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TW201807130A - Adhesive composition and antistatic surface-protective film - Google Patents

Adhesive composition and antistatic surface-protective film Download PDF

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Publication number
TW201807130A
TW201807130A TW106105564A TW106105564A TW201807130A TW 201807130 A TW201807130 A TW 201807130A TW 106105564 A TW106105564 A TW 106105564A TW 106105564 A TW106105564 A TW 106105564A TW 201807130 A TW201807130 A TW 201807130A
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meth
compound
acrylate
group
weight
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TW106105564A
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TWI753882B (en
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長倉毅
長谷川良
吉田弘幸
菱沼昌世
鈴木史恵
大津賀健太郎
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藤森工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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

Abstract

The present invention provides an adhesive composition and an antistatic surface-protection film. Which have less contaminant to the adherend that does not change over time and excellent antistatic performance upon peeling. The adhesive composition contains: a copolymer that is copolymerized by at least one of (a1) a (meth)acrylic acid ester monomer having a C1 to C4 alkyl group, at least one of (a2) a (meth)acrylic acid ester monomer having a C5 to C18 alkyl group, at least one of (B) a hydroxyl group-containing copolymerizable monomer, at least one of (C) a carboxyl group-containing copolymerizable monomer, at least one of (D) a polyalkylene glycol mono(meth)acrylic acid ester monomer; (H) an ionic compound having a melting point of 25 to 50 DEG C and being solid at 25 DEG C; (E) a bifunctional or multifunctional isocyanate compound; (F) a crosslinking accelerator; (G) a keto-enol tautomer compound.

Description

黏著劑組合物及抗靜電表面保護膜 Adhesive composition and antistatic surface protective film

本發明關於一種黏著劑組合物及表面保護膜。進一步詳細而言，關於一種具有抗靜電性能的表面保護膜用的黏著劑組合物、及使用有上述黏著劑組合物的表面保護膜。本發明提供一種即使被黏物為施加有低反射表面處理的偏光板時也對被黏物的污染少、且不經時劣化、具有優異抗剝離靜電性能的黏著劑組合物、及使用有該黏著劑組合物的抗靜電表面保護膜。 The invention relates to an adhesive composition and a surface protection film. In more detail, it is related with the adhesive composition for surface protective films which has antistatic performance, and the surface protective film using the said adhesive composition. The present invention provides an adhesive composition which has less pollution to the adherend and does not deteriorate with time even when the adherend is a polarizing plate to which a low-reflection surface treatment is applied, and which has an excellent anti-peel electrostatic property, and uses the same. Antistatic surface protective film of an adhesive composition.

在製備、搬運偏光板、相位差板、顯示器用的鏡片膜、防反射膜、硬塗膜、觸控面板用透明導電性膜等光學用膜、及使用了這些部件的顯示器等光學產品時，在該光學用膜的表面貼合表面保護膜，以防止在後續工序中的表面的污垢或損傷。作為光學產品的光學用膜的外觀檢查，為了節省剝離表面保護膜並再次貼合的手續、提高作業效率，有時也直接在將表面保護膜貼合於光學用膜的狀態下進行。 When preparing and transporting optical films such as polarizing plates, retardation plates, display lens films, anti-reflection films, hard coating films, transparent conductive films for touch panels, and optical products such as displays using these components, A surface protection film is attached to the surface of the optical film to prevent surface dirt or damage in subsequent processes. In order to save the process of peeling the surface protective film and attaching it again to improve the working efficiency, the visual inspection of the optical film as an optical product may be performed in a state where the surface protective film is bonded to the optical film.

以往，在光學產品的製備工序中，為了防止損傷或污垢的附著，通常在基材膜的一個面上使用設有黏著劑層的表面保護膜。表面保護膜經由微黏著力的黏著劑層而貼合於光 學用膜。使黏著劑層為微黏著力的原因在於，將使用過的表面保護膜從光學用膜的表面剝離去除時能夠容易地剝離，並使黏著劑不附著殘留在作為被黏物的產品的光學用膜上(即防止殘膠的產生)。 Conventionally, in the production process of an optical product, in order to prevent damage or adhesion of dirt, a surface protection film provided with an adhesive layer is usually used on one surface of a base film. The surface protection film is adhered to the light through a micro-adhesive adhesive layer Learning film. The reason for making the adhesive layer slightly adhesive is that it can be easily peeled off when the used surface protection film is peeled off from the surface of the optical film, and the adhesive is not adhered to the optical product which is an adherend. On the film (to prevent the generation of residual glue).

近年來，在液晶顯示器螢幕的生產工序中，雖然發生件數少，但仍發生了由於將貼合在光學用膜上的表面保護膜剝離去除時產生的剝離靜電電壓，而引起用於控制液晶顯示器面板的顯示畫面的驅動IC等電路組件遭到破壞的現象、或液晶分子的配向受到損害的現象。 In recent years, in the production process of liquid crystal display screens, although the number of occurrences is small, the peeling electrostatic voltage generated when the surface protection film attached to the optical film is peeled and removed, which causes the liquid crystal to be controlled. A phenomenon in which circuit components such as a driver IC of a display screen of a display panel are damaged or an alignment of liquid crystal molecules is damaged.

此外，為了降低液晶顯示器面板的耗電量，液晶材料的驅動電壓變低，伴隨於此，驅動IC的破壞電壓也變低。因此，將表面保護膜從作為被黏物的光學用膜上剝離時，為了防止因剝離靜電電壓高而導致的不良狀況，提出了一種使用含有將剝離靜電電壓抑制地較低的抗靜電劑的黏著劑層的表面保護膜。 In addition, in order to reduce the power consumption of the liquid crystal display panel, the driving voltage of the liquid crystal material is reduced, and with this, the breakdown voltage of the driving IC is also reduced. Therefore, when peeling a surface protection film from an optical film as an adherend, in order to prevent a defect caused by a high peeling electrostatic voltage, an antistatic agent containing a low antistatic agent that suppresses the peeling electrostatic voltage is proposed. Surface protective film for the adhesive layer.

例如，專利文獻1中記載了一種黏著劑組合物，其特徵在於，含有：以烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體為主要成分的(甲基)丙烯酸系聚合物、聚醚化合物、熔點為30℃以上的離子化合物。 For example, Patent Document 1 describes an adhesive composition comprising a (meth) acrylic system containing a (meth) acrylic acid ester monomer having a C1 to C14 carbon number of an alkyl group as a main component. Polymers, polyether compounds, ionic compounds with a melting point of 30 ° C or higher.

此外，專利文獻2中記載了一種黏著劑組合物，其含有：以0.1~4.9重量%的氧伸烷基單元的平均加成莫耳數為3~40的含有環氧烷基的反應性單體及50~99.9重量%的具有碳原子數為1~14的烷基的(甲基)丙烯酸酯作為單體成分的(甲基)丙烯酸系聚合物、鹼金屬鹽。 Further, Patent Document 2 describes an adhesive composition containing an epoxy alkylene group-containing reactive monomer having an average addition mol number of 0.1 to 4.9% by weight of an oxyalkylene unit of 3 to 40. And (meth) acrylic polymer having 50 to 99.9% by weight of a (meth) acrylate having an alkyl group having 1 to 14 carbon atoms as a monomer component, and an alkali metal salt.

此外，專利文獻3中記載了一種黏著劑組合物，其含有： 分子內具有羥基的丙烯酸類共聚物、鹼金屬鹽、分子內具有聚氧伸烷基的HLB值為1以上10以下的二甲基聚矽氧烷化合物。 In addition, Patent Document 3 describes an adhesive composition containing: An acrylic copolymer having a hydroxyl group in the molecule, an alkali metal salt, and a dimethyl polysiloxane compound having a HLB value of 1 to 10 in the molecule.

現有技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：日本特開2013-163783號公報 Patent Document 1: Japanese Patent Application Publication No. 2013-163783

專利文獻2：日本特開2012-237004號公報 Patent Document 2: Japanese Patent Application Publication No. 2012-237004

專利文獻3：日本特開2013-163744號公報 Patent Document 3: Japanese Patent Application Publication No. 2013-163744

現有技術中，在具有抗靜電性能的表面保護膜中，需要在黏著劑層中添加抗靜電劑。因此，抗靜電性能與對被黏物的污染性的關係為此消彼長的關係。但在近年，顯示面板的高畫質化、高品位化發展，存在耐污染性的評價標準變得更加嚴格的狀況，要求一種即使在依據嚴格的評價方法進行判定的結果中，也在被黏物的表面不存在污染性方面的問題的表面保護膜。 In the prior art, in a surface protection film having antistatic performance, an antistatic agent needs to be added to the adhesive layer. Therefore, the relationship between the antistatic performance and the contamination of the adherends has a relationship that is mutually exclusive. However, in recent years, high-quality and high-quality display panels have been developed, and the evaluation standards for pollution resistance have become more stringent. There is a demand for a display panel that is stuck even if it is judged based on a strict evaluation method. A surface protection film that does not have a problem with contamination on the surface of an object.

本發明鑒於上述情況而成，其技術問題在於提供一種對被黏物的污染少，且不經時劣化的、具有優異抗剝離靜電性的黏著劑組合物、及抗靜電表面保護膜。 The present invention has been made in view of the above circumstances, and a technical problem of the present invention is to provide an adhesive composition which has less contamination of adherends and does not deteriorate with time, and which has excellent anti-peel electrostatic properties, and an antistatic surface protective film.

本申請發明人們為了解決上述技術課題而進行了深入研究，結果發現，作為構成黏著劑組合物的丙烯酸系聚合物的主要成分，採用烷基的碳原子數為C1~C18的(甲基)丙 烯酸酯單體組，將其劃分為2個單體群組，從各單體群組中選擇至少一種的單體，設為特定的單體比例，由此，具有可降低對被黏物的污染的特殊的效果。 The inventors of the present application conducted intensive research in order to solve the above-mentioned technical problems, and as a result, found that as a main component of the acrylic polymer constituting the adhesive composition, (meth) acrylic acid having C1 to C18 alkyl groups was used The acrylate monomer group is divided into two monomer groups, and at least one kind of monomer is selected from each monomer group, and the specific monomer ratio is set, thereby reducing the adhesion to the adherend. Special effect of pollution.

進一步，藉由選擇對被黏物的污染方面不產生不良影響的抗靜電劑，並使黏著劑組合物含有此抗靜電劑，能夠得到對被黏物的污染少、且不經時劣化的具有優異抗剝離靜電性能的黏著劑組合物，能夠解決本發明的技術問題。 Furthermore, by selecting an antistatic agent that does not adversely affect the contamination of the adherend, and including the antistatic agent in the adhesive composition, it is possible to obtain an antistatic agent that has less contamination to the adherend and does not deteriorate over time. An adhesive composition having excellent anti-peeling electrostatic properties can solve the technical problem of the present invention.

即，本發明的技術思想在於：使作為構成黏著劑組合物的丙烯酸系聚合物為將(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體、(B)含有羥基的可共聚單體中的至少一種以上、(C)含有羧基的可共聚單體中的至少一種以上、(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上進行共聚而成的共聚物，前述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體由(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種所構成，藉由將前述(a1)與前述(a2)的含有比例(a2/a1)以質量比設定為特定的比例範圍，由此降低所得到的黏著劑對被黏物的污染。 That is, the technical idea of the present invention is that the acrylic polymer constituting the adhesive composition is a (meth) acrylic acid ester monomer having C1 to C18 carbon atoms in the (A) alkyl group, and (B) contains At least one or more of a hydroxyl-based copolymerizable monomer, (C) at least one or more of a carboxyl-containing copolymerizable monomer, (D) at least one of a polyalkylene glycol mono (meth) acrylate monomer In the copolymer obtained by the above copolymerization, the (meth) acrylic acid ester monomer having a carbon number of C1 to C18 in the (A) alkyl group includes a (methyl group having a carbon number of C1 to C4 in the (a1) alkyl group) ) At least one or more of the acrylate monomers, and (a2) at least one of the (meth) acrylate monomers having a carbon number of C5 to C18 in the (a2) alkyl group. The (a1) and the ( The content ratio (a2 / a1) of a2) is set to a specific ratio range by mass ratio, thereby reducing contamination of the adherend by the obtained adhesive.

為了解決上述技術問題，本發明提供一種黏著劑組合物，其含有丙烯酸系聚合物、抗靜電劑、交聯劑，其特徵在於，前述丙烯酸系聚合物為藉由不包含不含羥基的含氮乙烯 單體及含烷氧基的(甲基)丙烯酸烷基酯單體，而使下述物質進行共聚而成的共聚物：相對於前述丙烯酸系聚合物的100重量份，(A)總量為50~99.8重量份的烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體、作為可共聚單體組的、(B)0.1~14重量份含有羥基的可共聚單體中的至少一種以上、(C)0.01~1.0重量份含有羧基的可共聚單體中的至少一種以上、(D)超過0且為35重量份以下的聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上，前述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體由(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種以上構成，前述(a1)與前述(a2)的含有比例(a2/a1)以質量比為超過1且為50以下，前述抗靜電劑為(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物，前述交聯劑為(E)雙官能以上的異氰酸酯化合物，前述黏著劑組合物進一步含有(F)交聯促進劑、(G)酮-烯醇互變異構體化合物。 In order to solve the above technical problems, the present invention provides an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent. The acrylic polymer is characterized in that the acrylic polymer does not contain nitrogen containing no hydroxyl group. Ethylene A copolymer obtained by copolymerizing a monomer and an alkoxy-containing (meth) acrylic acid alkyl ester monomer and copolymerizing the following materials: The total amount of (A) is 100 parts by weight of the acrylic polymer. 50 to 99.8 parts by weight of the (meth) acrylic acid ester monomers having 1 to 18 carbon atoms of the alkyl group, and (B) 0.1 to 14 parts by weight of a copolymerizable monomer containing a hydroxyl group as a copolymerizable monomer group (C) at least one or more of (C) 0.01 to 1.0 part by weight of a copolymerizable monomer containing a carboxyl group, (D) more than 0 and 35 parts by weight or less of a polyalkylene glycol mono (meth) acrylic acid At least one or more of the ester monomers, the (A) alkyl (meth) acrylic acid ester monomer having a carbon number of C1 to C18 has (a1) an alkyl group having a carbon number of C1 to C4 (a methyl group) ) At least one or more of the acrylate monomers, and (a2) at least one or more of the (meth) acrylic acid ester monomers having a carbon number of C5 to C18, the (a1) and (a2) The content ratio (a2 / a1) is a mass ratio of more than 1 and 50 or less. The antistatic agent is (H) an ionic compound having a melting point of 25 to 50 ° C and a solid at a temperature of 25 ° C. The crosslinker is ( E ) A bifunctional or higher isocyanate compound, and the adhesive composition further contains (F) a cross-linking accelerator and (G) a keto-enol tautomer compound.

