbent; and a thermally conductive layer on the inside of the housing and the organic EL illumination the drying agent with a moisture absorbent used; thermally conductive layer inside the housing of the organic EL illumination, the heat dissipation layer, and their use with the above desiccant, moisture absorbent; thermally conductive layer inside the housing of the organic EL illumination, epoxy the heat dissipation layer system, and on which the desiccant, with the use of moisture absorbent; a cooling member for people, animals cooling apparatus, clothing, towels, sheets, etc., used on the opposite side of the body; for the pressing member fixing apparatus means an electrophotographic copying machine is mounted, an image forming electrophotographic printer; as mounted in an electrophotographic copying machine, electrophotographic printer or the like in an image forming apparatus 固定装置的加压构件本身;用作载置制膜装置的处理对象体的热流控制用传热部;用于载置制膜装置的处理对象体的热流控制用传热部;用于放射性物质容纳容器的外层与内饰之间;在设置有吸收太阳光线的太阳能面板的箱体中使用;在CCFL背光源的反射片材与铝制机箱之间使用;等。 The pressing member fixing apparatus itself; the heat flow used as a placement of the film forming apparatus body processed by the control transfer unit; heat processed body for mounting the film transfer apparatus control unit; radioactive material accommodated between the outer layer and the interior of the container; the use of solar panels is provided with absorption of the sun's rays in the housing; used between the reflective sheet and the CCFL backlight aluminum chassis; and the like.

[0113] 最后,在本发明的导热性压敏粘接剂组合物(F)、导热性压敏粘接性片状成形体(G)、导热性压敏粘接剂组合物(F)的制造方法、和导热性压敏粘接性片状成形体(G)的制造方法中,优选的导热性填料(B)为氢氧化铝和/或氧化铝。 [0113] Finally, in the thermally conductive pressure-sensitive adhesive composition (F) of the present invention, the thermally conductive pressure-sensitive adhesive sheet-like molded article (G), the thermally conductive pressure-sensitive adhesive composition (F), the method of manufacturing a manufacturing method, and thermal pressure-sensitive adhesive sheet-like molded article (G), preferably the thermally conductive filler (B) is aluminum hydroxide and / or aluminum oxide.

[0114]另外,在本发明的导热性压敏粘接剂组合物(F)、导热性压敏粘接性片状成形体 [0114] Further, in the thermally conductive pressure-sensitive adhesive composition (F) of the present invention, the thermally conductive pressure-sensitive adhesive sheet materials

(G)、导热性压敏粘接剂组合物(F)的制造方法、和导热性压敏粘接性片状成形体(G)的制造方法中,包含100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、90质量份以上且1200质量份以下的导热性填料(B),0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、和 The method of production method (G), the thermally conductive pressure-sensitive adhesive composition (F), the pressure-sensitive adhesive property and thermal conductivity the sheet material (G) in, comprising 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition ([alpha]), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (B) , 0.2 parts by mass or more and 8 parts by mass of a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D), and

0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa-S以下的多官能环氧化合物(E)的混合组合物,优选进一步含有相对于前述(甲基)丙烯酸类树脂组合物(A) 100质量份为45质量份以上且190质量份以下的磷酸酯(C)。 Mixed composition, 0.3 parts by mass or more and having a 5.0 parts by mass or less of functional groups of 2 or more and 10,000 or less and a viscosity at 25 ° C, 600mPa-S The following polyfunctional epoxy compound (E), and preferably further contains respect the parts of (a) 100 mass of (meth) acrylic resin composition is 45 parts by mass or more and 190 parts by mass of the phosphoric ester (C).

[0115]另外,在本发明的导热性压敏粘接剂组合物(F)、导热性压敏粘接性片状成形体 [0115] Further, in the thermally conductive pressure-sensitive adhesive composition (F) of the present invention, the thermally conductive pressure-sensitive adhesive sheet materials

(G)、导热性压敏粘接剂组合物(F)的制造方法、和导热性压敏粘接性片状成形体(G)的制造方法中,前述混合组合物优选进一步含有相对于前述(甲基)丙烯酸类树脂组合物(A) 100质量份为0.01质量份以上且10质量份以下的聚合引发剂。 The method of production method (G), the thermally conductive pressure-sensitive adhesive composition (F), the pressure-sensitive adhesive property and thermal conductivity the sheet material (G), the aforementioned mixed composition preferably further comprises the relative parts of (a) 100 mass of (meth) acrylic resin composition of 10 parts by mass or less 0.01 parts by mass or more and a polymerization initiator.

