TW202200741A - Adhesive composition for protective film of optical member and protective film of optical member - Google Patents

Adhesive composition for protective film of optical member and protective film of optical member Download PDF

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TW202200741A
TW202200741A TW110110286A TW110110286A TW202200741A TW 202200741 A TW202200741 A TW 202200741A TW 110110286 A TW110110286 A TW 110110286A TW 110110286 A TW110110286 A TW 110110286A TW 202200741 A TW202200741 A TW 202200741A
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meth
acrylic polymer
mass
specific
acrylic
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TW110110286A
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池元智拾
藤川春奈
鴨井彬
狩野肇
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日商日本電石工業股份有限公司
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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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double 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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2433/00—Presence of (meth)acrylic 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

An adhesive composition for a protective film of an optical member includes: a (meth)acrylic polymer (A) that has at least one of a hydroxyl group or a carboxy group, and that has a weight average molecular weight in a range of from more than 200,000 to 2,000,000 or less; a (meth)acrylic polymer (B) that has at least one of a hydroxyl group or a carboxy group, that has a glass transition temperature of from 0°C to 45°C, and that has a weight average molecular weight of from 6,000 to 150,000; a (meth)acrylic polymer (C) that has a glass transition temperature of 30°C or less, and that has a weight average molecular weight of from 6,000 to 150,000; and an isocyanate-based cross-linking agent (D), wherein a content of the (meth)acrylic polymer (B) is from 7 parts by mass to 70 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer (A), and a content of the (meth)acrylic polymer (C) is from 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer (A).

Description

光學構件保護薄膜用黏著劑組成物及光學構件保護薄膜Adhesive composition for optical member protective film and optical member protective film

本發明關於光學構件保護薄膜用黏著劑組成物及光學構件保護薄膜。The present invention relates to an adhesive composition for an optical member protective film and an optical member protective film.

為了保護各種物品的表面，廣泛使用具備黏著劑層之保護薄膜。尤其以偏光板為代表的各種光學構件大多使用保護薄膜。In order to protect the surface of various articles, a protective film with an adhesive layer is widely used. In particular, protective films are often used for various optical members including polarizing plates.

例如，日本特開2005-146151號公報中揭示一種表面保護片，係將使交聯性組成物以凝膠分率成為80%以上的方式進行交聯反應而成之感壓黏接劑塗覆於支持體上而得，該交聯性組成物含有：(A)至少由(甲基)丙烯酸烷基酯及含官能基之單體共聚而成之玻璃轉移溫度為-40℃以下的(甲基)丙烯酸系聚合物、(B)以(甲基)丙烯酸烷基酯作為主成分之玻璃轉移溫度80℃以上的(甲基)丙烯酸系聚合物、及(C)交聯劑，相對於上述(A)100重量份，係摻合5～20重量份之上述(B)。 又，日本特開2013-216769號公報中揭示一種表面保護片，係將由黏著劑組成物構成之黏著劑層形成於支持體之至少單面而成，該黏著劑組成物含有：玻璃轉移溫度未達0℃的聚合物(A)100質量份；重量平均分子量為1000以上且未達50000，玻璃轉移溫度為30～300℃的(甲基)丙烯酸系聚合物(B)0.05～3質量份；及特定之具有聚氧基伸烷基鏈之有機基聚矽氧烷化合物(C)。For example, Japanese Patent Laid-Open No. 2005-146151 discloses a surface protection sheet which is coated with a pressure-sensitive adhesive obtained by subjecting a crosslinkable composition to a crosslinking reaction so that the gel fraction becomes 80% or more. It is obtained on a support, and the cross-linkable composition contains: (A) at least a (meth)acrylic acid alkyl ester and a functional group-containing monomer copolymerized with a glass transition temperature below -40 ° C (methyl); base) an acrylic polymer, (B) a (meth)acrylic polymer having a glass transition temperature of 80°C or higher with an alkyl (meth)acrylate as the main component, and (C) a crosslinking agent, relative to the above (A) 100 parts by weight is a blend of 5 to 20 parts by weight of the above (B). In addition, Japanese Patent Laid-Open No. 2013-216769 discloses a surface protection sheet, which is formed by forming an adhesive layer composed of an adhesive composition on at least one side of a support, and the adhesive composition contains: a glass transition temperature 100 parts by mass of polymer (A) at 0°C; 0.05-3 parts by mass of (meth)acrylic polymer (B) having a weight-average molecular weight of 1,000 or more and less than 50,000, and a glass transition temperature of 30-300°C; and a specific organopolysiloxane compound (C) having a polyoxyalkylene chain.

[發明所欲解決之課題][The problem to be solved by the invention]

光學構件中使用之保護薄膜所使用的黏著劑組成物(以下，亦稱為「光學構件保護薄膜用黏著劑組成物」)，要求可形成一種黏著劑層，其係將保護薄膜貼附於光學構件之表面後，在需要保護的期間，不易發生從光學構件剝落、偏移等不良情況，且在不需要保護的階段，可有效地從光學構件剝離。 此處，不易發生從光學構件剝落、偏移等不良情況的黏著劑層，可利用將保護薄膜從光學構件以低速(亦即，0.3m/分鐘)剝離時測得之黏著力(所謂低速剝離力)來評價。又，可有效地從光學構件剝離的黏著劑層，可利用將保護薄膜從光學構件以高速(亦即，30m/分鐘)剝離時測得之黏著力(所謂高速剝離力)來評價。The adhesive composition used in the protective film used in optical members (hereinafter, also referred to as "adhesive composition for optical member protective film") is required to form an adhesive layer, which is used to attach the protective film to the optical member. After the surface of the member, in the period in which protection is required, it is less likely to cause problems such as peeling and displacement from the optical member, and in the stage where protection is not required, the optical member can be effectively peeled off. Here, for the adhesive layer, which is less prone to problems such as peeling and misalignment from the optical member, the adhesive force measured when the protective film is peeled off from the optical member at a low speed (that is, 0.3 m/min) (so-called low-speed peeling) can be used. force) to evaluate. In addition, the adhesive layer which can be effectively peeled from the optical member can be evaluated by the adhesive force (so-called high-speed peeling force) measured when the protective film is peeled off from the optical member at a high speed (ie, 30 m/min).