前述(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，以構成聚伸烷基二醇鏈的伸烷基氧的平均重複數為3~14，單體 中的二酯成分為0.2%以下為佳。 In the aforementioned (D) polyalkylene glycol mono (meth) acrylate monomer, the average repeat number of the alkylene oxide constituting the polyalkylene glycol chain is 3 to 14, and the monomer It is preferable that the diester component is 0.2% or less.

前述(F)交聯促進劑以選自由鋁螯合物、鈦螯合物、鐵螯合物組成的群組中的至少一種以上，相對於前述丙烯酸系聚合物100重量份，以0.001~0.5重量份的比例含有前述(F)交聯促進劑，以0.1~300重量份的比例含有前述(G)酮-烯醇互變異構體化合物，前述(G)/前述(F)的重量份比例為70~1000為佳。 The (F) crosslinking accelerator is at least one selected from the group consisting of an aluminum chelate, a titanium chelate, and an iron chelate, and is 0.001 to 0.5 with respect to 100 parts by weight of the acrylic polymer. The proportion by weight includes the aforementioned (F) crosslinking accelerator, and the aforementioned (G) keto-enol tautomer compound is contained in the proportion of 0.1 to 300 parts by weight, and the proportion of the aforementioned (G) / the aforementioned (F) by weight It is preferably 70 to 1000.

前述(B)含有羥基的可共聚單體以選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺組成的化合物群組中的至少一種以上為佳。 The (B) hydroxyl-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (methyl) ) 2-hydroxyethyl acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide Preferably, at least one of them is used.

前述(C)含有羧基的可共聚單體以選自由(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸組成的化合物群組中的至少一種以上為佳。 The (C) carboxyl-containing copolymerizable monomer is selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acryloxyethyl Hexahydrophthalic acid, 2- (meth) acryloxypropyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, 2- (meth) acrylic acid Ethoxyethyl succinic acid, 2- (meth) acryl ethoxyethylmaleic acid, carboxy polycaprolactone mono (meth) acrylate, 2- (meth) acryl ethoxyethyl tetra It is preferable that at least one or more of the compound group consisting of hydrogen phthalic acid is used.

作為前述可共聚單體組，以前述構成聚伸烷基二醇鏈的伸烷基氧的平均重複數為3~14、單體中的二酯成分為0.2%以下的前述(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，含有選自聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基 二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯中的至少一種以上為佳。 As the copolymerizable monomer group, the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain is 3 to 14, and the (D) polyelongation of the diester component in the monomer is 0.2% or less. Alkyl glycol mono (meth) acrylate monomer containing a polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene It is preferred that at least one of the diol (meth) acrylate and the ethoxy polyalkylene glycol (meth) acrylate is used.

丙烯酸系聚合物前述(E)雙官能以上的異氰酸酯化合物中，作為雙官能異氰酸酯化合物為非環式脂肪族異氰酸酯化合物，為使二異氰酸酯化合物與二醇化合物反應生成的化合物，由作為二異氰酸酯化合物的脂肪族二異氰酸酯、即選自由四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯組成的化合物群組中的一種，與作為二醇化合物的選自由2-甲基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、3-甲基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇單羥基新戊酸酯、聚乙二醇、聚丙二醇組成的化合物群組中的一種形成，作為三官能異氰酸酯化合物，含有六亞甲基二異氰酸酯化合物的異氰脲酸酯體、異佛爾酮二異氰酸酯化合物的異氰脲酸酯體、六亞甲基二異氰酸酯化合物的加成體、異佛爾酮二異氰酸酯化合物的加成體、六亞甲基二異氰酸酯化合物的縮二脲體、異佛爾酮二異氰酸酯化合物的縮二脲體、甲苯二異氰酸酯化合物的異氰脲酸酯體、苯二亞甲基二異氰酸酯化合物的異氰脲酸酯體、氫化苯二亞甲基二異氰酸酯化合物的異氰脲酸酯體、甲苯二異氰酸酯化合物的加成體、苯二亞甲基二異氰酸酯化合物的加成體、氫化苯二亞甲基二異氰酸酯化合物的加成體，相對於100重量份前述丙烯酸系聚合物，以0.1~10重量份的比例含有為佳。 In the acrylic polymer (E), the bifunctional or higher isocyanate compound is an acyclic aliphatic isocyanate compound as the difunctional isocyanate compound, and is a compound produced by reacting a diisocyanate compound with a diol compound. Aliphatic diisocyanate, that is, selected from the group of compounds consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate And a diol compound selected from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3- Propylene glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol monohydroxypivalate One of the compound groups consisting of polyethylene glycol, polypropylene glycol, and polypropylene glycol. As a trifunctional isocyanate compound, an isocyanurate containing a hexamethylene diisocyanate compound and an isocyanone diisocyanate compound are isocyanate. Urate body, hexamethylene diisocyanate Adducts of compounds, adducts of isophorone diisocyanate compounds, biuret bodies of hexamethylene diisocyanate compounds, biuret bodies of isophorone diisocyanate compounds, and toluene diisocyanate compounds Isocyanurate bodies, isocyanurate bodies of phthalimide diisocyanate compounds, isocyanurate bodies of hydrogenated phthalimide diisocyanate compounds, adducts of toluene diisocyanate compounds, benzene The adduct of a dimethylene diisocyanate compound and the adduct of a hydroxylylene diisocyanate compound are preferably contained in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.

相對於100重量份前述丙烯酸系聚合物，前述黏著 劑組合物以0.01~1.0重量份的比例進一步含有(I)HLB值為7~15的聚醚改性矽氧烷化合物為佳。 The aforementioned adhesion to 100 parts by weight of the acrylic polymer The agent composition preferably further contains (I) a polyether-modified silicone compound having an HLB value of 7 to 15 in a proportion of 0.01 to 1.0 parts by weight.

此外，本發明提供一種抗靜電表面保護膜，其特徵在於，在樹脂膜的一個面上層積有上述黏著劑組合物進行交聯的黏著劑層。 In addition, the present invention provides an antistatic surface protection film, characterized in that an adhesive layer for cross-linking the above-mentioned adhesive composition is laminated on one surface of a resin film.

此外，本發明提供一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將上述抗靜電表面保護膜貼合於實施使反射率為2%以下的低反射表面處理的偏光板後，剝離時的污染性良好。 In addition, the present invention provides an antistatic surface protection film, characterized in that the antistatic surface protection film is bonded to a polarizing plate subjected to a low reflection surface treatment with a reflectance of 2% or less via the adhesive layer, Pollution during peeling is good.

此外，本發明提供一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將上述抗靜電表面保護膜貼合於實施使反射率為2%以下的低反射表面處理的偏光板後，剝離時的剝離靜電電壓為±0.8kV以下，且前述黏著劑表面的表面電阻率為9.0×1011Ω/□以下。 In addition, the present invention provides an antistatic surface protection film, characterized in that the antistatic surface protection film is bonded to a polarizing plate subjected to a low reflection surface treatment with a reflectance of 2% or less via the adhesive layer, The peeling electrostatic voltage at the time of peeling was ± 0.8 kV or less, and the surface resistivity of the surface of the adhesive was 9.0 × 10 11 Ω / □ or less.

此外，本發明提供一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將上述抗靜電表面保護膜貼合於實施使反射率為2%以下的低反射表面處理、且實施有防眩處理的偏光板後，剝離時的剝離靜電電壓為±0.8kV以下，且前述黏著劑表面的表面電阻率為9.0×1011Ω/□以下。 In addition, the present invention provides an antistatic surface protection film characterized in that the antistatic surface protection film is bonded to the low-reflective surface treatment with a reflectance of 2% or less through the adhesive layer, and an anti- After the glare-treated polarizing plate, the peeling electrostatic voltage at the time of peeling was ± 0.8 kV or less, and the surface resistivity of the surface of the adhesive was 9.0 × 10 11 Ω / □ or less.

此外，本發明提供一種黏著膜，其特徵在於，在樹脂膜的一個面或兩面形成由上述黏著劑組合物交聯而成的黏著劑層。 In addition, the present invention provides an adhesive film characterized in that an adhesive layer formed by crosslinking the above-mentioned adhesive composition is formed on one or both sides of a resin film.

此外，本發明提供一種抗靜電表面保護膜，其由上述抗靜電表面保護膜構成，用於偏光板用保護膜的用途。 In addition, the present invention provides an antistatic surface protective film, which is composed of the antistatic surface protective film described above, and is used for a protective film for a polarizing plate.

此外，本發明提供一種抗靜電表面保護膜，其中，在前述樹脂膜的一個面，即與形成前述黏著劑層一側的相反面上，施加有抗靜電處理及防汙處理。 In addition, the present invention provides an antistatic surface protection film in which an antistatic treatment and an antifouling treatment are applied to one surface of the resin film, that is, the surface opposite to the side on which the adhesive layer is formed.

根據本發明，提供一種即使被黏物為施加有低反射表面處理的偏光板時，也對被黏物的污染少、且不經時劣化、具有優異剝離抗靜電性能的黏著劑組合物、及抗靜電表面保護膜。 According to the present invention, even when the adherend is a polarizing plate to which a low-reflection surface treatment is applied, there is provided an adhesive composition that has less contamination to the adherend, does not deteriorate over time, and has excellent peeling and antistatic properties, and Antistatic surface protective film.

以下基於較佳的實施方式，對本發明進行說明。 Hereinafter, the present invention will be described based on preferred embodiments.

本發明的黏著劑組合物為含有丙烯酸系聚合物、抗靜電劑、交聯劑的黏著劑組合物，其特徵在於，前述丙烯酸系聚合物為藉由不包含不含羥基的含氮乙烯單體及含烷氧基的(甲基)丙烯酸烷基酯單體，而使下述物質進行共聚而成的共聚物：相對於前述丙烯酸系聚合物的100重量份，(A)總量為50~99.8重量份的烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體、作為可共聚單體組的(B)0.1~14重量份含有羥基的可共聚單體中的至少一種以上、(C)0.01~1.0重量份含有羧基的可共聚單體中的至少一種以上、(D)超過0且為35重量份以下的聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上，前述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體由(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單 體中的至少一種以上、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種以上構成，前述(a1)與前述(a2)的含有比例(a2/a1)以質量比為超過1且為50以下，前述抗靜電劑為(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物，前述交聯劑為(E)雙官能以上的異氰酸酯化合物，前述黏著劑組合物進一步含有(F)交聯促進劑、(G)酮-烯醇互變異構體化合物。 The adhesive composition of the present invention is an adhesive composition containing an acrylic polymer, an antistatic agent, and a cross-linking agent. The acrylic polymer is a nitrogen-containing vinyl monomer that does not contain a hydroxyl group. And an alkoxy-containing (meth) acrylic acid alkyl ester monomer, and a copolymer obtained by copolymerizing the following materials: the total amount of (A) is 50 to 100 parts by weight of the acrylic polymer; At least one of 99.8 parts by weight of an alkyl group having a carbon number of C1 to C18 (meth) acrylate monomer, and (B) as a copolymerizable monomer group, 0.1 to 14 parts by weight of a copolymerizable monomer containing a hydroxyl group At least one of (C) 0.01 to 1.0 part by weight of a carboxyl group-containing copolymerizable monomer, (D) more than 0 and 35 parts by weight or less of a polyalkylene glycol mono (meth) acrylate monomer At least one of the above (A) alkyl (meth) acrylate monomers having a carbon number of C1 to C18 ((1)) (meth) acrylic acid esters having an alkyl group having a carbon number of C1 to C4 single And (a2) an alkyl group having at least one (meth) acrylic acid ester monomer having a carbon number of C5 to C18, and the content ratio (a2) of the (a1) and (a2) / a1) The mass ratio is more than 1 and 50 or less, the antistatic agent is (H) an ionic compound having a melting point of 25 to 50 ° C and solid at a temperature of 25 ° C, and the crosslinker is (E) difunctional In the above isocyanate compound, the adhesive composition further contains (F) a cross-linking accelerator and (G) a keto-enol tautomer compound.

(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體中，作為(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體的至少一種以上，可列舉出(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯。 (A) At least one kind of (meth) acrylic acid ester monomer having (C1 to C18) alkyl group as the (meth) acrylic acid ester monomer having (C1 to C4) alkyl group Examples of the above include butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) Isopropyl acrylate.

此外，作為(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體，可列舉出(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸異鯨蠟酯、(甲基)丙烯酸硬脂醇酯、(甲基)丙烯酸異硬脂醇酯等。 In addition, examples of the (meth) acrylate monomer having a carbon number of C5 to C18 for the (a2) alkyl group include amyl (meth) acrylate, hexyl (meth) acrylate, and (meth) acrylic acid. Heptyl, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, ( Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl esters, myristyl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, isocetyl (meth) acrylate, stearyl alcohol (meth) acrylate Esters, isostearyl alcohol (meth) acrylate, and the like.