实施例 Example

[0116] 以下通过实施例进一步详细说明本发明,但本发明不受实施例的限定。 [0116] The present invention will be described in further detail by way of Examples, but the present invention is not limited to the examples embodiment. 需要说明的是,这里使用的“份”、“%”在无特别说明时,为质量基准。 Incidentally, "parts" as used herein, "%" in the absence of special instructions, on a mass basis.

[0117] <硬度(柔软性)> [0117] <hardness (softness)>

如后所述那样制作导热性压敏粘接性片状成形体(G),切成30mmX50mm的大小,准备多张将制作时所使用的脱模膜(实施了脱模处理的聚对苯二甲酸乙二醇酯膜。以下称为“脱模PET膜”)进行剥离而得到的片材。 As described above the production of the thermally conductive pressure-sensitive adhesive sheet-like molded article (G), cut 30mmX50mm size, preparing a plurality of the release film when used in the production (release treatment of polyethylene terephthalate polyethylene terephthalate film is hereinafter referred to as "release PET film") obtained by peeling the sheet. 对该切出的片材使用滑石进行喷粉(粉打七),以达到6mm左右厚度的方式层叠相同的片材,载置于硬度计(高分子计器株式会社制“CL-150”、按照JIS K7312)的试样台上。 The sheet is cut out using powder of talc (play seven powder), in order to achieve a thickness of about 6mm laminate the same manner as a sheet, placed hardness meter (Kobunshi Keiki Co., Ltd. "CL-150", stage according to JIS K7312) of the sample. 然后,放下阻尼器(夕' >^一)开始测定。 Then, put the damper (Xi '> ^ a) to start the measurement. 将阻尼器到达试样的时刻起20秒后的值作为硬度的测定值读取。 The timing value reaches the damper 20 seconds to read a sample from the measured value as hardness. 将该结果示于表2。 The results are shown in Table 2. 需要说明的是,从脱模PET膜进行剥离时,对于粉碎而无法剥离的片材,作为无法评价。 Incidentally, when peeled from the release PET film, as the sheet can not be peeled off and pulverized, as could not be evaluated.

[0118] <拉伸强度> [0118] <Tensile strength>

如后所述那样制作导热性压敏粘接性片状成形体(G),将制作时使用的脱模PET膜剥离通过下述方法测定断裂强度。 The breaking strength was measured as above after making the thermally conductive pressure-sensitive adhesive sheet-like molded article (G), the release PET film to be used when making the peeling by the following method. 将该结果示于表2。 The results are shown in Table 2. 需要说明的是,从脱模PET膜剥离时,对于粉碎而无法剥离的片材,作为无法评价。 Incidentally, when the PET film is peeled from the release, as the sheet can not be peeled off and pulverized, as could not be evaluated.

[0119] 将冲裁刃(哑铃I号(夕' > > I号))装载于冲裁器(Dumb Bell Ltd.制SDL-100),拧紧螺丝。 [0119] The punching blade (dumbbell No. I (Xi '>> No. I)) mounted on the punching device (Dumb Bell Ltd. manufactured by SDL-100), tighten the screw. 组装塑料板和冲裁板,以冲裁器的长度方向为导热性压敏粘接性片状成形体(G)的MD方向的方式冲裁导热性压敏粘接性片状成形体(G),制作试验片。 Plastic plates and punching the assembly plate, is punched in the longitudinal direction of the heat-conductive and pressure-sensitive adhesive of the sheet material (G) in the MD direction of the thermally conductive manner punching pressure-sensitive adhesive sheet-like molded article (G ), to prepare a test piece. 组装万能试验机(岛津制作所制、AGIS-20kN),按下电源等待15分钟(测力传感器:lkN)。 Assembling a universal testing machine (manufactured by Shimadzu, AGIS-20kN), wait 15 minutes to press the power (load cell: lkN). 选择试验条件(试验速度:300mm/min),输入通过厚度计(T0Y0SEIKI制数字测厚机)测定的试验片的厚度。 Select test conditions (test speed: 300mm / min), the input thickness of the test piece was measured by a thickness gauge (T0Y0SEIKI thickness measuring machine manufactured by Digital). 将试验片夹持于卡盘开始试验,读取试验片断裂时的应力。 The test piece holding chuck start of the test, reading the stress rupture test piece.