將保護薄膜從光學構件剝離時，會有產生無法平順地剝離而發出啪啦啪啦的聲響即被稱為拉鍊(zipping)之現象(以下，亦稱為「拉鍊現象」)的情況。產生拉鍊現象的話，於將保護薄膜剝離後之光學構件的表面有時會觀察到條痕狀的缺陷(所謂拉鍊線)。因此，對於光學構件保護薄膜用黏著劑組成物，要求可形成能抑制拉鍊現象之黏著劑層。尤其假定貼附有保護薄膜之光學構件會長期間保存，故光學構件保護薄膜用黏著劑組成物，即使長期間貼附於光學構件時，亦可形成能抑制拉鍊現象之黏著劑層較理想。When the protective film is peeled off from the optical member, a phenomenon called zipping (hereinafter, also referred to as "zipping phenomenon") may occur without smooth peeling and a rattling sound occurs. When a zipper phenomenon occurs, streak-like defects (so-called zipper lines) may be observed on the surface of the optical member after peeling the protective film. Therefore, in the adhesive composition for optical member protective films, the formation of the adhesive layer which can suppress a zipper phenomenon is requested|required. In particular, it is assumed that the optical member to which the protective film is attached will be stored for a long period of time, so the adhesive composition for the optical member protective film can form an adhesive layer capable of suppressing the zipper phenomenon even when it is attached to the optical member for a long period of time.

但是，欲控制保護薄膜所具備之黏著劑層的低速剝離力及高速剝離力的話，由於兩者會展現出同樣的行為，故難以調整低速剝離力與高速剝離力之平衡。尤其近年由於撓性顯示器的興起，將保護薄膜貼附於曲面的機會增加。將保護薄膜貼附於曲面的話，相較於貼附於平面的情況，容易發生從光學構件剝落、偏移等不良情況。因此，對於保護薄膜所具備之黏著劑層，有尋求較以往更高之低速剝離力的傾向，變得更難調整低速剝離力與高速剝離力之平衡。However, if the low-speed peeling force and the high-speed peeling force of the adhesive layer included in the protective film are to be controlled, since both exhibit the same behavior, it is difficult to adjust the balance between the low-speed peeling force and the high-speed peeling force. In particular, due to the rise of flexible displays in recent years, opportunities for attaching protective films to curved surfaces have increased. When the protective film is attached to a curved surface, inconveniences such as peeling and displacement from the optical member are more likely to occur than when the protective film is attached to a flat surface. Therefore, there is a tendency to seek a higher low-speed peeling force than conventional ones for the adhesive layer included in the protective film, and it becomes more difficult to adjust the balance between the low-speed peeling force and the high-speed peeling force.

又，近年考量進一步改善作業性的觀點，有使保護薄膜從光學構件剝離之剝離速度更高速化的傾向。此外，隨著光學構件的薄型化，有因保護薄膜剝離時之拉鍊現象導致光學構件的表面缺陷更容易產生的傾向。拉鍊現象據認為係由於黏著劑層之黏著力的強弱所導致。通常，黏著劑層之黏著力會展現出貼附於被黏體後隨時間經過而變高的傾向，故拉鍊現象在例如將保護薄膜於如6個月之長期間貼附於光學構件時容易發生。又，黏著劑層之黏著力展現出剝離速度越快黏著力越高的傾向，故將保護薄膜從光學構件以高速剝離時，亦容易發生拉鍊現象。 因此，難以實現可形成兼顧低速剝離力與高速剝離力之平衡良好、及長期間貼附於光學構件後從光學構件以高速剝離時仍不易發生拉鍊現象之黏著劑層的光學構件保護薄膜用黏著劑組成物。Moreover, considering the viewpoint of further improving workability|operativity in recent years, there exists a tendency for the peeling speed|rate of peeling a protective film from an optical member to become higher. Moreover, with the reduction in thickness of an optical member, there exists a tendency for the surface defect of an optical member to generate|occur|produce more easily by the zipper phenomenon at the time of peeling a protective film. The zipper phenomenon is considered to be caused by the strength of the adhesive force of the adhesive layer. Usually, the adhesive force of the adhesive layer shows a tendency to increase with time after being attached to the adherend, so the zipper phenomenon is easy to attach a protective film to an optical member for a period of 6 months, for example. occur. In addition, the adhesive force of the adhesive layer shows a tendency that the higher the peeling speed, the higher the adhesive force. Therefore, when the protective film is peeled off from the optical member at a high speed, a zipper phenomenon is likely to occur. Therefore, it is difficult to realize an adhesive for optical member protective films that can form an adhesive layer that has a good balance between low-speed peeling force and high-speed peeling force, and that is not easily peeled from the optical member at high speed after being attached to the optical member for a long time. agent composition.

關於上述方面，日本特開2005-146151號公報及日本特開2013-216769號公報中並未提及抑制長期間貼附於光學構件後從光學構件以高速剝離時之拉鍊現象。Regarding the above point, Japanese Patent Application Laid-Open No. 2005-146151 and Japanese Patent Application Laid-Open No. 2013-216769 do not mention the suppression of the zipper phenomenon when the optical member is adhered to the optical member at a high speed and then peeled off at a high speed.

本發明所欲解決之課題係提供一種光學構件保護薄膜用黏著劑組成物，其可形成低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層；並提供光學構件保護薄膜。 [解決課題之手段]The problem to be solved by the present invention is to provide an adhesive composition for an optical member protective film, which can form a good balance between the low-speed peeling force and the high-speed peeling force, and even if it is adhered to the adherend for a long time, it can be removed from the adherend. An adhesive layer that is not prone to zipper phenomenon during high-speed peeling; and provides a protective film for optical components. [Means of Solving Problems]