相對於總量100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，以1~50重量份的比例含有(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體的至少一種、以50~99重量份的比例含有(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體的至少一種為佳，更佳為以3~45重量份的比例含有前述(a1)的至少一種、以55~97重量份的比例含有前述(a2)的至少一種，特別佳以5~45重量份的比例含有前述(a1)的至少一種、以55~95重量份的比例含有前述(a2)的至少一種，最佳以8~40重量份的比例含有前述(a1)的至少一種、以60~92重量份的比例含有前述(a2)的至少一種。 The carbon number of (a) alkyl group containing (a1) alkyl group is 1 to 50 parts by weight based on 100 parts by weight of (A) alkyl (C) alkyl group having (1) C18 carbon atoms. At least one type of (meth) acrylic acid ester monomer of C1 to C4, and at least one type of (meth) acrylic acid ester monomer having C5 to C18 containing (a2) alkyl group in a proportion of 50 to 99 parts by weight Preferably, at least one of the aforementioned (a1) is contained in a proportion of 3 to 45 parts by weight, and at least one of the aforementioned (a2) is contained in a proportion of 55 to 97 parts by weight, particularly preferably in a proportion of 5 to 45 parts by weight Contains at least one of the aforementioned (a1), at least one of the aforementioned (a2) in a ratio of 55 to 95 parts by weight, and preferably contains at least one of the aforementioned (a1) in an amount of 8 to 40 parts by weight, and 60 to 92 weight The proportion of parts contains at least one of the aforementioned (a2).

即，相對於100重量份前述丙烯酸系聚合物，(1)以50~99.8重量份的比例含有(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，且前述(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上與前述(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種的含有比例(a2/a1)以質量比為超過1且為50以下為佳。 That is, (1) a (meth) acrylic acid ester monomer having C1 to C18 carbon atoms of (A) an alkyl group in a proportion of 50 to 99.8 parts by weight relative to 100 parts by weight of the acrylic polymer, and the aforementioned (a1) At least one or more (meth) acrylate monomers having a carbon number of C1 to C4 in the alkyl group and (5) to C18 (meth) acrylate monomers having a carbon number in the (a2) alkyl group The content ratio (a2 / a1) of at least one of the compounds is preferably more than 1 and 50 or less by mass ratio.

(2)以62~99.5重量份的比例含有(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，且前述(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上與前述(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種的含有比例(a2/a1)以質量比為1.2~33更佳。 (2) A (meth) acrylic acid ester monomer having a carbon number of C1 to C18 in the proportion of 62 to 99.5 parts by weight of the (A) alkyl group, and the carbon number of the (a1) alkyl group is C1 to C4 The content ratio (a2 / a1) of at least one or more of the (meth) acrylic acid ester monomers to at least one of the (meth) acrylic acid ester monomers having a carbon number of C5 to C18 of the (a2) alkyl group The mass ratio is better from 1.2 to 33.

(3)以66~96.0重量份的比例含有(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，且前述(a1)烷基的碳原子 數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上與前述(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種的含有比例(a2/a1)以質量比為1.5~19特別佳。 (3) A (meth) acrylic acid ester monomer having a carbon number of C1 to C18 in the proportion of 66 to 96.0 parts by weight of the (A) alkyl group, and the carbon atom of the (a1) alkyl group Content ratio of at least one or more kinds of (meth) acrylate monomers having C1 to C4 and at least one kind of (meth) acrylate monomers having C5 to C18 alkyl groups in the (a2) alkyl group (a2 / a1) The mass ratio is particularly preferably 1.5 to 19.

(4)以70~93.0重量份的比例含有(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，且前述(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上與前述(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種的含有比例(a2/a1)以質量比為超過1.5且為11.5以下最佳。 (4) A (meth) acrylic acid ester monomer having a carbon number of C1 to C18 in the proportion of 70 to 93.0 parts by weight of the (A) alkyl group, and the carbon number of the (a1) alkyl group is C1 to C4 The content ratio (a2 / a1) of at least one or more of the (meth) acrylic acid ester monomers to at least one of the (meth) acrylic acid ester monomers having a carbon number of C5 to C18 of the (a2) alkyl group The mass ratio is preferably more than 1.5 and less than 11.5.

作為(B)含有羥基的可共聚單體，可列舉出(甲基)丙烯酸羥基烷基酯類、含羥基的(甲基)丙烯醯胺類等。作為這些物質的具體例，以選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺組成的化合物群組中的至少一種以上為佳。這些(B)含有羥基的可共聚單體與後述的(D)聚伸烷基二醇單(甲基)丙烯酸酯單體不同，不具有聚伸烷基二醇鏈。 Examples of (B) a copolymerizable monomer containing a hydroxyl group include hydroxyalkyl (meth) acrylates, (meth) acrylamidoamines containing a hydroxyl group, and the like. Specific examples of these substances are selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- At least one or more compounds from the group consisting of hydroxyethyl ester, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide Better. These (B) hydroxyl-containing copolymerizable monomers are different from the (D) polyalkylene glycol mono (meth) acrylate monomer described later, and do not have a polyalkylene glycol chain.

相對於前述丙烯酸系聚合物的100重量份，以總量為0.1~14重量份的比例含有(B)含有羥基的可共聚單體中的至少一種為佳，更佳為0.5~12重量份的比例，特別佳為2.0~10.0重量份的比例，最佳為2.5~10.0重量份的比例。 With respect to 100 parts by weight of the acrylic polymer, at least one of (B) a copolymerizable monomer containing a hydroxyl group is preferably contained in a proportion of 0.1 to 14 parts by weight in total, more preferably 0.5 to 12 parts by weight. The ratio is particularly preferably a ratio of 2.0 to 10.0 parts by weight, and most preferably a ratio of 2.5 to 10.0 parts by weight.

作為(C)含有羧基的可共聚單體，選自由(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、 2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸所組成的化合物群組中的至少一種以上為佳。 (C) A copolymerizable monomer containing a carboxyl group is selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxypropyl hexahydrophthalic acid, 2- (meth) acryloxyethyl Phthalic acid, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2 Preferably, at least one or more of the compound group consisting of (meth) acryloxyethyltetrahydrophthalic acid is used.

相對於前述丙烯酸系聚合物的100重量份，以總量為0.01~1.0重量份的比例含有(C)含有羧基的可共聚單體中的至少一種以上為佳，更佳為0.02~1.0重量份的比例，特別佳為0.03~0.8重量份的比例，最佳為0.05~0.8重量份的比例。 With respect to 100 parts by weight of the acrylic polymer, it is preferred that at least one of the copolymerizable monomers containing (C) a carboxyl group is contained in a ratio of 0.01 to 1.0 parts by weight in total, and more preferably 0.02 to 1.0 parts by weight. The ratio is particularly preferably 0.03 to 0.8 parts by weight, and most preferably 0.05 to 0.8 parts by weight.

作為(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，只要是在聚伸烷基二醇所具有的複數個羥基中一個羥基以(甲基)丙烯酸酯的方式被酯化的化合物即可。(甲基)丙烯酸酯基為聚合性基團，因此能夠共聚為前述丙烯酸系聚合物。其他羥基可以維持OH原狀，也可成為甲醚或乙醚等烷基醚、乙酸酯等飽和羧酸酯等。 As the (D) polyalkylene glycol mono (meth) acrylate monomer, as long as one of the plurality of hydroxyl groups possessed by the polyalkylene glycol is esterified as a (meth) acrylate Compound. Since the (meth) acrylate group is a polymerizable group, it can be copolymerized into the aforementioned acrylic polymer. The other hydroxyl groups may remain as OH, or may be alkyl ethers such as methyl ether or ether, and saturated carboxylic acid esters such as acetate.

作為聚伸烷基二醇所具有的伸烷基，可列舉出伸乙基、伸丙基、伸丁基等，但不限於此。聚伸烷基二醇可以是聚乙二醇、聚丙二醇、聚丁二醇等中的兩種以上的聚伸烷基二醇的共聚物。作為聚伸烷基二醇的共聚物，可列舉出聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇、聚乙二醇-聚丙二醇-聚丁二醇等，此等共聚物可以是嵌段共聚物、隨機共聚物。 Examples of the alkylene group included in the polyalkylene glycol include but not limited to ethylene, propyl, and butylene. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. Examples of the polyalkylene glycol copolymer include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene glycol. Diols, etc. These copolymers may be block copolymers, random copolymers.

(D)聚伸烷基二醇單(甲基)丙烯酸酯單體的構成聚伸 烷基二醇鏈的伸烷基氧的平均重複數以3~14為佳。「伸烷基氧的平均重複數」是指，在(D)聚伸烷基二醇單(甲基)丙烯酸酯單體的分子結構中所包含的「聚伸烷基二醇鏈」的部分中，伸烷基氧單元重複的平均數。 (D) Composition of polyalkylene glycol mono (meth) acrylate monomer The average repeat number of the alkylene oxide of the alkyl glycol chain is preferably from 3 to 14. The "average number of alkylene oxides" refers to the portion of the "polyalkylene glycol chain" included in the molecular structure of the (D) polyalkylene glycol mono (meth) acrylate monomer. The average number of repeating alkylene oxide units.

在(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中，以單體中的二酯成分為0.2%以下為佳，「單體中的二酯成分」是指，(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中包含的聚伸烷基二醇二(甲基)丙烯酸酯的含有率(重量%)。 In the (D) polyalkylene glycol mono (meth) acrylate monomer, it is preferable that the diester component in the monomer is 0.2% or less. The "diester component in the monomer" means (D ) The content rate (% by weight) of the polyalkylene glycol di (meth) acrylate contained in the polyalkylene glycol mono (meth) acrylate monomer.

作為(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，選自聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯中的至少一種以上為佳。 (D) Polyalkylene glycol mono (meth) acrylate monomer is selected from polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylic acid It is preferable that at least one or more of an ester and an ethoxy polyalkylene glycol (meth) acrylate is used.

更具體而言，可列舉出聚乙二醇-單(甲基)丙烯酸酯、聚丙二醇-單(甲基)丙烯酸酯、聚丁二醇-單(甲基)丙烯酸酯、聚乙二醇-聚丙二醇-單(甲基)丙烯酸酯、聚乙二醇-聚丁二醇-單(甲基)丙烯酸酯、聚丙二醇-聚丁二醇-單(甲基)丙烯酸酯、聚乙二醇-聚丙二醇-聚丁二醇-單(甲基)丙烯酸酯；甲氧基聚乙二醇-(甲基)丙烯酸酯、甲氧基聚丙二醇-(甲基)丙烯酸酯、甲氧基聚丁二醇-(甲基)丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、甲氧基-聚乙二醇-聚丁二醇-(甲基)丙烯酸酯、甲氧基-聚丙二醇-聚丁二醇-(甲基)丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-聚丁二醇-(甲基)丙烯酸酯；乙氧基聚乙二醇-(甲基)丙烯酸酯、乙氧基聚丙二醇-(甲基)丙烯酸酯、乙氧基聚丁二醇-(甲基)丙烯酸酯、 乙氧基-聚乙二醇-聚丙二醇-(甲基)丙烯酸酯、乙氧基-聚乙二醇-聚丁二醇-(甲基)丙烯酸酯、乙氧基-聚丙二醇-聚丁二醇-(甲基)丙烯酸酯、乙氧基-聚乙二醇-聚丙二醇-聚丁二醇-(甲基)丙烯酸酯等。 More specifically, polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, polybutylene glycol-mono (meth) acrylate, and polyethylene glycol- Polypropylene glycol-mono (meth) acrylate, polyethylene glycol-polybutylene glycol-mono (meth) acrylate, polypropylene glycol-polybutylene glycol-mono (meth) acrylate, polyethylene glycol- Polypropylene glycol-polybutylene glycol-mono (meth) acrylate; methoxy polyethylene glycol- (meth) acrylate, methoxy polypropylene glycol- (meth) acrylate, methoxy polybutylene Alcohol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, methyl Oxy-polypropylene glycol-polybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate; ethoxy polyethylene glycol- (Meth) acrylate, ethoxy polypropylene glycol- (meth) acrylate, ethoxy polybutylene glycol- (meth) acrylate, Ethoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, ethoxy-polypropylene glycol-polybutylene Alcohol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate and the like.

相對於100重量份前述丙烯酸系聚合物，以總量為超過0且為35重量份以下的比例含有(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上為佳，更佳為以超過0且為25重量份以下的比例含有，特別佳為以2.0~23.0重量份的比例含有，最佳為以4.0~20.0重量份的比例含有。 Containing at least one or more of (D) polyalkylene glycol mono (meth) acrylate monomers in a proportion of a total amount of more than 0 to 35 parts by weight based on 100 parts by weight of the acrylic polymer is Preferably, it is contained in a ratio of more than 0 and 25 parts by weight or less, particularly preferably in a proportion of 2.0 to 23.0 parts by weight, and most preferably in a proportion of 4.0 to 20.0 parts by weight.

作為(E)雙官能以上的異氰酸酯化合物，只要為選自1分子中具有至少2個以上異氰酸酯(NCO)基的聚異氰酸酯化合物中的至少一種以上或兩種以上即可。聚異氰酸酯化合物中有脂肪族系異氰酸酯、芳香族系異氰酸酯、非環式系異氰酸酯、脂環式系異氰酸酯等分類，均可使用。作為聚異氰酸酯化合物的具體例，可列舉出六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)、三甲基六亞甲基二異氰酸酯(TMDI)等脂肪族類異氰酸酯化合物；二苯甲烷二異氰酸酯(MDI)、二甲苯撐基二異氰酸酯(XDI)、氫化二甲苯撐基二異氰酸酯(H6XDI)、二甲基二亞苯基二異氰酸酯(TOID)、甲苯二異氰酸酯(TDI)等芳香族類異氰酸酯化合物。 The (E) difunctional or higher isocyanate compound may be at least one or two or more selected from polyisocyanate compounds having at least two or more isocyanate (NCO) groups in one molecule. Polyisocyanate compounds are classified into aliphatic isocyanates, aromatic isocyanates, acyclic isocyanates, and alicyclic isocyanates, and can be used. Specific examples of the polyisocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMDI); Diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), dimethyldiphenylene diisocyanate (TOID), toluene diisocyanate (TDI), etc. Aromatic isocyanate compounds.