[0120] <导热性压敏粘接性片状成形体的制作> [0120] <thermally conductive pressure-sensitive adhesive sheet-like molded article produced>

(实施例1) (Example 1)

向反应器中加入由丙烯酸2-乙基己酯94%和丙烯酸6%组成的单体混合物100份、2,2'-偶氮双异丁腈0.03份以及醋酸乙酯700份,均匀地溶解,氮置换后,在80°C下进行6小时聚合反应。 Was added monomers acrylate, 2-ethylhexyl acrylate and acrylic acid of 94% to 6% of the composition of the mixture in the reactor 100 parts of 2,2'-azobisisobutyronitrile and 0.03 parts by 700 parts of ethyl acetate, dissolved homogeneously after replaced with nitrogen at 80 ° C 6 hours of polymerization. 聚合转化率为97%。 The polymerization conversion was 97%. 将所得到的聚合物进行减压干燥使醋酸乙酯蒸发,获得有粘性的固体状的(甲基)丙烯酸酯聚合物(A1-1)。 (Meth) acrylate polymer (A1-1) The resulting polymer was dried under reduced pressure so as ethyl acetate evaporated to give viscous solid. (甲基)丙烯酸酯聚合物(Al-1)的重均分子量(Mw)为270,000,重均分子量(Mw)/数均分子量(Mn)为3.1。 The (meth) acrylate polymer (Al-1) weight average molecular weight (Mw) of 270,000, a weight average molecular weight (Mw) / number average molecular weight (Mn) of 3.1. 重均分子量(Mw)以及数均分子量(Mn)通过将四氢呋喃作为洗脱液的凝胶渗透色谱以标准聚苯乙烯换算求出。 The weight average molecular weight (Mw) and number average molecular weight (Mn) by tetrahydrofuran as eluent gel permeation chromatography in terms of polystyrene standard.

[0121] 接着,用电子天秤计量将季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯以及季戊四醇二丙烯酸酯以60:35:5的比例混合而成的多官能性单体1.0份、丙烯酸2-乙基己酯(2EHA) 70份、有机过氧化物热聚合引发剂(1,6_双(叔丁基过氧化羰基氧基)己烷(I分钟半衰期温度为150°C)) 1.0份、多官能环氧化合物(Nagase ChemteX Corporation制、EX-1410、官能团数:4、粘度:320mPa S、总氯:0.5% >、环氧当量:160) 1.0份,将它们与上述(甲基)丙烯酸酯聚合物(Al-1) 30份混合。 [0121] Next, measurement of the electronic balance with pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate 60: 35: 5 ratio obtained by mixing a polyfunctional monomer 1.0 parts of 2-ethylhexyl acrylate, acrylate (2EHA) 70 parts of an organic peroxide thermal polymerization initiator (1,6_-bis (t-butylperoxy carbonyloxy) hexane (I-minute half-life temperature 150 ° C)) 1.0 parts of a polyfunctional epoxy oxygen compounds (Nagase ChemteX Corporation, Ltd., EX-1410, number of functional groups: 4, viscosity: 320mPa S, total chlorine: 0.5%>, epoxy equivalent: 160) 1.0 parts of them with the (meth) acrylate polymer (Al-1) 30 parts of mixed. 混合使用恒温槽(东机产业株式会社制、商品名“VISCOMATE 150III”)以及Hobart混合器(株式会社小平制作所制、商品名“ACM-5LVT型”、容量:5L)。 Use thermostatic mixing tank (Toki Sangyo Co., Ltd., trade name "VISCOMATE 150III") and Hobart mixer (manufactured by Kodaira Seisakusho Co., Ltd., trade name "ACM-5LVT type" Capacity: 5L). Hobart容器的温度设定为60°C,使转速刻度为3搅拌10分钟。 Hobart vessel temperature was set to 60 ° C, the rotational speed of the scale 3 is stirred for 10 minutes. 将该工序称为第I混合工序。 This step is called step I of mixing.