用以解決課題之具體手段包含下列態樣。 ＜1＞一種光學構件保護薄膜用黏著劑組成物，含有： (甲基)丙烯酸系聚合物(A)，具有羥基及羧基中之至少一者，且重量平均分子量超過20萬且在200萬以下之範圍； (甲基)丙烯酸系聚合物(B)，具有羥基及羧基中之至少一者，玻璃轉移溫度為0℃以上且45℃以下之範圍，且重量平均分子量為6000以上且15萬以下之範圍； (甲基)丙烯酸系聚合物(C)，玻璃轉移溫度為-30℃以下，且重量平均分子量為6000以上且15萬以下之範圍；及 異氰酸酯系交聯劑(D)； 上述(甲基)丙烯酸系聚合物(B)之含量，相對於上述(甲基)丙烯酸系聚合物(A)100質量份為7質量份以上且70質量份以下之範圍， 上述(甲基)丙烯酸系聚合物(C)之含量，相對於上述(甲基)丙烯酸系聚合物(A)100質量份為0.5質量份以上且5質量份以下之範圍。 ＜2＞如＜1＞之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(A)具有羥基，且羥值為0.3mgKOH/g以上且40mgKOH/g以下之範圍。 ＜3＞如＜1＞或＜2＞之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(A)具有羧基，且酸價為0.7mgKOH/g以上且24mgKOH/g以下之範圍。 ＜4＞如＜1＞～＜3＞中任1項之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(B)具有羥基，且羥值為0.3mgKOH/g以上且40mgKOH/g以下之範圍。 ＜5＞如＜1＞～＜4＞中任1項之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(B)具有羧基，且酸價為0.7mgKOH/g以上且24mgKOH/g以下之範圍。 ＜6＞如＜1＞～＜5＞中任1項之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(C)之羥值為40mgKOH/g以下。 ＜7＞如＜1＞～＜6＞中任1項之光學構件保護薄膜用黏著劑組成物，其中，上述(甲基)丙烯酸系聚合物(C)之重量平均分子量比上述(甲基)丙烯酸系聚合物(B)之重量平均分子量小。 ＜8＞如＜1＞～＜7＞中任1項之光學構件保護薄膜用黏著劑組成物，含有抗靜電劑。 ＜9＞如＜1＞～＜8＞中任1項之光學構件保護薄膜用黏著劑組成物，含有聚醚改性聚矽氧化合物。 ＜10＞一種光學構件保護薄膜，具備： 基材；及 黏著劑層，係設置於前述基材上，且由如＜1＞～＜9＞中任1項之光學構件保護薄膜用黏著劑組成物形成。 [發明之效果]Specific means for solving the problem include the following aspects. <1> An adhesive composition for an optical member protective film, comprising: (Meth)acrylic polymer (A), having at least one of a hydroxyl group and a carboxyl group, and having a weight-average molecular weight in the range of more than 200,000 and less than 2,000,000; (Meth)acrylic polymer (B) having at least one of a hydroxyl group and a carboxyl group, a glass transition temperature in the range of 0°C or higher and 45°C or lower, and a weight average molecular weight in the range of 6,000 or more and 150,000 or less; (Meth)acrylic polymer (C), the glass transition temperature is -30°C or lower, and the weight average molecular weight is in the range of 6,000 or more and 150,000 or less; and Isocyanate based crosslinking agent (D); Content of the said (meth)acrylic-type polymer (B) is the range of 7 mass parts or more and 70 mass parts or less with respect to 100 mass parts of said (meth)acrylic-type polymers (A), Content of the said (meth)acrylic-type polymer (C) is the range of 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of said (meth)acrylic-type polymer (A). <2> The adhesive composition for an optical member protective film according to <1>, wherein the (meth)acrylic polymer (A) has a hydroxyl group and has a hydroxyl value of not less than 0.3 mgKOH/g and not more than 40 mgKOH/g Scope. <3> The adhesive composition for optical member protective films according to <1> or <2>, wherein the (meth)acrylic polymer (A) has a carboxyl group and has an acid value of 0.7 mgKOH/g or more and 24 mgKOH /g or less. <4> The adhesive composition for optical member protective films according to any one of <1> to <3>, wherein the (meth)acrylic polymer (B) has a hydroxyl group, and the hydroxyl value is 0.3 mgKOH/ The range of g or more and 40 mgKOH/g or less. <5> The adhesive composition for optical member protective films according to any one of <1> to <4>, wherein the (meth)acrylic polymer (B) has a carboxyl group and has an acid value of 0.7 mgKOH/ The range of g or more and 24 mgKOH/g or less. <6> The adhesive composition for optical member protective films according to any one of <1> to <5>, wherein the (meth)acrylic polymer (C) has a hydroxyl value of 40 mgKOH/g or less. <7> The adhesive composition for an optical member protective film according to any one of <1> to <6>, wherein the weight average molecular weight of the (meth)acrylic polymer (C) is higher than the (meth) The weight average molecular weight of the acrylic polymer (B) is small. <8> The adhesive composition for optical member protective films according to any one of <1> to <7>, which contains an antistatic agent. <9> The adhesive composition for optical member protective films according to any one of <1> to <8>, comprising a polyether-modified polysiloxane compound. <10> An optical member protection film, comprising: substrate; and The adhesive layer is provided on the aforementioned base material, and is formed from the adhesive composition for optical member protective films according to any one of <1> to <9>. [Effect of invention]

根據本發明，可提供一種光學構件保護薄膜用黏著劑組成物，能形成低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層；並可提供光學構件保護薄膜。According to the present invention, it is possible to provide an adhesive composition for an optical member protective film, which can form a good balance between the low-speed peeling force and the high-speed peeling force, and is peeled off from the adherend at a high speed even after being attached to the adherend for a long period of time. It is also an adhesive layer that is not prone to zipper phenomenon; and can provide a protective film for optical components.

以下，針對本發明之具體實施形態進行詳細說明。惟，本發明不受下列實施形態任何限定，在本發明之目的範圍內可加以適當變更而實施。Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the object of the present invention.

本說明書中，利用「～」表示之數值範圍，意指包含「～」之前後記載之數值分別作為最小值及最大值的範圍。 本說明書中階段性記載之數值範圍內，以某數值範圍記載之上限值或下限值亦可置換成另一階段性記載之數值範圍的上限值或下限值。又，本說明書中記載之數值範圍內，以某數值範圍記載之上限值或下限值也可置換成實施例所示之值。 本說明書中，2以上之較佳態樣的組合係更佳態樣。 本說明書中，就各成分的量而言，當存在多種該當於各成分之物質時，除非另有說明，否則意指多種物質之合計量。In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In the numerical range described in stages in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical value range described in another stage. In addition, within the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in an Example. In this specification, a combination of two or more preferred aspects is a more preferred aspect. In this specification, regarding the amount of each component, when a plurality of substances corresponding to each component are present, unless otherwise specified, the total amount of the plurality of substances is meant.

本說明書中，「(甲基)丙烯酸系聚合物」意指來自具有(甲基)丙烯醯基之單體的構成單元的含有率為全部構成單元[亦即，(甲基)丙烯酸系聚合物之全部構成單元]之50質量%以上的聚合物。 本說明書中，「(甲基)丙烯酸系單體」意指具有(甲基)丙烯醯基之單體。In this specification, the "(meth)acrylic polymer" means that the content rate of the structural unit derived from the monomer having a (meth)acryloyl group is all the structural units [that is, the (meth)acrylic polymer 50% by mass or more of the polymer of the total constituent units]. In this specification, "(meth)acrylic-type monomer" means the monomer which has a (meth)acryloyl group.

本說明書中，「(甲基)丙烯酸」係包含「丙烯酸」及「甲基丙烯酸」之兩者的用語，「(甲基)丙烯酸酯」係包含「丙烯酸酯」及「甲基丙烯酸酯」之兩者的用語，「(甲基)丙烯醯基」係包含「丙烯醯基」及「甲基丙烯醯基」之兩者的用語。In this specification, "(meth)acrylic acid" is a term that includes both "acrylic acid" and "methacrylic acid", and "(meth)acrylate" is a term that includes "acrylate" and "methacrylate". The terms of both, "(meth)acryloyl group" is a term including both "acryloyl group" and "methacryloyl group".