作為三官能以上的異氰酸酯化合物，可列舉出雙官能異氰酸酯化合物(1分子中具有2個NCO基的化合物)的縮二脲改性體或異氰脲酸酯改性體、與三羥甲基丙烷(TMP)或甘油等三元以上的多元醇(1分子中具有至少3個以上OH基的化合物) 的加成體(多元醇改性體)等。 Examples of the trifunctional or higher isocyanate compounds include biuret-modified or isocyanurate-modified products of bifunctional isocyanate compounds (compounds having two NCO groups in one molecule), and trimethylolpropane. (TMP) or glycerol such as glycerol (a compound having at least 3 OH groups in one molecule) Adducts (modified polyols) and the like.

作為(E)雙官能以上的異氰酸酯化合物，可僅使用(E-1)三官能異氰酸酯化合物或僅使用(E-2)雙官能異氰酸酯化合物。也可同時使用(E-1)三官能異氰酸酯化合物和(E-2)雙官能異氰酸酯化合物。 As the (E) difunctional or higher isocyanate compound, only (E-1) a trifunctional isocyanate compound or only (E-2) a difunctional isocyanate compound can be used. It is also possible to use (E-1) a trifunctional isocyanate compound and (E-2) a difunctional isocyanate compound simultaneously.

進一步，作為用於本發明的(E-1)三官能異氰酸酯化合物，以含有選自由六亞甲基二異氰酸酯化合物的異氰脲酸酯體、異佛爾酮二異氰酸酯化合物的異氰脲酸酯體、六亞甲基二異氰酸酯化合物的加成體、異佛爾酮二異氰酸酯化合物的加成體、六亞甲基二異氰酸酯化合物的縮二脲體、異佛爾酮二異氰酸酯化合物的縮二脲體組成的(E-1-1)第一脂肪族類的異氰酸酯化合物群組中的至少一種以上，及選自由甲苯二異氰酸酯化合物的異氰脲酸酯體、二甲苯撐基二異氰酸酯化合物的異氰脲酸酯體、氫化二甲苯撐基二異氰酸酯化合物的異氰脲酸酯體、甲苯二異氰酸酯化合物的加成體、二甲苯撐基二異氰酸酯化合物的加成體、氫化二甲苯撐基二異氰酸酯化合物的加成體組成的(E-1-2)第二芳香族類的異氰酸酯化合物群組中的至少一種以上為佳。以同時使用(E-1-1)第一脂肪族類的異氰酸酯化合物組和(E-1-2)第二芳香族類的異氰酸酯化合物組為佳。在本發明中，作為(E-1)三官能異氰酸酯化合物，藉由同時使用選自(E-1-1)第一脂肪族類的異氰酸酯化合物群組中的至少一種以上、選自(E-1-2)第二芳香族類的異氰酸酯化合物群組中的至少一種以上，能夠進一步改善低速剝離區域及高速剝離區域的黏著力的平衡。 Furthermore, as the (E-1) trifunctional isocyanate compound used in the present invention, an isocyanurate containing an isocyanurate body selected from a hexamethylene diisocyanate compound and an isophorone diisocyanate compound is used. Body, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, biuret body of hexamethylene diisocyanate compound, biuret of isophorone diisocyanate compound (E-1-1) at least one or more of the first aliphatic isocyanate compound group, and an isocyanurate body consisting of a toluene diisocyanate compound, or an isocyanurate compound containing a xylylene diisocyanate compound. Cyanurate body, isocyanurate body of hydrogenated xylylene diisocyanate compound, adduct body of toluene diisocyanate compound, adduct body of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate It is preferable that at least one or more of the (E-1-2) second aromatic isocyanate compound group composed of the adduct of the compound. It is preferable to use (E-1-1) the first aliphatic isocyanate compound group and (E-1-2) the second aromatic isocyanate compound group at the same time. In the present invention, as the (E-1) trifunctional isocyanate compound, at least one selected from the group of (E-1-1) first aliphatic isocyanate compounds is used together and selected from (E- 1-2) At least one or more of the second aromatic isocyanate compound group can further improve the balance of the adhesive force in the low-speed peeling region and the high-speed peeling region.

此外，(E-1)三官能異氰酸酯化合物以含有選自前述(E-1-1)第一脂肪族類的異氰酸酯化合物群組中的至少一種以上、以及選自前述(E-1-2)第二芳香族類的異氰酸酯化合物群組中的至少一種以上，相對於100重量份前述丙烯酸系聚合物，其總量佳含有0.5~5.0重量份為佳。此外，選自(E-1-1)第一脂肪族類的異氰酸酯化合物群組中的至少一種以上與選自(E-1-2)第二芳香族類的異氰酸酯化合物群組中的至少一種以上的混合比例，即(E-1-1)：(E-1-2)之重量比以10%：90%~90%：10%的範圍內為佳。 The (E-1) trifunctional isocyanate compound contains at least one or more members selected from the aforementioned (E-1-1) first aliphatic isocyanate compound group, and is selected from the aforementioned (E-1-2) At least one or more of the second aromatic isocyanate compound group is preferably contained in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the acrylic polymer. In addition, at least one selected from the group of (E-1-1) first aliphatic isocyanate compounds and at least one selected from the group of (E-1-2) second aromatic isocyanate compounds The above mixing ratio, that is, the weight ratio of (E-1-1) :( E-1-2) is preferably within a range of 10%: 90% to 90%: 10%.

進一步，作為本發明中使用的(E-2)雙官能異氰酸酯化合物，以非環式脂肪族異氰酸酯化合物，為使二異氰酸酯化合物與二醇化合物反應生成的化合物為佳。 Furthermore, as the (E-2) difunctional isocyanate compound used in the present invention, an acyclic aliphatic isocyanate compound is preferably a compound formed by reacting a diisocyanate compound with a diol compound.

例如，在以通式「O=C=N-X-N=C=O」(其中，X為2價基團)表示二異氰酸酯化合物、以通式「HO-Y-OH」(其中，Y為2價基團)表示二醇化合物時，作為使二異氰酸酯化合物與二醇化合物反應而生成的化合物，例如可列舉出以下述通式Z表示的化合物。 For example, a diisocyanate compound is represented by the general formula "O = C = NXN = C = O" (where X is a divalent group), and a general formula "HO-Y-OH" (where Y is a divalent group) When a diol compound represents a diol compound, examples of the compound produced by reacting a diisocyanate compound with a diol compound include compounds represented by the following general formula Z.

[通式Z]O=C=N-X-(NH-CO-O-Y-O-CO-NH-X)n-N=C=O [Formula Z] O = C = NX- (NH-CO-OYO-CO-NH-X) n -N = C = O

其中，n為0以上的整數。n為0時，通式Z表示「O=C=N-X-N=C=O」。作為雙官能非環式脂肪族異氰酸酯化合物，也可以含有通式Z中n為0的化合物(未與二醇化合物反應的二異氰酸酯化合物)，但以含有n為1以上的整數的化合物作為必要成分為佳。雙官能非環式脂肪族異氰酸酯化合物可以是 由通式Z中n相異的複數個化合物所組成的混合物。 Here, n is an integer of 0 or more. When n is 0, the general formula Z represents "O = C = N-X-N = C = O". The bifunctional acyclic aliphatic isocyanate compound may contain a compound in which n is 0 in the general formula Z (a diisocyanate compound that has not reacted with a diol compound), but a compound containing n having an integer of 1 or more may be used as an essential component. Better. The bifunctional acyclic aliphatic isocyanate compound may be A mixture composed of a plurality of compounds in which n is different in the general formula Z.

通式「O=C=N-X-N=C=O」所表示的二異氰酸酯化合物為脂肪族二異氰酸酯。X以非環式的脂肪族2價基團為佳。作為前述脂肪族二異氰酸酯，以選自由四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯組成的化合物群組中的一種或兩種以上所組成為佳。 The diisocyanate compound represented by the general formula "O = C = N-X-N = C = O" is an aliphatic diisocyanate. X is preferably an acyclic aliphatic divalent group. The aliphatic diisocyanate is selected from a compound group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. One or two or more of the groups are preferred.

通式「HO-Y-OH」所表示的二醇化合物為脂肪族二醇。Y以非環式的脂肪族2價基團為佳。作為前述二醇化合物，以選自由2-甲基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、3-甲基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇單羥基新戊酸酯、聚乙二醇、聚丙二醇所組成的化合物群組中的一種或兩種以上組成為佳。 The diol compound represented by the general formula "HO-Y-OH" is an aliphatic diol. Y is preferably an acyclic aliphatic divalent group. The diol compound is selected from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol monohydroxypivalate, poly One or two or more compounds in a compound group composed of ethylene glycol and polypropylene glycol are preferred.

前述(E-1)三官能異氰酸酯化合物與(E-2)雙官能異氰酸酯化合物的重量比(E-1/E-2)以1~90為佳。相對於100重量份前述丙烯酸系聚合物，前述(E)雙官能以上的異氰酸酯化合物的比例以0.1~10重量份為佳。 The weight ratio (E-1 / E-2) of the (E-1) trifunctional isocyanate compound to the (E-2) difunctional isocyanate compound is preferably 1 to 90. The proportion of the isocyanate compound having a difunctional or higher (E) ratio is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.

在將聚異氰酸酯化合物作為交聯劑時，(F)交聯促進劑只要是對前述丙烯酸系聚合物與交聯劑的反應(交聯反應)發揮作為催化劑功能的物質即可，可列舉出三級胺等胺類化合物、金屬螯合物、有機錫化合物、有機鉛化合物、有機鋅化合物等有機金屬化合物等。本發明中，作為交聯促進劑，以金屬螯合物或有機錫化合物為佳。 When a polyisocyanate compound is used as the crosslinking agent, the (F) crosslinking accelerator may be any substance that functions as a catalyst for the reaction (crosslinking reaction) between the acrylic polymer and the crosslinking agent, and three examples thereof are exemplified. Amine compounds such as amines, metal chelates, organic tin compounds, organic lead compounds, and organic zinc compounds such as organic zinc compounds. In the present invention, as the crosslinking accelerator, a metal chelate compound or an organic tin compound is preferred.

作為金屬螯合物，為在中心金屬原子M上結合有1個以上的多牙配位子L的化合物。金屬螯合物可以具有也可以不具有結合在金屬原子M上的1個以上的單牙配位子X。例如，將金屬原子M為1個的金屬螯合物的通式表示為M(L)m(X)n時，m≧1、n≧0。m為2以上時，m個L可以為相同的配位子，也可以為相異的配位子。n為2以上時，n個X可以為相同的配位子，也可以為相異的配位子。 The metal chelate is a compound in which one or more polydentate ligands L are bonded to a central metal atom M. The metal chelate may or may not have one or more monodentate ligands X bonded to the metal atom M. For example, when the general formula of a metal chelate compound having one metal atom M is represented by M (L) m (X) n , m ≧ 1 and n ≧ 0. When m is 2 or more, m Ls may be the same ligand or different ligands. When n is 2 or more, n Xs may be the same ligand or different ligands.

作為金屬原子M，可列舉出Fe、Ni、Mn、Cr、V、Ti、Ru、Zn、Al、Zr、Sn等。 Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, and Sn.

作為多牙配位子L，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醯基酯(oleyl acetoacetate)、乙醯乙酸月桂酯(lauryl acetoacetate)、乙醯乙酸硬脂醇酯(stearyl acetoacetate)等β-酮酯，或乙醯丙酮(別名2,4-戊二酮)、2,4-己二酮、苯甲醯丙酮等β-二酮。這些物質為酮-烯醇互變異構體化合物，也可以是在多牙配位子L中烯醇經過去質子化的烯醇化物(例如乙醯丙酮化物)。 Examples of the polydentate ligand L include methyl ethyl acetate, ethyl ethyl acetate, octyl ethyl acetate, oleyl acetoacetate, and lauryl acetoacetate. Β-ketoesters such as stearyl acetoacetate, or β-diketones such as acetoacetone (alias 2,4-pentanedione), 2,4-hexanedione, and benzophenone acetone . These substances are keto-enol tautomer compounds, and may also be enolates (for example, acetamidine acetonate) in which the enol is deprotonated in the polydentate ligand L.

作為單牙配位子X，可列舉出氯原子、溴原子等鹵素原子、戊醯基、己醯基、2-乙基己醯基、辛醯基、壬醯基、癸醯基、十二醯基、十八醯基等醯氧基、甲氧基、乙氧基、正丙氧基、異丙氧基、丁氧基等烷氧基等。 Examples of the monodentate ligand X include halogen atoms such as a chlorine atom and a bromine atom, pentamyl, hexyl, 2-ethylhexyl, octyl, nonyl, decyl, and dodecyl. , Alkoxy such as octadecyl, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy and the like.

作為金屬螯合物的具體例，可列舉出三(2,4-戊二酮(pentanedionato))合鐵(III)、三乙醯丙酮鐵、三乙醯丙酮鈦、三乙醯丙酮釕、雙乙醯丙酮鋅、三乙醯丙酮鋁、四乙醯丙酮鋯、三(2,4-己二酮)合鐵(III)、雙(2,4-己二酮)合鋅、 三(2,4-己二酮)合鈦、三(2,4-己二酮)合鋁、四(2,4-己二酮)合鋯等。 Specific examples of the metal chelate include tris (2,4-pentanedionato) iron (III), iron triacetonate, titanium triacetonium acetone, ruthenium triacetonate, ruthenium triacetonate, Zinc acetoacetone, aluminum triacetate acetone, zirconium acetoacetone, tris (2,4-hexadione) iron (III), bis (2,4-hexadione) zinc, Tris (2,4-hexadione) titanium, tris (2,4-hexadione) aluminum, tetras (2,4-hexadione) zirconium, and the like.