[0122]接着,计量憐酸酯(Ajinomoto Fine-Techno C0., Inc.制、商品名才7 才765”、化合物名“磷酸三芳基异丙基化物”)70份、氢氧化铝(日本轻金属株式会社制、商品名“BF-083”、平均粒径:8 μ m、BET比表面积:0.8m2/g) 400份、氧化铝(昭和电工株式会社制、商品名“AL-47-H”、平均粒径:2 μ m、BET比表面积:1.lm2/g) 400份、和氧化锌(株式会社7 [0122] Next, measurement pity ester (Ajinomoto Fine-Techno C0., Inc., trade name 765 was only 7 "compound name" isopropyl triaryl phosphate compound "), 70 parts of aluminum hydroxide (Nippon Light Metal Co., Ltd., trade name "BF-083", average particle diameter: 8 μ m, BET specific surface area: 0.8m2 / g) 400 parts of alumina (Showa Denko K.K., product name "AL-47-H" average particle size: 2 μ m, BET specific surface area: 1.lm2 / g) 400 parts, and zinc oxide (manufactured by 7

^夕制、A ff卜5 WZ-051D1份,投入上述Hobart容器中,将Hobart容器的温度设定为60°C,使转速刻度为5搅拌10分钟。 ^ Xi system, A ff Bu 5 WZ-051D1 parts, into the above vessel Hobart, the temperature of the vessel was set to Hobart 60 ° C, the rotational speed of the scale 5 is stirred for 10 minutes. 将该工序称为第2混合工序。 This step is called a second mixing step.

[0123] 接着,将经过上述第I和第2混合工序而得到的混合组合物垂落至厚度75 μ m的脱模PET膜上,在该混合组合物上进一步被覆厚度75 μ m的其它脱模PET膜。 [0123] Next, after the first and the second mixing step I to obtain a mixed composition release PET film drawn to a thickness of 75 μ m, and further coated with 75 μ m thickness on the release of the mixed composition further PET film. 使混合组合物被脱模PET膜夹持而成的该层叠体通过两者间隔设为0.45mm的辊之间,成形为片状。 The laminate between the mixed composition is sandwiched between a release PET film by both the interval to 0.45mm rollers, formed into a sheet. 其后,将该层叠体投入炉中,以150°C加热15分钟。 Thereafter, the laminate into a furnace and heated to 150 ° C 15 min. 通过该加热工序,使(甲基)丙烯酸酯单体和多官能性单体进行聚合反应,另外几乎同时使(甲基)丙烯酸酯聚合物(Al-1)以及(甲基)丙烯酸酯单体的聚合物进行交联反应,得到导热性压敏粘接性片状成形体(以下简单标记为“片材”)(Gl)0需要说明的是,由片材(Gl)中的残存单体量计算(甲基)丙烯酸酯单体的聚合转化率,结果为99.9%。 By this heating step, the (meth) acrylate monomer and a polyfunctional monomer polymerization reaction, while almost additional (meth) acrylate polymer (Al-1) and (meth) acrylate monomer polymer crosslinking reaction, to give the thermally conductive pressure-sensitive adhesive sheet materials (hereinafter, simply referred to as "sheet") (Gl) 0 Incidentally, the residual monomers by the sheet (of Gl) in calculating (meth) acrylate monomer polymerization conversion is found to be 99.9%.

[0124](实施例2乃至6、以及比较例1乃至3) [0124] (Example 2 and the 6, and 3 and the Comparative Example 1)

将各物质的配合如表2所示那样进行变更,除此以外与实施例1同样地操作,制作实施例1~6的片材(G2~G6)以及比较例1~4的片材(GCl~GC4)。 Each of the mating material as shown in Table 2 for the change, except in the same manner as in Example 1, a sheet produced in Example (G2 ~ G6) 1 ~ 6 and Comparative Example embodiments of a sheet (GCl 1 ~ 4 is ~ GC4). 将评价结果示于表2。 The evaluation results are shown in Table 2. 需要说明的是,实施例6中使用的多官能环氧化合物为Nagase ChemteX Corporation制的EX-1310 (官能团数:3、粘度=1lOmPa ·S、总氯:0.5% >、环氧当量:180)。 Incidentally, a polyfunctional epoxy compound used in Example 6 was manufactured by Nagase ChemteX Corporation EX-1310 (number of functional groups: 3, viscosity = 1lOmPa · S, total chlorine: 0.5%>, epoxy equivalent: 180) .