本說明書中，「n-」意指正，「i-」意指異，「s-」意指第二，「t-」意指第三。In this specification, "n-" means positive, "i-" means different, "s-" means second, and "t-" means third.

本說明書中，「黏著劑組成物」意指交聯反應結束前的液狀或糊劑狀物質。 本說明書中，「黏著劑層」意指由黏著劑組成物中之交聯反應結束後之物質構成的膜。In this specification, the "adhesive composition" means a liquid or paste-like substance before the completion of the crosslinking reaction. In this specification, the "adhesive layer" means a film composed of a substance after the cross-linking reaction in the adhesive composition is completed.

本說明書中，「被黏體」係指光學構件。In this specification, the "adhered body" refers to an optical member.

本說明書中，「低速剝離力」意指將黏著於被黏體之保護薄膜從被黏體沿保護薄膜之長邊方向以低速(亦即，0.3m/分鐘)進行180°剝離時測得的黏著力。此外，詳細的測定方法如後述實施例所示。 本說明書中，「適當的低速剝離力」意指不易發生從被黏體剝落、偏移等不良情況之程度之強度的黏著力。In this specification, "low-speed peeling force" means the value measured when the protective film adhered to the adherend is peeled from the adherend at 180° at a low speed (ie, 0.3 m/min) along the longitudinal direction of the protective film. Adhesion. In addition, the detailed measurement method is shown in the Example mentioned later. In this specification, "appropriate low-speed peeling force" means an adhesive force of such a strength that troubles such as peeling off from the adherend and misalignment are unlikely to occur.

本說明書中，「高速剝離力」意指將黏著於被黏體之保護薄膜從被黏體沿保護薄膜之長邊方向以高速(亦即，30m/分鐘)進行180°剝離時測得的黏著力。此外，詳細的測定方法如後述實施例所示。 本說明書中，「適當的高速剝離力」意指可從被黏體有效地剝離之程度之強度的黏著力。In this specification, "high-speed peeling force" means the adhesion measured when the protective film adhered to the adherend is peeled from the adherend at 180° at a high speed (ie, 30 m/min) along the longitudinal direction of the protective film. force. In addition, the detailed measurement method is shown in the Example mentioned later. In this specification, "appropriate high-speed peeling force" means the adhesive force of the intensity|strength which peels effectively from a to-be-adhered body.

本說明書中，「低速剝離力與高速剝離力之平衡良好的黏著劑層」，意指具有不易發生從被黏體剝落、偏移等不良情況，且可從被黏體有效地剝離之程度之強度之黏著力的黏著劑層。In this specification, "an adhesive layer with a good balance between low-speed peeling force and high-speed peeling force" means a layer that is less likely to be peeled off from the adherend, misaligned, etc., and can be effectively peeled from the adherend. Adhesive layer for strength of adhesion.

[光學構件保護薄膜用黏著劑組成物] 本發明之光學構件保護薄膜用黏著劑組成物(以下，亦簡稱為「黏著劑組成物」。)含有：(甲基)丙烯酸系聚合物(A)[以下，亦稱為「特定(甲基)丙烯酸系聚合物(A)」。]，具有羥基及羧基中之至少一者，且重量平均分子量超過20萬且在200萬以下之範圍；(甲基)丙烯酸系聚合物(B)[以下，亦稱為「特定(甲基)丙烯酸系聚合物(B)」。]，具有羥基及羧基中之至少一者，玻璃轉移溫度為0℃以上且45℃以下之範圍，且重量平均分子量為6000以上且15萬以下之範圍；(甲基)丙烯酸系聚合物(C)[以下，亦稱為「特定(甲基)丙烯酸系聚合物(C)」。]，玻璃轉移溫度為-30℃以下，且重量平均分子量為6000以上且15萬以下之範圍；及異氰酸酯系交聯劑(D)；上述(甲基)丙烯酸系聚合物(B)之含量，相對於上述(甲基)丙烯酸系聚合物(A)100質量份為7質量份以上且70質量份以下之範圍，上述(甲基)丙烯酸系聚合物(C)之含量，相對於上述(甲基)丙烯酸系聚合物(A)100質量份為0.5質量份以上且5質量份以下之範圍。 根據本發明之黏著劑組成物，可形成低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層。 本發明之黏著劑組成物可發揮如此之效果的理由尚不明，但據本案發明人等推測如下。惟，以下之推測並非對本發明之黏著劑組成物作限定性解釋，而係作為一例進行說明。[Adhesive composition for optical member protective films] The adhesive composition for optical member protective films of the present invention (hereinafter, also simply referred to as "adhesive composition") contains: (meth)acrylic polymer (A) [hereinafter, also referred to as "specific (methyl) ) acrylic polymer (A)". ], having at least one of hydroxyl group and carboxyl group, and the weight average molecular weight exceeds 200,000 and is in the range of 2,000,000 or less; (meth)acrylic polymer (B) [hereinafter, also referred to as "specific (methyl) Acrylic polymer (B)". ], having at least one of a hydroxyl group and a carboxyl group, a glass transition temperature in the range of 0°C or more and 45°C or less, and a weight average molecular weight in the range of 6,000 or more and 150,000 or less; (meth)acrylic polymer (C ) [hereinafter, also referred to as "specific (meth)acrylic polymer (C)". ], the glass transition temperature is below -30°C, and the weight average molecular weight is in the range of 6,000 or more and 150,000 or less; and the isocyanate-based crosslinking agent (D); the content of the above-mentioned (meth)acrylic polymer (B), With respect to the range of 7 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic polymer (A), the content of the (meth)acrylic polymer (C) is relative to the (meth)acrylic polymer (C) above. 100 mass parts of base) acrylic polymer (A) are the range of 0.5 mass part or more and 5 mass parts or less. According to the adhesive composition of the present invention, it is possible to form an adhesive with a good balance between low-speed peeling force and high-speed peeling force, and even if it is adhered to the adherend for a long time and then peeled off from the adherend at high speed, the zipper phenomenon is unlikely to occur. Floor. The reason why the adhesive composition of the present invention can exhibit such an effect is not clear, but the inventors of the present invention speculate as follows. However, the following speculation is not intended to limit the explanation of the adhesive composition of the present invention, but to illustrate it as an example.