作為有機錫化合物，可列舉出二烷基氧化錫、或二烷基錫的脂肪酸鹽、二價錫的脂肪酸鹽等。在以往，使用二丁錫化合物較多，但近年來，指出了有機錫化合物的毒性的問題，特別是二丁錫化合物所含有的三丁錫(TBT)，以作為內分泌擾亂物質而受到擔憂。從安全性的角度出發，以二辛錫化合物等長鏈烷基錫化合物為佳。作為具體的有機錫化合物，可列舉出二辛基氧化錫、二月桂酸二辛基錫等。雖然暫時也可使用Sn化合物，但鑒於未來要求使用安全性更高的物質的趨勢，以使用與Sn相比安全性高的Al、Ti、Fe等的金屬螯合物為佳。 Examples of the organotin compound include dialkyltin oxide, fatty acid salts of dialkyltin, and fatty acid salts of divalent tin. Dibutyltin compounds have been used in the past, but in recent years, the toxicity of organotin compounds has been pointed out. In particular, tributyltin (TBT) contained in dibutyltin compounds has been concerned as an endocrine disrupting substance. From the viewpoint of safety, a long-chain alkyltin compound such as a dioctyltin compound is preferred. Specific examples of the organic tin compound include dioctyltin oxide and dioctyltin dilaurate. Although Sn compounds may be used for the time being, in view of the trend of using more safe substances in the future, it is better to use metal chelates such as Al, Ti, Fe, etc., which are safer than Sn.

作為本發明的黏著劑組合物中的(F)交聯促進劑，以選自由鋁螯合物、鈦螯合物、鐵螯合物構成的群組中的至少一種以上為佳。 The (F) crosslinking accelerator in the adhesive composition of the present invention is preferably at least one or more selected from the group consisting of an aluminum chelate, a titanium chelate, and an iron chelate.

相對於100重量份前述丙烯酸系聚合物，以含有0.001~0.5重量份(F)交聯促進劑為佳。 It is preferable to contain 0.001-0.5 weight part (F) crosslinking accelerator with respect to 100 weight part of said acrylic polymer.

作為(G)酮-烯醇互變異構體化合物，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油基酯、乙醯乙酸月桂酯、乙醯乙酸硬脂醇酯等β-酮酯，或乙醯丙酮、2,4-己二酮、苯甲醯丙酮等β-二酮。這些物質藉由在以聚異氰酸酯化合物為交聯劑的黏著劑組合物中，對交聯劑具有的異氰酸酯基進行阻斷(block)，能夠抑制添加交聯劑後黏著劑組合物的過度的黏度上升或凝膠化，從而延長黏著劑組合物的適用期。 Examples of (G) keto-enol tautomer compounds include methyl ethyl acetate, ethyl ethyl acetate, octyl ethyl acetate, oleyl ethyl acetate, lauryl ethyl acetate, and ethyl acetate Β-ketoesters such as stearyl acetate, or β-diketones such as acetone, 2,4-hexanedione, and benzophenone. These substances can suppress the excessive viscosity of the adhesive composition after adding the crosslinking agent by blocking the isocyanate group of the crosslinking agent in the adhesive composition using the polyisocyanate compound as the crosslinking agent. Rise or gel, thereby extending the pot life of the adhesive composition.

相對於100重量份前述丙烯酸系聚合物，以含有0.1~300重量份(G)酮-烯醇互變異構體化合物為佳。 It is preferable to contain 0.1 to 300 parts by weight (G) of a keto-enol tautomer compound with respect to 100 parts by weight of the acrylic polymer.

由於(G)酮-烯醇互變異構體化合物與(F)交聯促進劑相反、具有抑制交聯的效果，因此，以適當地設定(G)酮-烯醇互變異構體化合物相對於(F)交聯促進劑的比例為佳。從延長黏著劑組合物的適用期，提高貯藏穩定性來看，(G)/(F)的重量份比例以70~1000為佳，更佳為70~700，特別佳為80~600。 The (G) keto-enol tautomer compound is opposite to the (F) cross-linking accelerator and has the effect of inhibiting cross-linking. Therefore, the (G) keto-enol tautomer compound is appropriately set relative to (F) The proportion of the crosslinking accelerator is preferred. From the perspective of extending the pot life of the adhesive composition and improving storage stability, the weight ratio of (G) / (F) is preferably 70 to 1,000, more preferably 70 to 700, and particularly preferably 80 to 600.

此外，本發明的黏著劑組合物含有(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物作為抗靜電劑。由於這些抗靜電劑的熔點低，且具有長鏈烷基，因此推測與丙烯酸系聚合物的親和性高。 In addition, the adhesive composition of the present invention contains (H) an ionic compound having a melting point of 25 to 50 ° C and being solid at a temperature of 25 ° C as an antistatic agent. Since these antistatic agents have a low melting point and have a long-chain alkyl group, it is estimated that they have high affinity with acrylic polymers.

作為(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物，為具有陽離子和陰離子的離子化合物，陽離子可列舉出吡啶鎓陽離子、咪唑鎓陽離子、嘧啶鎓陽離子、吡鎓陽離子、吡咯啶鎓陽離子、銨陽離子等含氮鎓陽離子或鏻陽離子、鋶陽離子等，陰離子可列舉出六氟磷酸鹽(PF6 -)、硫氰酸鹽(SCN-)、烷基苯磺酸鹽(RC6H4SO3 -)、過氯酸鹽(ClO4 -)、四氟硼酸鹽(BF4 -)、雙(氟磺醯基)亞胺鹽(FSI)、雙(三氟甲烷磺醯基)亞胺鹽(TFSI)、三氟甲烷磺酸鹽(TF)等無機或有機陰離子的化合物。以在常溫(例如25℃)時為固體為佳，根據烷基的鏈長或取代基的位置、個數等的選擇能夠獲得熔點為25~50℃之物。陽離子以四級含氮鎓陽離子為佳，可列舉出1-烷基吡啶鎓(2~6位的碳原子可以具有取代基，也可以不具 有。)等四級吡啶鎓陽離子、1,3-二烷基咪唑鎓(2、4、5位的碳原子可以具有取代基，也可以不具有。)等的四級咪唑鎓陽離子、四烷基銨等的四級銨陽離子等。 (H) An ionic compound having a melting point of 25 to 50 ° C and being solid at a temperature of 25 ° C is an ionic compound having a cation and an anion. Examples of the cation include a pyridinium cation, an imidazolium cation, a pyrimidinium cation, and a pyridine. Cation, pyrrolidine cation, ammonium cation or phosphonium cation containing nitrogen cation, sulfonium cation, anion include hexafluorophosphate (PF 6 -), thiocyanate (SCN -), alkylbenzenesulfonate salt (RC 6 H 4 SO 3 - ), perchlorate (ClO 4 -), tetrafluoroborate (BF 4 -), bis (fluorosulfonyl acyl) imide salt (FSI), bis (trifluoromethyl Compounds of inorganic or organic anions such as methanesulfonyl) imide (TFSI), trifluoromethanesulfonate (TF). It is preferably solid at normal temperature (for example, 25 ° C), and a substance having a melting point of 25 to 50 ° C can be obtained according to the choice of the chain length of the alkyl group, the position and number of substituents, and the like. The cation is preferably a quaternary nitrogen-containing cation, and examples thereof include 1-alkylpyridinium (the carbon atom at the 2 to 6 position may or may not have a substituent.), Etc. Dialkyl imidazolium (quaternary imidazolium cations such as carbon atoms at the 2, 4, and 5 positions may or may not have a substituent.), Quaternary ammonium cations, such as tetraalkyl ammonium, and the like.

相對於100重量份前述丙烯酸系聚合物，以總量為0.01~5.0重量份的比例含有(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物中的至少一種以上為佳。 It is preferable to contain at least one or more of (H) an ionic compound having a melting point of 25 to 50 ° C. and being solid at a temperature of 25 ° C. to 100 parts by weight of the acrylic polymer in a total amount of 0.01 to 5.0 parts by weight. .

作為(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物的具體例，例如可列舉出1-辛基吡啶鎓六氟磷酸鹽、1-壬基吡啶鎓六氟磷酸鹽、2-甲基-1-十二烷基吡啶鎓六氟磷酸鹽、1-辛基吡啶鎓十二烷基苯磺酸鹽、1-十二烷基吡啶鎓硫氰酸鹽、1-十二烷基吡啶鎓十二烷基苯磺酸鹽、4-甲基-1-辛基吡啶鎓六氟磷酸鹽等。 Specific examples of the (H) ionic compound having a melting point of 25 to 50 ° C at a temperature of 25 ° C include 1-octylpyridinium hexafluorophosphate and 1-nonylpyridinium hexafluorophosphate , 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate, 1-deca Dialkylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like.

黏著劑組合物可任意含有(I)HLB值為7~15的聚醚改性矽氧烷化合物。聚醚改性矽氧烷化合物為具有聚醚基的矽氧烷化合物，除通常的矽氧烷單元[-SiR1 2-O-]以外，具有含有聚醚基的矽氧烷單元[-SiR1(R2O(R3O)nR4)-O-]。其中R1為一種或兩種以上的烷基或芳基，R2及R3為一種或兩種以上的伸烷基，R4為一種或兩種以上的烷基或醯基等(末端基團)。作為聚醚基，可列舉出聚氧乙烯基[(C2H4O)n]或聚氧丙烯基[(C3H6O)n]等聚氧伸烷基。 The adhesive composition may optionally contain (I) a polyether-modified silicone compound having an HLB value of 7 to 15. The polyether-modified silicone compound is a silicone compound having a polyether group. In addition to the normal silicone unit [-SiR 1 2 -O-], it has a polyether group-containing silicone unit [-SiR 1 (R 2 O (R 3 O) n R 4 ) -O-]. Where R 1 is one or two or more alkyl or aryl groups, R 2 and R 3 are one or two or more alkylene groups, R 4 is one or two or more alkyl or fluorenyl groups (terminal groups group). Examples of the polyether group include polyoxyalkylene groups such as polyoxyethylene group [(C 2 H 4 O) n ] and polyoxypropylene group [(C 3 H 6 O) n ].

例如，對於具有氫化矽基的聚有機矽氧烷主鏈，藉由對具有不飽和鍵及聚氧伸烷基的有機化合物進行矽氫化反應，使其接枝，能夠得到聚醚改性矽氧烷化合物。具體而言，可列舉出二甲基矽氧烷‧甲基(聚氧乙烯)矽氧烷共聚物、二 甲基矽氧烷‧甲基(聚氧乙烯)矽氧烷‧甲基(聚氧丙烯)矽氧烷共聚物、二甲基矽氧烷‧甲基(聚氧丙烯)矽氧烷聚合物等。聚醚改性矽氧烷化合物的HLB值能夠藉由選擇聚醚基與矽氧烷基的比例來進行調整。 For example, for a polyorganosiloxane main chain having a hydridosilyl group, a polyether-modified siloxane can be obtained by performing a hydrosilation reaction on an organic compound having an unsaturated bond and a polyoxyalkylene group, and grafting the compound. TAN compounds. Specific examples include dimethylsiloxane, methyl (polyoxyethylene) siloxane copolymer, Methylsiloxane, methyl (polyoxyethylene) silicone, methyl (polyoxypropylene) silicone copolymer, dimethylsiloxane, methyl (polyoxypropylene) silicone polymer, etc. . The HLB value of the polyether-modified silicone compound can be adjusted by selecting the ratio of the polyether group to the silicone group.

藉由在黏著劑組合物中添加(I)HLB值為7~15的聚醚改性矽氧烷化合物，能夠改善黏著劑的黏著力及污染性。黏著劑組合物不含有聚醚改性矽氧烷化合物時，成本進一步降低。 By adding (I) a polyether-modified silicone compound having an HLB value of 7 to 15 to the adhesive composition, the adhesive force and contamination of the adhesive can be improved. When the adhesive composition does not contain a polyether-modified silicone compound, the cost is further reduced.

聚醚改性矽氧烷化合物，以HLB值為7~15的聚醚改性矽氧烷化合物為佳。HLB是指例如在JIS K3211(界面活性劑用語)等中規定的親水親油平衡(親水性親油性比)。 The polyether-modified silicone compound is preferably a polyether-modified silicone compound having an HLB value of 7 to 15. HLB refers to, for example, the hydrophilic-lipophilic balance (hydrophilic-lipophilic ratio) specified in JIS K3211 (surfactant term).

此外，相對於100重量份前述丙烯酸系聚合物，以0.01~1.0重量份的比例含有(I)HLB值為7~15的聚醚改性矽氧烷化合物為佳，更佳為0.05~0.8重量份的比例，特別佳為0.1~0.5重量份的比例。 In addition, it is preferable to contain (I) a polyether-modified silicone compound having an HLB value of 7 to 15 with respect to 100 parts by weight of the acrylic polymer, and more preferably 0.05 to 0.8 by weight. The proportion of parts is particularly preferably a proportion of 0.1 to 0.5 parts by weight.

本發明的黏著劑組合物中所使用的丙烯酸系聚合物，能夠藉由使下述物質進行共聚而合成：作為(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種以上，作為可共聚單體組的(B)含有羥基的可共聚單體中的至少一種以上、(C)含有羧基的可共聚單體中的至少一種以上、(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上。丙烯酸系聚合物的聚合方法沒有特別限定，可使用溶液聚合、乳化聚合等適當的聚合方法。 The acrylic polymer used in the adhesive composition of the present invention can be synthesized by copolymerizing a (meth) acrylic acid ester monoester having a carbon number of C1 to C18 as the (A) alkyl group. The (a1) alkyl group has at least one type of (meth) acrylic acid ester monomer of C1 to C4, and the (a2) alkyl group has (C5 to C18) (meth) acrylic acid ester At least one or more of the monomers, (B) at least one or more of a hydroxyl-containing copolymerizable monomer as a copolymerizable monomer group, (C) at least one or more of a copolymerizable monomer containing a carboxyl group, (D) At least one or more of polyalkylene glycol mono (meth) acrylate monomers. The polymerization method of the acrylic polymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.

在製備主劑的共聚物時，為了減少水分混入黏著劑組合物，以使用無水的有機溶劑的溶液聚合等在無水條件下進行聚合反應為佳。特別是由於(D)聚伸烷基二醇單(甲基)丙烯酸酯單體的親水性高，因此以使用含水率低者為佳伸烷。 In the preparation of the copolymer of the main agent, in order to reduce the mixing of moisture into the adhesive composition, it is preferable to perform the polymerization reaction under anhydrous conditions, such as solution polymerization using an anhydrous organic solvent. In particular, since (D) a polyalkylene glycol mono (meth) acrylate monomer has high hydrophilicity, it is preferable to use a lower alkylene oxide if the water content is low.