[0125][表 2] [0125] [Table 2]

Figure CN103874739AD00211

Claims (17)

  1. 1.导热性压敏粘接剂组合物(F),其在含有如下(A)、(B)、(D)、(E)的混合组合物中:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、 90质量份以上且1200质量份以下的导热性填料(B)、 0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、 0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E), 进行所述(甲基)丙烯酸酯单体(α I)和所述多官能性单体(D)的聚合反应、以及所述(甲基)丙烯酸酯聚合物(Al)和/或含有来源于所述(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应而成。 1. thermally conductive pressure-sensitive adhesive composition (F), which contained the following (A), (B), (D), (E) a mixed composition: 100 parts by mass of a (meth) acrylic acid ester polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition ([alpha]), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (B), 0.2 parts by mass or more and 8 parts by mass of a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D), 0.3 parts by mass 5.0 parts by mass or more and having the following functional groups or more and 10000 or less of 2 and 25 ° C viscosity of 600mPa s or less polyfunctional epoxy compound (E), the polymerization reaction of the (meth) acrylate monomer (α I) and the polyfunctional monomer (D), and the (meth) acrylate polymer (Al) and / or derived from the containing (meth) crosslinked polymer structural units of the acrylate monomer (α I) from the reaction.
  2. 2.根据权利要求1所述的导热性压敏粘接剂组合物(F),其中,所述导热性填料(B)为氢氧化铝和/或氧化铝。 The thermally conductive pressure-sensitive adhesive composition (F) according to claim 1, wherein the thermally conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  3. 3.根据权利要求1或2所述的导热性压敏粘接剂组合物(F),其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A)IOO质量份为45质量份以上且190质量份以下的磷酸酯(C)。 The thermally conductive pressure-sensitive adhesive composition (F) of claim 1 or claim 2, wherein the composition further contains a mixture of the (meth) acrylic resin composition (A) IOO 190 parts by mass or less parts by mass of the phosphoric ester (C) and 45 parts by mass or more.
  4. 4.根据权利要求1~3中任一项所述的导热性压敏粘接剂组合物(F),其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为0.01质量份以上且10质量份以下的聚合引发剂。 The 1 to 3, the thermally conductive pressure-sensitive adhesive composition (F) according to any one of claims, wherein the composition further comprises mixing the (meth) acrylic resin composition with respect to parts of (a) 100 parts by mass of polymerization of 10 parts by mass or less and 0.01 mass initiator.
  5. 5.导热性压敏粘接`性片状成形体(G), 其将含有下述(Α)、(B)、(D)、(E)的混合组合物成形为片状后,或者在将所述混合组合物成形为片状的同时,进行下述(甲基)丙烯酸酯单体(α I)和下述多官能性单体(D)的聚合反应、以及下述(甲基)丙烯酸酯聚合物(Al)和/或含有来源于下述(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应而成; 所述(A)、(B)、(D)、(E)为:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、 90质量份以上且1200质量份以下的导热性填料(B)、 0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、 0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E)。 The mixed composition of the thermally conductive pressure-sensitive adhesive sheet-like molded '(G), which comprises the following (Α), (B), (D), (E) is molded into a sheet, or the mixed composition was molded into a sheet at the same time, the following (meth) acrylate monomer (α I) below and a polyfunctional monomer (D) a polymerization reaction, and the following (meth) crosslinked acrylate polymers (Al) and / or a polymer containing structural units derived from (meth) acrylate monomer (α I) obtained by the reaction; the (a), (B), (D), (E) as follows: 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition ([alpha] ), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (B), 0.2 parts by mass or more and 8 parts by mass of a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D), 0.3 parts by mass 5.0 parts by mass or more and having a viscosity of 2 or more and 10,000 or less and a functional group 600mPa s at 25 ° C or less of the polyfunctional epoxy compound (E).