本發明之黏著劑組成物含有：特定(甲基)丙烯酸系聚合物(A)，具有羥基及羧基中之至少一者，且重量平均分子量較高；特定(甲基)丙烯酸系聚合物(B)，具有羥基及羧基中之至少一者，玻璃轉移溫度較高，且重量平均分子量較低；特定(甲基)丙烯酸系聚合物(C)，玻璃轉移溫度較低，且重量平均分子量較低；及異氰酸酯系交聯劑(D)。又，特定(甲基)丙烯酸系聚合物(B)之含量，比特定(甲基)丙烯酸系聚合物(A)之含量少，特定(甲基)丙烯酸系聚合物(C)之含量比特定(甲基)丙烯酸系聚合物(B)之含量少。 據認為因為本發明之黏著劑組成物具有如上述之構成，故由本發明之黏著劑組成物形成之黏著劑層中，特定(甲基)丙烯酸系聚合物(B)會適度地集中在表面附近(所謂與被黏體之界面附近)，並藉由與異氰酸酯系交聯劑(D)反應而形成交聯結構。據認為由於特定(甲基)丙烯酸系聚合物(B)的玻璃轉移溫度較高，所形成之交聯結構較硬。因此，據認為黏著劑層之表面附近適度存在較硬的部分。又，據認為由本發明之黏著劑組成物形成之黏著劑層中，特定(甲基)丙烯酸系聚合物(C)會適度集中在表面附近(所謂與被黏體之界面附近)。據認為由於特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度較低，故於黏著劑層之表面附近適度存在較柔軟的部分。 據認為將如此之黏著劑層貼附於被黏體時，藉由於黏著劑層與被黏體之界面附近適度存在較硬的部分，黏著劑層對於被黏體之潤濕不會過度，黏著劑層展現適當的高速剝離力。因此，據推測若為本發明之黏著劑組成物，可形成低速剝離力與高速剝離力之平衡良好的黏著劑層。 另一方面，黏著劑層對於被黏體之潤濕不足的話，長期間貼附於被黏體後從被黏體以高速剝離時，容易發生拉鍊現象。針對此點，據認為由本發明之黏著劑組成物形成之黏著劑層，在其與被黏體之界面附近適度存在較柔軟的部分，故會適度地潤濕被黏體。因此，據認為因黏著劑層對於被黏體之潤濕不足所致之拉鍊現象受到抑制。因此，據推測若為本發明之黏著劑組成物，可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層。 亦即，由本發明之黏著劑組成物形成之黏著劑層中，特定(甲基)丙烯酸系聚合物(B)及特定(甲基)丙烯酸系聚合物(C)適度地集中在與被黏體之界面附近，並形成較硬的部分與較柔軟的部分，藉此適度地調整黏著劑層對於被黏體之潤濕。因此，據推測由本發明之黏著劑組成物形成之黏著劑層，其低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象。The adhesive composition of the present invention contains: a specific (meth)acrylic polymer (A), which has at least one of a hydroxyl group and a carboxyl group, and has a relatively high weight average molecular weight; a specific (meth)acrylic polymer (B) ), having at least one of hydroxyl group and carboxyl group, higher glass transition temperature and lower weight average molecular weight; specific (meth)acrylic polymer (C), lower glass transition temperature and lower weight average molecular weight ; and an isocyanate-based crosslinking agent (D). In addition, the content of the specific (meth)acrylic polymer (B) is smaller than the content of the specific (meth)acrylic polymer (A), and the content of the specific (meth)acrylic polymer (C) is smaller than that of the specific (meth)acrylic polymer (C) The content of the (meth)acrylic polymer (B) is small. Since the adhesive composition of the present invention has the above-mentioned constitution, it is considered that the specific (meth)acrylic polymer (B) is appropriately concentrated in the vicinity of the surface in the adhesive layer formed from the adhesive composition of the present invention. (so-called near the interface with the adherend), and by reacting with the isocyanate-based crosslinking agent (D), a crosslinked structure is formed. It is considered that since the glass transition temperature of the specific (meth)acrylic polymer (B) is high, the formed cross-linked structure is hard. Therefore, it is considered that a relatively hard portion is moderately present in the vicinity of the surface of the adhesive layer. In addition, in the adhesive layer formed from the adhesive composition of the present invention, it is considered that the specific (meth)acrylic polymer (C) is appropriately concentrated in the vicinity of the surface (the so-called vicinity of the interface with the adherend). It is considered that since the glass transition temperature of the specific (meth)acrylic polymer (C) is low, a relatively soft portion is moderately present in the vicinity of the surface of the adhesive layer. It is considered that when such an adhesive layer is attached to an adherend, since there is a moderately hard portion near the interface between the adhesive layer and the adherend, the adhesive layer does not wet the adherend excessively, and the adhesion The agent layer exhibits an appropriate high-speed peel force. Therefore, it is presumed that the adhesive composition of the present invention can form an adhesive layer with a good balance between the low-speed peeling force and the high-speed peeling force. On the other hand, if the wetting of the adhesive layer to the adherend is insufficient, the zipper phenomenon is likely to occur when the adhesive layer is attached to the adherend for a long time and then peeled off from the adherend at a high speed. In view of this, it is considered that the adhesive layer formed from the adhesive composition of the present invention moderately wets the adherend because a relatively soft portion exists in the vicinity of the interface with the adherend. Therefore, it is considered that the zipper phenomenon due to insufficient wetting of the adhesive layer with respect to the adherend is suppressed. Therefore, it is presumed that the adhesive composition of the present invention can form an adhesive layer in which a zipper phenomenon is unlikely to occur even when it is adhered to an adherend for a long time and then peeled off from the adherend at a high speed. That is, in the adhesive layer formed from the adhesive composition of the present invention, the specific (meth)acrylic polymer (B) and the specific (meth)acrylic polymer (C) are appropriately concentrated on the adherend. In the vicinity of the interface, a harder part and a softer part are formed, so as to moderately adjust the wetting of the adhesive layer to the adherend. Therefore, it is presumed that the adhesive layer formed of the adhesive composition of the present invention has a good balance between the low-speed peeling force and the high-speed peeling force, and even if it is adhered to the adherend for a long time and then peeled off from the adherend at high speed, the The zipper phenomenon is not easy to occur.

以下，本說明書中，將特定(甲基)丙烯酸系聚合物(A)、特定(甲基)丙烯酸系聚合物(B)、及特定(甲基)丙烯酸系聚合物(C)總稱為「特定(甲基)丙烯酸系聚合物」。Hereinafter, in this specification, the specific (meth)acrylic polymer (A), the specific (meth)acrylic polymer (B), and the specific (meth)acrylic polymer (C) are collectively referred to as "specific (meth)acrylic polymer".