為了避免黏著劑組合物的黏度上升，對於用於製備主劑的共聚物的各單體，以極力降低作為交聯劑作用的多官能性(雙官能性以上)的單體的量為佳。特別是由於(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中所對應的二酯成分為雙官能性單體的二(甲基)丙烯酸酯，因此以使用二酯成分少者為佳伸烷。 In order to avoid an increase in the viscosity of the adhesive composition, it is preferable that the amount of the polyfunctional (more than bifunctional) monomer that acts as a cross-linking agent is minimized for each monomer used to prepare the copolymer of the main agent. In particular, since the corresponding diester component in the (D) polyalkylene glycol mono (meth) acrylate monomer is a di (meth) acrylate of a bifunctional monomer, the number of diester components used is small. Those are good alkane.

本發明的黏著劑組合物可藉由在前述丙烯酸系聚合物中，進一步適當添加任意添加劑即(E)雙官能以上的異氰酸酯化合物、(F)交聯促進劑、(G)酮-烯醇互變異構體化合物、(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物而製備。 The adhesive composition of the present invention can further appropriately add any additives to the acrylic polymer, that is, (E) a bifunctional or higher isocyanate compound, (F) a cross-linking accelerator, and (G) a keto-enol interaction. Isomer compounds, (H) ionic compounds having a melting point of 25 to 50 ° C, which are solid at a temperature of 25 ° C, are prepared.

本發明的黏著劑組合物為使前述丙烯酸系聚合物在不包含不含有羥基的含氮乙烯單體、及含烷氧基的(甲基)丙烯酸烷基酯單體的情況下而進行共聚而成的共聚物。 The adhesive composition of the present invention is obtained by copolymerizing the acrylic polymer without containing a nitrogen-containing vinyl monomer that does not contain a hydroxyl group, and an alkyl (meth) acrylate monomer that contains an alkoxy group. Into a copolymer.

此外，作為前述不含有羥基的含氮乙烯單體，例如可列舉出含有N,N-二烷基取代胺基或N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基-2-吡咯啶酮、N-乙烯基己內醯胺、N-乙烯基-2-哌啶酮等N-乙烯基取代內醯胺類；N-(甲基)丙烯醯基嗎福林或N-(甲基)丙烯醯基吡咯啶等N-(甲基)丙烯醯基取代環狀胺類；含丙烯醯基的銨鹽等含丙烯醯基的離子化合物等。 In addition, examples of the nitrogen-containing vinyl monomer not containing a hydroxyl group include acrylic monomers containing N, N-dialkyl-substituted amino groups or N, N-dialkyl-substituted amido groups; N-ethylene N-vinyl substituted lactams such as N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidone; N- (meth) acryl fluorenyl morpholin Or N- (meth) acrylfluorenyl substituted cyclic amines such as N- (meth) acrylfluorenyl pyrrolidine; acrylfluorenyl-containing ionic compounds such as ammonium salts containing acrylfluorenyl.

作為含丙烯醯基的離子化合物的具體例，可列舉出(甲基)丙烯酸二甲氨基甲酯甲基六氟磷酸鹽[(CH3)3N+CH2OCOCQ=CH2．PF6 -，其中，Q=H或CH3]、(甲基)丙烯酸二甲氨基乙酯甲基雙(三氟甲烷磺醯基)醯亞胺鹽[(CH3)3N+(CH2)2OCOCQ=CH2．(CF3SO2)2N-，其中，Q=H或CH3]、甲基丙烯酸二甲氨基甲酯甲基雙(氟磺醯基)醯亞胺鹽[(CH3)3N+CH2OCOCQ=CH2．(FSO2)2N-，其中，Q=H或CH3]等。 Specific examples of the propylene fluorenyl group-containing ionic compound include dimethylaminomethyl (meth) acrylate methylhexafluorophosphate [(CH 3 ) 3 N + CH 2 OCOCQ = CH 2 . PF 6 - where Q = H or CH 3 ], dimethylaminoethyl (meth) acrylate methylbis (trifluoromethanesulfonyl) fluorene imine salt [(CH 3 ) 3 N + (CH 2 ) 2 OCOCQ = CH 2 . (CF 3 SO 2 ) 2 N - where Q = H or CH 3 ], dimethylaminomethyl methacrylate methylbis (fluorosulfonyl) fluorene imine salt [(CH 3 ) 3 N + CH 2 OCOCQ = CH 2 . (FSO 2) 2 N -, where, Q = H or CH 3] and the like.

此外，作為前述含烷氧基的(甲基)丙烯酸烷基酯單體，例如可列舉出(甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基乙酯、(甲基)丙烯酸-2-丙氧基乙酯、(甲基)丙烯酸-2-異丙氧基乙酯、(甲基)丙烯酸-2-丁氧基乙酯、(甲基)丙烯酸-2-甲氧基丙酯、(甲基)丙烯酸-2-乙氧基丙酯、(甲基)丙烯酸-2-丙氧基丙酯、(甲基)丙烯酸-2-異丙氧基丙酯、(甲基)丙烯酸-2-丁氧基丙酯、(甲基)丙烯酸-3-甲氧基丙酯、(甲基)丙烯酸-3-乙氧基丙酯、(甲基)丙烯酸-3-丙氧基丙酯、(甲基)丙烯酸-3-異丙氧基丙酯、(甲基)丙烯酸-3-丁氧基丙酯、(甲基)丙烯酸-4-甲氧基丁酯、(甲基)丙烯酸-4-乙氧基丁酯、(甲基)丙烯酸-4-丙氧基丁酯、(甲基)丙烯酸-4-異丙氧基丁酯、(甲基)丙烯酸-4-丁氧基丁酯等。 Examples of the alkoxy-containing (meth) acrylic acid alkyl ester monomer include, for example, 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate Ester, 2-propoxyethyl (meth) acrylate, 2-isopropoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, (meth) acrylic acid 2-methoxypropyl, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate Ester, 2-butoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) acrylic acid- 3-propoxypropyl, 3-isopropoxypropyl (meth) acrylate, 3-butoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate , 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxybutyl (meth) acrylate, (meth) acrylic acid- 4-butoxybutyl ester and the like.

這些含烷氧基的(甲基)丙烯酸烷基酯單體具有(甲基)丙烯酸烷基酯中的烷基的原子被烷氧基取代的結構。由於含烷氧基的(甲基)丙烯酸烷基酯單體不具有聚伸烷基二醇結構，因此含烷氧基的(D)聚伸烷基二醇單(甲基)丙烯酸酯單體不屬於含烷氧基的(甲基)丙烯酸烷基酯單體。 These alkoxy group-containing alkyl (meth) acrylate monomers have a structure in which an atom of an alkyl group in the alkyl (meth) acrylate is substituted with an alkoxy group. Since the alkoxy group-containing (meth) acrylic acid alkyl ester monomer does not have a polyalkylene glycol structure, the alkoxy group-containing (D) polyalkylene glycol mono (meth) acrylate monomer It does not belong to the alkoxy-containing alkyl (meth) acrylate monomer.

本發明的特徵在於解決了以下技術問題，即提供一種即使黏著劑組合物中所含的丙烯酸系聚合物不包含不含有羥基的含氮乙烯單體及含烷氧基的(甲基)丙烯酸烷基酯單體，對被黏物污染少，且不經時劣化的具有優異抗剝離靜電性能的黏著劑組合物、及抗靜電表面保護膜。 The present invention is characterized by solving the technical problem of providing an acrylic polymer contained in an adhesive composition that does not include a nitrogen-containing vinyl monomer that does not contain a hydroxyl group and a (meth) acrylic acid alkyl group that contains an alkoxy group. Based on an ester monomer, an adhesive composition having excellent anti-peeling electrostatic properties and less anti-adhesion properties due to less contamination to adherends, and an antistatic surface protective film.

作為任意的添加劑成分，在本發明的黏著劑組合物中，可適當添加界面活性劑、硬化促進劑、可塑劑、填充劑、硬化延遲劑、加工助劑、抗老化劑、抗氧化劑等習知的添加劑。這些添加劑可單獨使用，也可兩種以上合併使用。 As an arbitrary additive component, conventionally, a surfactant, a hardening accelerator, a plasticizer, a filler, a hardening delaying agent, a processing aid, an anti-aging agent, an antioxidant and the like can be appropriately added to the adhesive composition of the present invention. Additives. These additives may be used alone or in combination of two or more.

將前述黏著劑組合物進行交聯而成的黏著劑層，在低速的剝離速度0.3m/min下的黏著力以0.05~0.1N/25mm，在高速的剝離速度30m/min下的黏著力佳為1.0N/25mm以下為佳。藉此，能夠得到黏著力受剝離速度影響的變化少的性能，即使高速剝離，也能夠快速地剝離。此外，為了重新黏貼，即使暫時剝離抗靜電表面保護膜時也不需要過大的力，容易地從被黏物上剝離。 The adhesive layer obtained by cross-linking the aforementioned adhesive composition has a low-speed peeling speed of 0.3 m / min and an adhesive force of 0.05 to 0.1 N / 25 mm, and a high-speed peeling speed of 30 m / min. It is preferably 1.0N / 25mm or less. Thereby, it is possible to obtain performance with little change in the adhesive force that is affected by the peeling speed, and it is possible to peel off quickly even at high speed peeling. In addition, for re-adhesion, even if the antistatic surface protective film is temporarily peeled off, an excessive force is not required, and it is easily peeled from the adherend.

將本發明的黏著劑組合物進行交聯而成的黏著劑層(交聯後的黏著劑)的凝膠分率以95~100%為佳。像這樣藉由將凝膠分率設置得高，在低速的剝離速度中黏著力不會成為過大，能夠降低未聚合單體或低聚物從前述丙烯酸系聚合物中溶出，改善污染性和高溫、高濕度下的耐久性，抑制被黏物的污染。 The gel fraction of the adhesive layer (crosslinked adhesive) obtained by crosslinking the adhesive composition of the present invention is preferably 95 to 100%. By setting the gel fraction so high, the adhesive force does not become too large at a low speed peeling speed, which can reduce the dissolution of unpolymerized monomers or oligomers from the acrylic polymer, and improve contamination and high temperature. 、 Durability under high humidity, inhibit pollution by sticky matter.

本發明的抗靜電表面保護膜係由在樹脂膜的一個面或兩面上形成使黏著劑組合物交聯而成的黏著劑層而形 成。由於本發明的抗靜電表面保護膜係由平衡良好地添加上述(A)~(H)的各成分的黏著劑組合物交聯的黏著劑層所形成，因此具有優異抗靜電性能，在低速的剝離速度、及高速的剝離速度中黏著力的平衡優異，進一步耐久性及污染性也優異。因此，能夠適用於偏光板的表面保護膜的用途，產業上的利用價值高。 The antistatic surface protection film of the present invention is formed by forming an adhesive layer formed by cross-linking an adhesive composition on one or both sides of a resin film. to make. Since the antistatic surface protective film of the present invention is formed of an adhesive layer crosslinked with the adhesive composition in which the components (A) to (H) are added in a well-balanced manner, it has excellent antistatic properties, The peeling speed and the high-speed peeling speed are excellent in the balance of adhesive force, and further excellent in durability and stain resistance. Therefore, it can apply to the use of the surface protection film of a polarizing plate, and it has high industrial use value.

作為被黏物的偏光板，可列舉出實施使反射率為2%以下的低反射表面處理的偏光板(LR偏光板)、實施使反射率為2%以下的低反射表面處理且實施防眩處理的偏光板(AG-LR偏光板)。 Examples of a polarizing plate to be adhered include a polarizing plate (LR polarizing plate) that has a low-reflective surface treatment with a reflectance of 2% or less, a low-reflective surface treatment that has a reflectance of 2% or less, and an anti-glare Processed polarizer (AG-LR polarizer).

使前述黏著劑組合物交聯而成的黏著劑層的表面電阻率以9.0×1011Ω/□以下為佳。此外，將前述抗靜電表面保護膜經由前述黏著劑層貼合於前述偏光板後，在剝離時的剝離靜電電壓以「±0.8kV以下」為佳。此外，在本發明中，「±0.8kV以下」是指0~-0.8kV及0~+0.8kV，即-0.8~+0.8kV之含意。若表面電阻率大，則在將抗靜電表面保護膜從被黏物上剝離時，釋放因帶電而產生的靜電的性能差。因此，藉由使表面電阻率充分地小，能夠降低伴隨被黏物剝離黏著劑層時產生的靜電而產生的剝離靜電電壓，抑制對被黏物的電控制電路等的影響。 The surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is preferably 9.0 × 10 11 Ω / □ or less. In addition, after the antistatic surface protective film is bonded to the polarizing plate through the adhesive layer, the peeling electrostatic voltage at the time of peeling is preferably “± 0.8 kV or less”. In addition, in the present invention, "below ± 0.8kV" means 0 to -0.8kV and 0 to + 0.8kV, that is, -0.8 to + 0.8kV. If the surface resistivity is large, when the antistatic surface protective film is peeled from the adherend, the performance of releasing static electricity generated by charging is poor. Therefore, by sufficiently reducing the surface resistivity, it is possible to reduce the peeling electrostatic voltage caused by the static electricity generated when the adherend is peeled from the adhesive layer, and to suppress the influence on the electrical control circuit and the like of the adherend.

作為黏著劑層的基材膜和保護黏著面的剝離膜(間隔物(separator))，可使用聚酯膜等樹脂膜等。 As the base film of the adhesive layer and the release film (separator) for protecting the adhesive surface, a resin film such as a polyester film can be used.