  6. 6.根据权利要求5所述的导热性压敏粘接性片状成形体(G),其中,所述导热性填料(B)为氢氧化招和/或氧化招。 6. The molded article (G), wherein the thermally conductive filler (B) move hydroxide and / or oxide trick The thermally conductive sheet-like pressure-sensitive adhesive according to claim 5.
  7. 7.根据权利要求5或6所述的导热性压敏粘接性片状成形体(G),其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为45质量份以上且190质量份以下的磷酸酯(C)。 The thermally conductive sheet-like pressure-sensitive adhesive of claim 5 or claim 6, wherein the molded body (G), wherein the composition further comprises mixing of the (meth) acrylic resin composition (A ) 100 parts by mass to 190 parts by mass of the phosphoric ester (C) and 45 parts by mass or more.
  8. 8.根据权利要求5~7中任一项所述的导热性压敏粘接性片状成形体(G),其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为0.01质量份以上且10质量份以下的聚合引发剂。 5 to 7, according to any one of the thermally conductive pressure-sensitive adhesive sheet-like molded article (G) as claimed in claim, wherein the composition further comprises mixing the (meth) acrylic resin with respect to composition (a) 100 parts by mass of 0.01 parts by mass or more and 10 parts by mass of a polymerization initiator.
  9. 9.导热性压敏粘接剂组合物(F)的制造方法,其包含如下工序:制作含有下述(A)、(B)、(D)、(E)的混合组合物的工序,所述(A)、(B)、(D)、(E)为:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(Α)、 ` 90质量份以上且1200质量份以下的导热性填料(B)、 ` 0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、 ` 0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E);以及在所述混合组合物中,进行所述(甲基)丙烯酸酯单体(α I)和所述多官能性单体(D)的聚合反应、以及所述(甲基)丙烯酸酯聚合物(Al)和/或含有来源于所述(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应的工序。 9. A method of manufacturing a thermally conductive pressure-sensitive adhesive composition (F), comprising the steps of: making a mixed composition containing the following (A), (B), (D), (E), and the said (a), (B), (D), (E) as follows: 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of (a yl) acrylic resin composition (Α), `90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (B), 0.2 parts by mass or more and more 'having a plurality of polymerizable unsaturated bonds 8 parts by mass or less functional monomers (D), '0.3 parts by mass or more and 5.0 parts by mass of 2 or more and having a viscosity at 10,000 or less and a functional group 600mPa s at 25 ° C or less polyfunctional epoxy compound (E); and in the mixed composition, for the (meth) acrylate monomer (α I) and the polyfunctional monomer (D) polymerization, and the (meth) acrylate polymer (Al ) and / or a polymer containing derived from the (meth) acrylate monomer of the structural unit (α I) of the crosslinking reaction step.
  10. 10.根据权利要求9所述的导热性压敏粘接剂组合物(F)的制造方法,其中,所述导热性填料(B)为氢氧化铝和/或氧化铝。 10. A method of manufacturing a thermally conductive pressure-sensitive adhesive composition (F) according to claim 9, wherein the thermally conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  11. 11.根据权利要求9或10所述的导热性压敏粘接剂组合物(F)的制造方法,其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为45质量份以上且190质量份以下的磷酸酯(C)。 11. The method of claim 9 or 10 for producing the thermally conductive pressure-sensitive adhesive composition (F) as claimed in claim, wherein the composition further comprises mixing the (meth) acrylic resin composition with respect to the ( parts a) 100 parts by mass of 45 mass or more and 190 parts by mass or less phosphoric ester (C).
  12. 12.根据权利要求9~11中任一项所述的导热性压敏粘接剂组合物(F)的制造方法,其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为0.01质量份以上且10质量份以下的聚合引发剂。 12. The method of manufacturing a thermally conductive 9-11 sensitive adhesive composition according to any one of the (F) as claimed in claim, wherein the composition further comprises mixing of the (meth) acrylic the resin composition (a) 100 parts by mass of 0.01 parts by mass or more and 10 parts by mass of a polymerization initiator.