[特定(甲基)丙烯酸系聚合物(A)] 本發明之黏著劑組成物含有具有羥基及羧基中之至少一者，且重量平均分子量超過20萬且在200萬以下之範圍的(甲基)丙烯酸系聚合物(A)[亦即，特定(甲基)丙烯酸系聚合物(A)]。 本發明之黏著劑組成物可僅含有1種特定(甲基)丙烯酸系聚合物(A)，亦可含有2種以上。[Specific (meth)acrylic polymer (A)] The adhesive composition of the present invention contains a (meth)acrylic polymer (A) having at least one of a hydroxyl group and a carboxyl group, and having a weight-average molecular weight of more than 200,000 and within a range of 2,000,000 or less [that is, a specific ( Meth)acrylic polymer (A)]. The adhesive composition of this invention may contain only 1 type of specific (meth)acrylic-type polymer (A), and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(A)，可為均聚物亦可為共聚物。又，特定(甲基)丙烯酸系聚合物(A)，可為在羥基及羧基中僅具有羥基之聚合物，亦可為僅具有羧基之聚合物，也可為具有羥基及羧基之兩者之聚合物。 特定(甲基)丙烯酸系聚合物(A)，例如可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體的均聚物，亦可為於不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體的均聚物中，藉由取代而導入羥基及羧基中之至少一者而得者，也可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體之共聚物，亦可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體、與不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體以外之單體的共聚物，也可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體以外之單體、與不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體的共聚物。 特定(甲基)丙烯酸系聚合物(A)之較佳態樣，係特定(甲基)丙烯酸系聚合物(A)藉由含有後述來自具有羥基之單體之構成單元及來自具有羧基之單體之構成單元中之至少一者，而具有羥基及羧基中之至少一者的態樣。The specific (meth)acrylic polymer (A) may be a homopolymer or a copolymer. In addition, the specific (meth)acrylic polymer (A) may be a polymer having only a hydroxyl group among a hydroxyl group and a carboxyl group, a polymer having only a carboxyl group, or a combination of both a hydroxyl group and a carboxyl group. polymer. The specific (meth)acrylic polymer (A) may be, for example, a homopolymer of a (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, or may be a homopolymer that does not have a hydroxyl group and a carboxyl group In the homopolymer of any one of the (meth)acrylic monomers, at least one of a hydroxyl group and a carboxyl group is introduced by substitution, or a (methyl) group having at least one of a hydroxyl group and a carboxyl group may be used. (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, and a (meth)acrylic acid-based monomer not having either a hydroxyl group or a carboxyl group A copolymer of a monomer other than a monomer may be a monomer other than a (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, and a (meth) base) copolymers of acrylic monomers. A preferable aspect of the specific (meth)acrylic polymer (A) is that the specific (meth)acrylic polymer (A) contains a structural unit derived from a monomer having a hydroxyl group described later and a monomer derived from a carboxyl group. At least one of the structural units of the body has a form of at least one of a hydroxyl group and a carboxyl group.

＜來自具有羥基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(A)，宜含有來自具有羥基之單體之構成單元。 本說明書中，「來自具有羥基之單體之構成單元」，意指具有羥基之單體進行加成聚合而形成的構成單元。<Constituent unit derived from a monomer having a hydroxyl group> The specific (meth)acrylic polymer (A) preferably contains a structural unit derived from a monomer having a hydroxyl group. In this specification, "the structural unit derived from the monomer which has a hydroxyl group" means the structural unit formed by addition-polymerizing the monomer which has a hydroxyl group.

具有羥基之單體的種類並無特別限定。 具有羥基之單體之具體例，可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸3-甲基-3-羥基丁酯、(甲基)丙烯酸1,1-二甲基-3-羥基丁酯、(甲基)丙烯酸1,3-二甲基-3-羥基丁酯、(甲基)丙烯酸2,2,4-三甲基-3-羥基戊酯、(甲基)丙烯酸2-乙基-3-羥基己酯、N-羥基乙基(甲基)丙烯醯胺、甘油單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、及聚(乙二醇-丙二醇)單(甲基)丙烯酸酯。 具有羥基之單體宜為(甲基)丙烯酸羥基烷基酯，為具有碳數為1～5之羥基烷基之(甲基)丙烯酸羥基烷基酯更佳，為具有碳數為2～4之羥基烷基之(甲基)丙烯酸羥基烷基酯尤佳，為丙烯酸4-羥基丁酯特佳。The kind of the monomer having a hydroxyl group is not particularly limited. Specific examples of the monomer having a hydroxyl group include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxypropyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylate base) 3-methyl-3-hydroxybutyl acrylate, 1,1-dimethyl-3-hydroxybutyl (meth)acrylate, 1,3-dimethyl-3-hydroxybutyl (meth)acrylate Esters, 2,2,4-trimethyl-3-hydroxypentyl (meth)acrylate, 2-ethyl-3-hydroxyhexyl (meth)acrylate, N-hydroxyethyl (meth)acrylate Amines, glycerol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and poly(ethylene glycol-propylene glycol) mono(meth)acrylate. The monomer having a hydroxyl group is preferably a hydroxyalkyl (meth)acrylate, more preferably a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group with a carbon number of 1 to 5, and a hydroxyalkyl (meth)acrylate with a carbon number of 2 to 4 The hydroxyalkyl (meth)acrylate is particularly preferred, and 4-hydroxybutyl acrylate is particularly preferred.

特定(甲基)丙烯酸系聚合物(A)含有來自具有羥基之單體之構成單元時，可僅含有1種來自具有羥基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (A) contains the structural unit derived from the monomer which has a hydroxyl group, it may contain only 1 type of constitutional unit derived from the monomer which has a hydroxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(A)含有來自具有羥基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(A)中之來自具有羥基之單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元，宜為0.1質量%以上且10質量%以下之範圍，為0.5質量%以上且8質量%以下之範圍更佳，為1質量%以上且5質量%以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(A)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元為0.1質量%以上，意指特定(甲基)丙烯酸系聚合物(A)有意圖地含有來自具有羥基之單體之構成單元。 特定(甲基)丙烯酸系聚合物(A)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元為10質量%以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象之黏著劑層的傾向。When the specific (meth)acrylic polymer (A) contains a structural unit derived from a monomer having a hydroxyl group, the content rate of the structural unit derived from a monomer having a hydroxyl group in the specific (meth)acrylic polymer (A) Although not particularly limited, for example, it is preferably in the range of 0.1 mass % or more and 10 mass % or less, and preferably 0.5 mass % or more and 8 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (A). The range is more preferable, and the range of 1 mass % or more and 5 mass % or less is especially preferable. The content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (A) is 0.1 mass % or more with respect to all the structural units of the specific (meth)acrylic polymer (A), It means that a specific (meth)acrylic-type polymer (A) contains the structural unit derived from the monomer which has a hydroxyl group intentionally. When the content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (A) is 10 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (A) , there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed.