在基材膜中，在樹脂膜的形成有黏著劑層一側的相反面上，能夠實施基於聚矽氧(silicone)系、氟系的脫模劑或塗布劑、二氧化矽微粒子等的防汙處理，基於抗靜電劑的塗布或 摻混等的抗靜電處理。 In the base film, on the side opposite to the side where the adhesive layer is formed of the resin film, it is possible to implement a silicone-based, fluorine-based release agent or coating agent, and silicon dioxide fine particles. Stain treatment, coating based on antistatic agent or Antistatic treatment by blending etc.

在剝離膜的與黏著劑層的黏著面相貼合的一側的面上，藉由聚矽氧系、氟系的脫模劑等實施脫模處理。 The release film is subjected to a release treatment with a silicone-based, fluorine-based release agent, or the like on the side of the release film that is in contact with the adhesive surface of the adhesive layer.

[實施例] [Example]

以下藉由實施例對本發明進行進一步說明。 The present invention is further described below by using examples.

<黏著劑組合物的製備> <Preparation of Adhesive Composition>

[實施例1] [Example 1]

向具備攪拌器、溫度計、回流冷卻器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換反應裝置內的空氣。然後，向反應裝置中加入15重量份丙烯酸甲酯、85重量份丙烯酸2-乙基己酯、10.0重量份丙烯酸8-羥基辛酯、0.1重量份丙烯酸、10重量份聚丙二醇單丙烯酸酯(n=12)，同時加入60重量份溶劑(乙酸乙酯)。然後，花費2小時滴入0.1重量份作為聚合起始劑的偶氮二異丁腈，在65℃、反應6小時，得到重量平均分子量為50萬的、用於實施例1的丙烯酸系聚合物溶液。對上述丙烯酸系聚合物溶液加入9.0重量份乙醯丙酮並攪拌後，加入2.0重量份CORONATE HX(六亞甲基二異氰酸酯化合物的異氰脲酸酯體)、0.1重量份三乙醯丙酮鈦、1.0重量份1-壬基吡啶鎓六氟磷酸鹽、0.1重量份聚醚改性矽氧烷化合物(HLB=7)，進行攪拌混合，得到實施例1的黏著劑組合物。 Nitrogen was introduced into a reaction device including a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube, and the air in the reaction device was replaced with nitrogen. Then, 15 parts by weight of methyl acrylate, 85 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 parts by weight of acrylic acid, and 10 parts by weight of polypropylene glycol monoacrylate (n = 12), while adding 60 parts by weight of a solvent (ethyl acetate). Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the reaction was performed at 65 ° C. for 6 hours to obtain an acrylic polymer having a weight average molecular weight of 500,000 and used in Example 1. Solution. After adding 9.0 parts by weight of acetoacetone to the acrylic polymer solution and stirring, 2.0 parts by weight of CORONATE HX (isocyanurate body of hexamethylene diisocyanate compound), 0.1 parts by weight of titanium triacetamone acetone, 1.0 part by weight of 1-nonylpyridinium hexafluorophosphate and 0.1 part by weight of a polyether-modified silicone compound (HLB = 7) were stirred and mixed to obtain the adhesive composition of Example 1.

[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]

除了使實施例1的黏著劑組合物的組成，分別成為表1及表2前述以外，以與實施例1相同的方式，得到實施例2~6及比較例1~3的黏著劑組合物。 The adhesive compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that the composition of the adhesive composition of Example 1 was as described in Tables 1 and 2, respectively.

在表1及表2中，將(a1)組與(a2)組的總量作為100重量份而求得的重量份的數值均在括弧中表示。此外，在表1及表2中使用的各成分的簡略符號的化合物名稱表示於表3及表4。此外，CORONATE(註冊商標)HX、CORONATE HL及CORONATE L均為TOSOH CORPORATION的商品號，Takenate(註冊商標)D-140N、D-127N、D-110N為三井化學股份有限公司的商品名。 In Tables 1 and 2, the numerical values of parts by weight obtained by taking the total amount of the (a1) group and the (a2) group as 100 parts by weight are shown in parentheses. In addition, the compound names of abbreviated symbols of each component used in Tables 1 and 2 are shown in Tables 3 and 4. In addition, CORONATE (registered trademark) HX, CORONATE HL, and CORONATE L are trade names of TOSOH CORPORATION, and Takenate (registered trademark) D-140N, D-127N, D-110N are trade names of Mitsui Chemicals Co., Ltd.

對於表3的(D)組，「n」的數值為構成聚伸烷基二醇鏈的伸烷基氧的平均重複數。實施例1~6中使用的(D)聚伸烷基二醇單(甲基)丙烯酸酯單體(D-1~D-5)中，構成聚伸烷基二醇鏈的伸烷基氧的平均重複數為3~14，單體中的二酯成分為0.2%以下。 For the group (D) in Table 3, the value of "n" is the average number of repeats of the alkylene oxide constituting the polyalkylene glycol chain. Among the (D) polyalkylene glycol mono (meth) acrylate monomers (D-1 to D-5) used in Examples 1 to 6, the alkylene oxide constituting the polyalkylene glycol chain The average number of repeats is 3 to 14, and the diester component in the monomer is 0.2% or less.

<雙官能異氰酸酯化合物的合成> <Synthesis of Bifunctional Isocyanate Compound>

合成例1、2的雙官能異氰酸酯化合物藉由下述方法合成。如表5及表6所示，將二異氰酸酯與二醇化合物以莫耳比：NCO/OH=16的比例混合，在120℃進行3小時反應，然後使用薄膜蒸發裝置在減壓下除去未反應的二異氰酸酯，得到目標的雙官能異氰酸酯化合物。 The bifunctional isocyanate compounds of Synthesis Examples 1 and 2 were synthesized by the following method. As shown in Tables 5 and 6, the diisocyanate and the diol compound were mixed at a molar ratio of NCO / OH = 16, and the reaction was performed at 120 ° C for 3 hours, and then the unreacted reaction was removed under reduced pressure using a thin film evaporation device. Diisocyanate to give the desired difunctional isocyanate compound.

<抗靜電表面保護膜的製備> <Preparation of Antistatic Surface Protective Film>

[實施例1] [Example 1]

將如上前述製備的實施例1的黏著劑組合物塗布在由經聚矽氧樹脂塗布的聚對苯二甲酸乙二酯(PET)膜構成的剝離膜上之後，藉由在90℃進行乾燥，除去溶劑，得到黏著劑層厚度為25μm的黏著片。之後，在一個面上將經過抗靜電及防汙處理的聚對苯二甲酸乙二酯(PET)膜的與經過抗靜電及防汙處理的面的相反面上，轉印黏著片，得到具有「經過抗靜電及防汙處理的PET膜/黏著劑層/剝離膜(經有機矽樹脂塗布的PET膜)」的層積結構的實施例1的抗靜電表面保護膜。 The adhesive composition of Example 1 prepared as described above was coated on a release film composed of a silicone resin-coated polyethylene terephthalate (PET) film, and then dried at 90 ° C. The solvent was removed to obtain an adhesive sheet having an adhesive layer thickness of 25 μm. Then, an adhesive sheet was transferred on one side of the antistatic and antifouling-treated polyethylene terephthalate (PET) film on the side opposite to the antistatic and antifouling surface to obtain The antistatic surface protective film of Example 1 with the laminated structure of "PET film / adhesive layer / peel film (organic silicone resin-coated PET film) subjected to antistatic and antifouling treatment".

[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]

以與上述的實施例1的抗靜電表面保護膜相同的方式，得到實施例2~6及比較例1~3的抗靜電表面保護膜。 In the same manner as the antistatic surface protective film of Example 1 described above, the antistatic surface protective films of Examples 2 to 6 and Comparative Examples 1 to 3 were obtained.

<試驗方法及評價> <Test method and evaluation>

將實施例1~6及比較例1~3中的抗靜電表面保護膜在23℃、50%RH的氣氛下熟化7天後，剝離剝離膜(經聚矽氧樹脂塗布的PET膜)，將露出黏著劑層的抗靜電表面保護膜作為表面電阻率的測定樣品。 After the antistatic surface protective films in Examples 1 to 6 and Comparative Examples 1 to 3 were aged in an atmosphere of 23 ° C and 50% RH for 7 days, the release film (polysiloxane-coated PET film) was peeled, and The antistatic surface protective film with the adhesive layer exposed was used as a sample for measuring surface resistivity.

進一步，將此露出黏著劑層的抗靜電表面保護膜經由黏著劑層貼合在偏光板的表面，放置1天後，以50℃、5個大氣壓、20分鐘進行高壓釜處理，在室溫下進一步放置12小時，作為黏著力、剝離靜電電壓、及污染性的測定樣品。被黏物的偏光板為LR偏光板或AG-LR偏光板。 Furthermore, the antistatic surface protective film with the adhesive layer exposed was bonded to the surface of the polarizing plate via the adhesive layer, and after being left for 1 day, the autoclave treatment was performed at 50 ° C, 5 atmospheres, and 20 minutes, and at room temperature It was further left for 12 hours, and it was set as the measurement sample of adhesive force, peeling electrostatic voltage, and contamination. The adhered polarizer is an LR polarizer or an AG-LR polarizer.

<黏著力> <Adhesion>

用拉伸試驗機將上述得到的測定樣品(將25mm寬的抗靜電表面保護膜貼合於實施有LR處理或AG-LR處理的偏光板的表面的測定樣品)在180°方向上，在低速的剝離速度(0.3m/min)及高速的剝離速度(30m/min)下剝離，將測定的剝離強度作為黏著力(N/25mm)。 Using a tensile tester, the measurement sample obtained above (a measurement sample in which a 25 mm wide antistatic surface protective film was bonded to the surface of a polarizing plate subjected to LR treatment or AG-LR treatment) was rotated at a low speed in a direction of 180 °. The peeling was performed at a high peeling speed (0.3 m / min) and a high-speed peeling speed (30 m / min), and the measured peeling strength was used as the adhesive force (N / 25 mm).

<表面電阻率> <Surface resistivity>

在熟化後，貼合於偏光板前，剝離剝離膜(經聚矽氧樹脂塗布的PET膜)，露出黏著劑層，使用電阻率計Hiresta UP-HT450(Mitsubishi Chemical Analytech Co.,Ltd.製造)測定黏著劑層的表面電阻率(Ω/□)。 After curing, before bonding to the polarizing plate, the release film (polysiloxane-coated PET film) was peeled off to expose the adhesive layer, and measured using a resistivity meter Hiresta UP-HT450 (Mitsubishi Chemical Analytech Co., Ltd.) Surface resistivity of the adhesive layer (Ω / □).

<剝離靜電電壓> <Peel electrostatic voltage>

將上述獲得的測定樣品以30m/min的拉伸速度進行180°剝離時，使用高精度靜電感測器SK-035、SK-200(KEYENCE CORPORATION製造)，對實施有LR處理或AG-LR處理的偏光板帶電所產生的電壓(靜電電壓)，進行測定，將測定值的最大值作為剝離靜電電壓(kV)。 When the measurement sample obtained above was peeled 180 ° at a tensile speed of 30 m / min, a high-precision electrostatic sensor SK-035, SK-200 (manufactured by Keyence Corporation) was used, and the LR process or the AG-LR process was performed. The voltage (static voltage) generated by the charging of the polarizing plate was measured, and the maximum value of the measured value was taken as the peeling electrostatic voltage (kV).

<污染性> <Pollution>

使用貼合機，在玻璃板的一個面上，經由兩面黏著膠帶等黏著劑層貼合偏光板。之後，在實施有LR處理或AG-LR處理的偏光板的表面上，使用貼合機貼合抗靜電表面保護膜的黏著劑層。在23℃、50%RH的環境下經過3天及30天期間的保存後，剝離抗靜電表面保護膜，以目視觀察偏光板的表面的污染狀態。 Using a bonding machine, the polarizing plate is bonded to one surface of the glass plate through an adhesive layer such as an adhesive tape on both sides. After that, the adhesive layer of the antistatic surface protective film was bonded to the surface of the polarizing plate subjected to the LR process or the AG-LR process using a bonding machine. After storage at 23 ° C and 50% RH for 3 days and 30 days, the antistatic surface protective film was peeled off, and the state of contamination on the surface of the polarizing plate was visually observed.

對於表面污染性，將對於偏光板的表面在3天保存及30天保存中均無污染的情況評價為「○」，3天保存及30天保存的任一中有少許污染的情況評價為「△」，有污染的情況評價為「×」。 Regarding the surface contamination, the case where the surface of the polarizing plate was not contaminated during storage for 3 days and 30 days was evaluated as "○", and the case where there was slight contamination for either of 3 days or 30 days was evaluated as "" △ ", the case where there is pollution is evaluated as" × ".

評價結果如表7所示。此外，表面電阻率藉由將「m×10+n」以「mE+n」的方式標記(其中，m為任意的實數值，n為正整數)。 The evaluation results are shown in Table 7. In addition, the surface resistivity is marked by “m × 10 + n ” as “mE + n” (where m is an arbitrary real value and n is a positive integer).

實施例1~6的抗靜電表面保護膜對於實施有LR處理或AG-LR處理的偏光板的被黏物，在低速的剝離速度0.3m/min下的黏著力為0.05~0.1N/25mm，高速的剝離速度30m/min下的黏著力為1.0N/25mm以下，表面電阻率為9.0×10+11Ω/□以下，剝離靜電電壓為±0~0.8kV，3天保存及30天保存的污染性優異。 The antistatic surface protective film of Examples 1 to 6 has an adhesive force of 0.05 to 0.1 N / 25 mm at a low-speed peeling speed of 0.3 m / min for the adherend of the polarizing plate subjected to LR treatment or AG-LR treatment. High-speed peeling speed: Adhesion at 30m / min is 1.0N / 25mm or less, surface resistivity is 9.0 × 10 +11 Ω / □ or less, peeling electrostatic voltage is ± 0 ~ 0.8kV, 3 days storage and 30 days storage Excellent pollution.

此外，關於丙烯酸系聚合物中不含有(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體的比較例1的抗靜電表面保護膜，其剝離靜電電壓高，污染性稍差。 In addition, the antistatic surface protective film of Comparative Example 1 of the (meth) acrylic acid ester monomer of C1 to C4 which does not contain (a1) alkyl in the acrylic polymer, has a high peeling electrostatic voltage and contamination. Slightly worse.