  13. 13.导热性压敏粘接性片状成形体(G)的制造方法,其包含如下工序:制作含有下述(Α)、(B)、(D)、(E)的混合组合物的工序,所述(Α)、(B)、(D)、(E)为:100质量份的含有(甲基)丙烯酸酯聚合物(Al)和(甲基)丙烯酸酯单体(α I)的(甲基)丙烯酸类树脂组合物(A)、 90质量份以上且1200质量份以下的导热性填料(B)、 0.2质量份以上且8质量份以下的具有多个聚合性不饱和键的多官能性单体(D)、 0.3质量份以上且5.0质量份以下的具有2以上且10000以下的官能团且25°C下的粘度为600mPa s以下的多官能环氧化合物(E);以及、 将所述混合组合物成形为片状后,或者在将所述混合组合物成形为片状的同时,进行所述(甲基)丙烯酸酯单体(α I)和所述多官能性单体(D)的聚合反应、以及所述(甲基)丙烯酸酯聚合物(Al)和/或含有来源于所述(甲基)丙烯酸酯单体(α I)的结构单元的聚合物的交联反应的工序 Comprising the following step of producing (Α), (B), (D), (E) a mixed composition: 13. A method of manufacturing a thermally conductive pressure-sensitive adhesive of the sheet material (G), comprising the steps of the (Α), (B), (D), (E) as follows: 100 parts by mass of a (meth) acrylate polymer (Al) and (meth) acrylate monomer (α I) of the (meth) acrylic resin composition (a), 90 parts by mass or more and 1200 parts by mass of the thermally conductive filler (B), 0.2 parts by mass or more and 8 parts by mass or less having a plurality of polymerizable unsaturated bonds plurality functional monomers (D), 0.3 parts by mass or more and 5.0 parts by mass or less 10000 or less and having two or more functional groups and a viscosity of 600mPa s at 25 ° C or less polyfunctional epoxy compound (E); and the after mixing the composition was molded into a sheet, or the mixed composition into a sheet is performed while the (meth) acrylate monomer (α I) and the polyfunctional monomer ( crosslinking and polymer D) polymerization, and the (meth) acrylate polymer (Al) / comprising or derived from the (meth) acrylate monomer of the structural unit (α I) of process
  14. 14.根据权利要求13所述的导热性压敏粘接性片状成形体(G)的制造方法,其中,所述导热性填料(B)为氢氧化铝和/或氧化铝。 14. The method of manufacturing a thermally conductive pressure-sensitive adhesive as claimed in claim 13 of the sheet-like molded article (G), wherein the thermally conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  15. 15.根据权利要求13或14所述的导热性压敏粘接性片状成形体(G)的制造方法,其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为45质量份以上且190质量份以下的磷酸酯(C)。 15. A molded body manufacturing method (G), wherein the mixed composition further contains (meth) acrylic resin composition according to the thermal conductivity with respect to the sheet-like pressure-sensitive adhesive of claim 13 or claim 14 100 parts by mass of (a) is 190 parts by mass or less phosphoric ester (C) and 45 parts by mass or more.
  16. 16.权利要求13~15中任一项所述的导热性压敏粘接性片状成形体(G)的制造方法,其中,所述混合组合物进一步含有相对于所述(甲基)丙烯酸类树脂组合物(A) 100质量份为0.01质量份以上且10质量份以下的聚合引发剂。 16. A according to any of claims 13 to 15, one of the thermally conductive pressure-sensitive adhesive sheet-like molded body manufacturing method (G), wherein the composition further comprises mixing of the (meth) acrylic acid parts of (a) 100 mass based resin composition is 0.01 parts by mass or more and 10 parts by mass of a polymerization initiator.
  17. 17.电子部件,其具备散热体以及贴合于该散热体的权利要求1~4中任一项所述的导热性压敏粘接剂组合物(F),或者具备散热体以及贴合于该散热体的权利要求5~8中任一项所述的导热性压敏粘接性片状成形体(G)。 17. The electronic component includes a radiator, and the rights attached to the heat sink in claim 1 to 4, the thermally conductive pressure-sensitive adhesive composition (F) according to any one of, or includes a heat sink bonded to the body and the pressure-sensitive adhesive sheet-like thermal conductivity to any of claim 5 to 8, the cooling body is molded of claims (G).
CN 201280050873 2011-10-28 2012-10-16 Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component CN103874739A (en)

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