＜來自具有羧基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(A)宜含有來自具有羧基之單體之構成單元。 本說明書中，「來自具有羧基之單體之構成單元」，意指具有羧基之單體進行加成聚合而形成的構成單元。<Constituent unit derived from a monomer having a carboxyl group> The specific (meth)acrylic polymer (A) preferably contains a structural unit derived from a monomer having a carboxyl group. In this specification, "the structural unit derived from the monomer which has a carboxyl group" means the structural unit formed by addition-polymerizing the monomer which has a carboxyl group.

具有羧基之單體的種類並無特別限定。 具有羧基之單體之具體例，可列舉：丙烯酸、甲基丙烯酸、巴豆酸、馬來酸酐、富馬酸、伊康酸、戊烯二酸、檸康酸、ω-羧基-聚己內酯單(甲基)丙烯酸酯[例如，ω-羧基-聚己內酯(n≒2)單丙烯酸酯]、及琥珀酸酯[例如，琥珀酸2-丙烯醯氧乙酯]。 具有羧基之單體宜為丙烯酸。The kind of the monomer having a carboxyl group is not particularly limited. Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, fumaric acid, itaconic acid, glutaric acid, citraconic acid, ω-carboxy-polycaprolactone Mono(meth)acrylate [eg, ω-carboxy-polycaprolactone (n≒2) monoacrylate], and succinate [eg, 2-acrylooxyethyl succinate]. The monomer having a carboxyl group is preferably acrylic acid.

特定(甲基)丙烯酸系聚合物(A)含有來自具有羧基之單體之構成單元時，可僅含有1種來自具有羧基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (A) contains the structural unit derived from the monomer which has a carboxyl group, it may contain only 1 type of structural unit derived from the monomer which has a carboxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(A)含有來自具有羧基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(A)中之來自具有羧基之單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元，宜為0.1質量%以上且5質量%以下之範圍，為0.3質量%以上且3質量%以下之範圍更佳，為0.5質量%以上且1.5質量%以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(A)中之來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元為0.1質量%以上，意指特定(甲基)丙烯酸系聚合物(A)有意圖地含有來自具有羧基之單體之構成單元。 特定(甲基)丙烯酸系聚合物(A)中之來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元為5質量%以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象之黏著劑層的傾向。When the specific (meth)acrylic polymer (A) contains a structural unit derived from a monomer having a carboxyl group, the content rate of the structural unit derived from a monomer having a carboxyl group in the specific (meth)acrylic polymer (A) Although not particularly limited, for example, it is preferably in the range of 0.1 mass % or more and 5 mass % or less, and preferably 0.3 mass % or more and 3 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (A). The range is more preferable, and the range of 0.5 mass % or more and 1.5 mass % or less is especially preferable. The content rate of the structural unit derived from the monomer which has a carboxyl group in the specific (meth)acrylic polymer (A) is 0.1 mass % or more with respect to all the structural units of the specific (meth)acrylic polymer (A), It means that a specific (meth)acrylic-type polymer (A) contains the structural unit derived from the monomer which has a carboxyl group intentionally. When the content rate of the structural unit derived from the monomer which has a carboxyl group in the specific (meth)acrylic polymer (A) is 5 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (A) , there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed.

＜來自(甲基)丙烯酸烷基酯單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(A)宜含有來自(甲基)丙烯酸烷基酯單體之構成單元。 來自(甲基)丙烯酸烷基酯單體之構成單元有助於黏著力的調整。<Constituent unit derived from alkyl (meth)acrylate monomer> The specific (meth)acrylic polymer (A) preferably contains a structural unit derived from an alkyl (meth)acrylate monomer. The structural unit derived from the alkyl (meth)acrylate monomer contributes to the adjustment of the adhesive force.

本說明書中，「來自(甲基)丙烯酸烷基酯單體之構成單元」，意指(甲基)丙烯酸烷基酯單體進行加成聚合而形成的構成單元。 此外，本說明書中之「(甲基)丙烯酸烷基酯單體」不包含具有羥基及羧基中之至少一者之(甲基)丙烯酸烷基酯單體。In this specification, "the structural unit derived from the (meth)acrylic-acid alkylester monomer" means the structural unit formed by addition-polymerizing the (meth)acrylic-acid alkylester monomer. In addition, the "(meth)acrylic-acid alkylester monomer" in this specification does not contain the (meth)acrylic-acid alkylester monomer which has at least one of a hydroxyl group and a carboxyl group.

(甲基)丙烯酸烷基酯單體的種類並無特別限定。 (甲基)丙烯酸烷基酯單體宜為無取代之(甲基)丙烯酸烷基酯單體。 (甲基)丙烯酸烷基酯單體之烷基可為直鏈狀、分支鏈狀、或環狀中之任一者。 就烷基之碳數而言，例如考量黏著力的觀點，宜為1以上且18以下之範圍，為1以上且12以下之範圍更佳，為1以上且8以下之範圍尤佳。 尤其烷基之碳數為1以上且8以下之範圍的話，會有所形成之黏著劑層對於被黏體適度地潤濕擴開，展現更適當的低速剝離力的傾向。The type of the (meth)acrylic acid alkyl ester monomer is not particularly limited. The alkyl (meth)acrylate monomer is preferably an unsubstituted alkyl (meth)acrylate monomer. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably in the range of 1 or more and 18 or less, more preferably in the range of 1 or more and 12 or less, and particularly preferably in the range of 1 or more and 8 or less, from the viewpoint of, for example, adhesive force. In particular, when the carbon number of the alkyl group is in the range of 1 or more and 8 or less, the formed adhesive layer tends to moderately wet and spread with respect to the adherend, thereby showing a more appropriate low-speed peeling force.

(甲基)丙烯酸烷基酯單體之具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯、及(甲基)丙烯酸異莰酯。 (甲基)丙烯酸烷基酯單體宜為選自丙烯酸正丁酯及丙烯酸2-乙基己酯中之至少1種。Specific examples of the alkyl (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, and isobornyl (meth)acrylate. The alkyl (meth)acrylate monomer is preferably at least one selected from n-butyl acrylate and 2-ethylhexyl acrylate.

特定(甲基)丙烯酸系聚合物(A)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，可僅含有1種來自(甲基)丙烯酸烷基酯單體之構成單元，亦可含有2種以上。When the specific (meth)acrylic polymer (A) contains a structural unit derived from an alkyl (meth)acrylate monomer, it may contain only one structural unit derived from an alkyl (meth)acrylate monomer, or Two or more types may be contained.