此外，關於相對於(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的總量100重量份，丙烯酸系聚合物以80重量份的比例含有(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體，含有超過20重量份的(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體的比較例2的抗靜電表面保護膜，其黏著力過大，表面電阻率高，剝離靜電電壓高，且污染性差。 In addition, the acrylic polymer contains (a1) an alkyl group in a proportion of 80 parts by weight with respect to 100 parts by weight of the total number of (meth) acrylic acid ester monomers having C1 to C18 carbon atoms with respect to the (A) alkyl group. Comparative Example 2 of a (meth) acrylic acid ester monomer having C1 to C4 and a (meth) acrylic acid ester monomer having C5 to C18 having more than 20 parts by weight of an (a2) alkyl group Anti-static surface protective film, its adhesive force is too large, the surface resistivity is high, the peeling electrostatic voltage is high, and the pollution is poor.

此外，關於丙烯酸系聚合物中不含有(D)聚伸烷基二醇單(甲基)丙烯酸酯單體的比較例3的抗靜電表面保護膜，其表面電阻率高，剝離靜電電壓高，且污染性差。 In addition, regarding the antistatic surface protective film of Comparative Example 3 in which the acrylic polymer did not contain (D) polyalkylene glycol mono (meth) acrylate monomer, the surface resistivity was high and the peeling electrostatic voltage was high. And poor pollution.

由此，比較例1~3的抗靜電表面保護膜無法兼顧對被黏物的污染的抑制與優異的抗剝離靜電性能。 Therefore, the antistatic surface protective films of Comparative Examples 1 to 3 were unable to achieve both the suppression of contamination of the adherend and the excellent anti-peeling electrostatic performance.

Claims (14)

一種黏著劑組合物，係含有丙烯酸系聚合物、抗靜電劑、交聯劑之黏著劑組合物，其特徵在於，前述丙烯酸系聚合物為藉由不包含不含羥基的含氮乙烯單體及含烷氧基的(甲基)丙烯酸烷基酯單體，而使下述物質進行共聚而成的共聚物：相對於前述丙烯酸系聚合物的100重量份，總量為50~99.8重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體、作為可共聚單體組的、0.1~14重量份(B)含有羥基的可共聚單體中的至少一種以上、0.01~1.0重量份(C)含有羧基的可共聚單體中的至少一種以上、超過0且為35重量份以下的(D)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上，前述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體由(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種以上、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種以上構成，前述(a1)與前述(a2)的含有比例(a2/a1)以質量比為超過1且為50以下，前述抗靜電劑為(H)熔點為25~50℃的在溫度25℃時為固體的離子化合物， 前述交聯劑為(E)雙官能以上的異氰酸酯化合物，前述黏著劑組合物進一步含有(F)交聯促進劑、(G)酮-烯醇互變異構體化合物。 An adhesive composition is an adhesive composition containing an acrylic polymer, an antistatic agent, and a cross-linking agent. The acrylic polymer is characterized in that the acrylic polymer does not contain a hydroxyl-containing vinyl monomer and A copolymer obtained by copolymerizing an alkoxy group-containing (meth) acrylic acid alkyl ester monomer with the following content: 50 to 99.8 parts by weight relative to 100 parts by weight of the acrylic polymer. (A) At least one of a (meth) acrylic acid ester monomer having a C1 to C18 alkyl group, and a copolymerizable monomer group of 0.1 to 14 parts by weight (B) a copolymerizable monomer containing a hydroxyl group (D) Polyalkylene glycol mono (meth) acrylate monomer of at least one or more, 0.01 to 1.0 part by weight (C) of a copolymerizable monomer containing a carboxyl group, more than 0 and 35 parts by weight or less At least one of the above (A) alkyl (meth) acrylate monomers having a carbon number of C1 to C18 ((1)) (meth) acrylic acid esters having an alkyl group having a carbon number of C1 to C4 At least one or more of the monomers and at least one or more of the (a2) alkyl (meth) acrylate monomers having a carbon number of C5 to C18 The content ratio (a2 / a1) of the (a1) and the (a2) is in a mass ratio of more than 1 and less than 50, and the antistatic agent (H) has a melting point of 25 to 50 ° C at a temperature of 25 ° C. Solid ionic compounds, The crosslinking agent is (E) a difunctional or higher isocyanate compound, and the adhesive composition further contains (F) a crosslinking accelerator and (G) a keto-enol tautomer compound. 如申請專利範圍第1項所述的黏著劑組合物，其中，前述(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，其構成聚伸烷基二醇鏈的伸烷基氧的平均重複數為3~14，單體中的二酯成分為0.2%以下。 The adhesive composition according to item 1 of the scope of patent application, wherein the (D) polyalkylene glycol mono (meth) acrylate monomer comprises an alkylene group of a polyalkylene glycol chain. The average repeat number of oxygen is 3 to 14, and the diester component in the monomer is 0.2% or less. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，前述(F)交聯促進劑為選自由鋁螯合物、鈦螯合物、鐵螯合物組成的群組中的至少一種以上，相對於前述丙烯酸系聚合物100重量份，以0.001~0.5重量份的比例含有前述(F)交聯促進劑、以0.1~300重量份的比例含有前述(G)酮-烯醇互變異構體化合物，前述(G)/前述(F)的重量份比例為70~1000。 The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the (F) crosslinking accelerator is selected from the group consisting of an aluminum chelate, a titanium chelate, and an iron chelate. At least one or more kinds, containing the (F) crosslinking accelerator in an amount of 0.001 to 0.5 parts by weight, and the (G) keto-enol in an amount of 0.1 to 300 parts by weight based on 100 parts by weight of the acrylic polymer. The tautomeric compound has a weight ratio of (G) / (F) of 70 to 1,000. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，前述(B)含有羥基的可共聚單體為選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺組成的化合物群組中的至少一種以上，前述(C)含有羧基的可共聚單體為選自由(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二 甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸組成的化合物群組中的至少一種以上。 The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the (B) hydroxyl-containing copolymerizable monomer is selected from the group consisting of (meth) acrylic acid 8-hydroxyoctyl ester and (meth) acrylic acid 6 -Hydroxyhexyl ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide At least one or more compounds from the group consisting of N-hydroxyethyl (meth) acrylamide, and the (C) carboxyl-containing copolymerizable monomer is selected from (meth) acrylic acid and (meth) acrylic acid carboxyl groups Ethyl ester, carboxypentyl (meth) acrylate, 2- (meth) acryloxyethylhexahydrophthalic acid, 2- (meth) acryloxypropylhexahydrophthalic acid, 2- (meth) acryloxyethyl phthalate Formic acid, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2- (formyl) Group) at least one or more of the compound group consisting of acryloxyethyl tetrahydrophthalic acid. 如申請專利範圍第2項所述的黏著劑組合物，其中，作為前述可共聚單體組的前述構成聚伸烷基二醇鏈的伸烷基氧的平均重複數為3~14、單體中的二酯成分為0.2%以下的前述(D)聚伸烷基二醇單(甲基)丙烯酸酯單體，含有選自聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯中的至少一種以上。 The adhesive composition according to item 2 of the scope of patent application, wherein the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain as the copolymerizable monomer group is 3 to 14, and the monomer The above (D) polyalkylene glycol mono (meth) acrylate monomer in which the diester component is 0.2% or less, and is selected from the group consisting of polyalkylene glycol mono (meth) acrylate and methoxy At least one of polyalkylene glycol (meth) acrylate and ethoxy polyalkylene glycol (meth) acrylate. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，相對於100重量份前述丙烯酸系聚合物，以0.1~10重量份的比例含有前述(E)雙官能以上的異氰酸酯化合物，前述(E)雙官能以上的異氰酸酯化合物中，作為雙官能異氰酸酯化合物為非環式脂肪族異氰酸酯化合物，為使二異氰酸酯化合物與二醇化合物反應生成的化合物，由作為二異氰酸酯化合物的脂肪族二異氰酸酯、即選自由四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯組成的化合物群組中的一種，與作為二醇化合物的選自由2-甲基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、3-甲基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇單羥基新戊酸酯、聚乙二 醇、聚丙二醇組成的化合物群組中的一種形成；作為三官能異氰酸酯化合物，含有六亞甲基二異氰酸酯化合物的異氰脲酸酯體、異佛爾酮二異氰酸酯化合物的異氰脲酸酯體、六亞甲基二異氰酸酯化合物的加成體、異佛爾酮二異氰酸酯化合物的加成體、六亞甲基二異氰酸酯化合物的縮二脲體、異佛爾酮二異氰酸酯化合物的縮二脲體、甲苯二異氰酸酯化合物的異氰脲酸酯體、二甲苯撐基二異氰酸酯化合物的異氰脲酸酯體、氫化二甲苯撐基二異氰酸酯化合物的異氰脲酸酯體、甲苯二異氰酸酯化合物的加成體、二甲苯撐基二異氰酸酯化合物的加成體、氫化二甲苯撐基二異氰酸酯化合物的加成體。 The adhesive composition according to item 1 or 2 of the scope of application for a patent, wherein the adhesive composition contains 0.1 to 10 parts by weight of the isocyanate compound having the above (E) difunctionality with respect to 100 parts by weight of the acrylic polymer, Among the above-mentioned (E) difunctional or higher isocyanate compounds, the difunctional isocyanate compound is an acyclic aliphatic isocyanate compound, and the compound formed by reacting a diisocyanate compound with a diol compound is an aliphatic diisocyanate that is a diisocyanate compound. Namely, one selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and The diol compound is selected from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2- Ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol monohydroxypivalate, polyethylene glycol One of a group of compounds consisting of alcohol and polypropylene glycol; as a trifunctional isocyanate compound, an isocyanurate body containing a hexamethylene diisocyanate compound and an isocyanurate body of an isophorone diisocyanate compound , Adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, biuret body of hexamethylene diisocyanate compound, biuret body of isophorone diisocyanate compound , Isocyanurate body of toluene diisocyanate compound, isocyanurate body of xylylene diisocyanate compound, isocyanurate body of hydrogenated xylylene diisocyanate compound, addition of toluene diisocyanate compound Adults, adducts of xylylene diisocyanate compounds, and adducts of hydrogenated xylylene diisocyanate compounds. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，相對於100重量份前述丙烯酸系聚合物，以0.01~1.0重量份的比例進一步含有(I)HLB值為7~15的聚醚改性矽氧烷化合物。 The adhesive composition according to item 1 or 2 of the scope of patent application, further comprising (I) an HLB value of 7 to 15 with respect to 100 parts by weight of the acrylic polymer at a ratio of 0.01 to 1.0 part by weight. Polyether modified siloxane compound. 一種抗靜電表面保護膜，其特徵在於，在樹脂膜的一個面上層積有如申請專利範圍第1至7項中任一項所述的黏著劑組合物進行交聯的黏著劑層。 An antistatic surface protection film, characterized in that an adhesive layer according to any one of claims 1 to 7 of the scope of patent application is laminated on one surface of a resin film to be crosslinked. 一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將如申請專利範圍第8項所述的抗靜電表面保護膜貼合於實施使反射率為2%以下的低反射表面處理的偏光板後，剝離時的污染性良好。 An antistatic surface protective film characterized in that the antistatic surface protective film described in item 8 of the scope of patent application is bonded to the low-reflective surface treatment with a reflectance of 2% or less through the adhesive layer. After the polarizing plate, the contamination at the time of peeling was good. 一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將申請專利範圍第8項所述的抗靜電表面保護膜貼合於實 施使反射率為2%以下的低反射表面處理的偏光板後，剝離時的剝離靜電電壓為±0.8kV以下，且前述黏著劑表面的表面電阻率為9.0×1011Ω/□以下。 An antistatic surface protective film characterized in that the antistatic surface protective film described in item 8 of the scope of patent application is bonded to polarized light with a low-reflective surface treatment having a reflectance of 2% or less through the adhesive layer. After the board, the peeling electrostatic voltage at the time of peeling was ± 0.8 kV or less, and the surface resistivity of the surface of the adhesive was 9.0 × 10 11 Ω / □ or less. 一種抗靜電表面保護膜，其特徵在於，經由前述黏著劑層，將如申請專利範圍第8項所述的抗靜電表面保護膜貼合於實施使反射率為2%以下的低反射表面處理、且實施防眩處理的偏光板後，剝離時的剝離靜電電壓為±0.8kV以下，且前述黏著劑表面的表面電阻率為9.0×1011Ω/□以下。 An antistatic surface protective film, characterized in that the antistatic surface protective film described in item 8 of the scope of patent application is bonded to the low-reflective surface treatment with a reflectance of 2% or less via the adhesive layer, In addition, after the polarizing plate subjected to the anti-glare treatment, the peeling electrostatic voltage at the time of peeling was ± 0.8 kV or less, and the surface resistivity of the surface of the adhesive was 9.0 × 10 11 Ω / □ or less. 一種黏著膜，其特徵在於，在樹脂膜的一個面或兩面形成由如申請專利範圍第1~7項任一項所述的黏著劑組合物交聯而成的黏著劑層。 An adhesive film is characterized in that an adhesive layer formed by cross-linking the adhesive composition according to any one of claims 1 to 7 of a patent application range is formed on one or both sides of a resin film. 一種抗靜電表面保護膜，其由如申請專利範圍第8項所述的抗靜電表面保護膜構成，用於偏光板用保護膜的用途。 An antistatic surface protection film is composed of the antistatic surface protection film according to item 8 of the scope of application for patent, and is used for the use of a protective film for polarizing plates. 如申請專利範圍第8項所述的抗靜電表面保護膜，在前述樹脂膜的一個面，即與形成前述黏著劑層一側的相反面上，施加有抗靜電處理及防汙處理。 According to the antistatic surface protection film described in item 8 of the scope of patent application, an antistatic treatment and an antifouling treatment are applied to one surface of the resin film, that is, the surface opposite to the side on which the adhesive layer is formed.
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