特定(甲基)丙烯酸系聚合物(A)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，特定(甲基)丙烯酸系聚合物(A)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元，宜為50質量%以上，為50質量%以上且99質量%以下之範圍更佳，為60質量%以上且99質量%以下之範圍尤佳，為70質量%以上且99質量%以下之範圍特佳。 此處，特定(甲基)丙烯酸系聚合物(A)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(A)之全部構成單元為50質量%以上，意指來自(甲基)丙烯酸烷基酯單體之構成單元係作為構成特定(甲基)丙烯酸系聚合物(A)之構成單元之主成分而含有。When the specific (meth)acrylic polymer (A) contains a structural unit derived from an alkyl (meth)acrylate monomer, the alkyl (meth)acrylate derived from the specific (meth)acrylic polymer (A) The content rate of the structural unit of the base ester monomer is not particularly limited, but for example, it is preferably 50% by mass or more, 50% by mass or more and 99% by mass relative to all the structural units of the specific (meth)acrylic polymer (A). The range of mass % or less is more preferable, the range of 60 mass % or more and 99 mass % or less is particularly preferable, and the range of 70 mass % or more and 99 mass % or less is particularly preferable. Here, the content rate of the structural unit derived from the (meth)acrylic-acid alkylester monomer in the specific (meth)acrylic-type polymer (A) with respect to the whole of the specific (meth)acrylic-type polymer (A) A structural unit is 50 mass % or more, and it means that the structural unit derived from a (meth)acrylic-acid alkylester monomer is contained as a main component of the structural unit which comprises a specific (meth)acrylic-type polymer (A).

＜其他構成單元＞ 特定(甲基)丙烯酸系聚合物(A)，在發揮本發明之效果的範圍內，可含有上述構成單元以外的構成單元(所謂其他構成單元)。<Other components> A specific (meth)acrylic-type polymer (A) may contain the structural unit (so-called other structural unit) other than the said structural unit in the range which exhibits the effect of this invention.

構成其他構成單元的單體，例如可列舉：以(甲基)丙烯酸苄酯及(甲基)丙烯酸苯氧基乙酯為代表的具有芳香族環之(甲基)丙烯酸酯；以(甲基)丙烯酸甲氧基乙酯及(甲基)丙烯酸乙氧基乙酯為代表的(甲基)丙烯酸烷氧基烷基酯；以苯乙烯、α-甲基苯乙烯、第三丁基苯乙烯、對氯苯乙烯、氯甲基苯乙烯、及乙烯基甲苯為代表的芳香族單乙烯系單體；以丙烯腈及甲基丙烯腈為代表的氰化乙烯系單體；及以甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、及叔碳酸乙烯酯(vinyl-versatate)為代表的乙烯酯。又，可列舉該等單體之各種衍生物。Examples of monomers constituting other structural units include (meth)acrylates having an aromatic ring represented by benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; ) Alkoxyalkyl (meth)acrylate represented by methoxyethyl acrylate and ethoxyethyl (meth)acrylate; styrene, α-methylstyrene, tert-butylstyrene , aromatic monovinyl monomers represented by p-chlorostyrene, chloromethylstyrene, and vinyltoluene; vinyl cyanide monomers represented by acrylonitrile and methacrylonitrile; and vinyl formate , vinyl acetate, vinyl propionate, and vinyl-versatate represented by vinyl esters. Moreover, various derivatives of these monomers can be mentioned.

特定(甲基)丙烯酸系聚合物(A)含有其他構成單元時，可僅含有1種其他構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (A) contains another structural unit, only 1 type of other structural unit may be contained, and 2 or more types may be contained.

特定(甲基)丙烯酸系聚合物(A)含有其他構成單元時，特定(甲基)丙烯酸系聚合物(A)中之其他構成單元的含有率並無特別限定，可因應目的適當設定。When a specific (meth)acrylic-type polymer (A) contains another structural unit, the content rate of the other structural unit in a specific (meth)acrylic-type polymer (A) is not specifically limited, According to the objective, it can set suitably.

＜＜特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度＞＞ 特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度(亦稱為「Tg」。)並無特別限定，例如，宜為-40℃以下，為-50℃以下更佳，為-60℃以下尤佳。 特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度為-40℃以下的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。又，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度的下限並無特別限定，例如，宜為-70℃以上。<<The glass transition temperature of the specific (meth)acrylic polymer (A)>> The glass transition temperature (also referred to as "Tg") of the specific (meth)acrylic polymer (A) is not particularly limited. For example, it is preferably -40°C or lower, more preferably -50°C or lower, and -60 ℃ or lower is particularly preferred. When the glass transition temperature of the specific (meth)acrylic polymer (A) is -40° C. or lower, there is a tendency to form an adhesive layer with a better balance between the low-speed peeling force and the high-speed peeling force. Moreover, there exists a tendency for the adhesive bond layer which does not easily generate|occur|produce a zipper phenomenon to be formed even if it adheres to the to-be-adhered body for a long time and peels from the to-be-adhered body at a high speed. The lower limit of the glass transition temperature of the specific (meth)acrylic polymer (A) is not particularly limited, but, for example, it is preferably -70°C or higher.

特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度，係將由下式1計算求出之絕對溫度(單位：K；以下相同。)換算成攝氏溫度(單位：℃；以下相同。)而得的值。 1/Tg＝m1/Tg1+m2/Tg2+･･･+m(k-1)/Tg(k-1)+mk/Tgk  (式1)The glass transition temperature of the specific (meth)acrylic polymer (A) is obtained by converting the absolute temperature (unit: K; the same below.) calculated by the following formula 1 into the Celsius temperature (unit: °C; the same below.) the value obtained. 1/Tg＝m1/Tg1+m2/Tg2+･･･+m(k-1)/Tg(k-1)+mk/Tgk (Formula 1)

式1中，Tg1、Tg2、･･･、Tg(k-1)、及Tgk，分別表示將構成特定(甲基)丙烯酸系聚合物(A)之各單體製成均聚物時以絕對溫度表示之玻璃轉移溫度。m1、m2、･･･、m(k-1)、及mk，分別表示構成特定(甲基)丙烯酸系聚合物(A)之各單體的莫耳分率，m1+m2+･･･+m(k-1)+mk＝1。 此外，藉由從絕對溫度減去273，可將絕對溫度換算成攝氏溫度，藉由於攝氏溫度加上273，可將攝氏溫度換算成絕對溫度。In Formula 1, Tg1, Tg2, ･･･, Tg(k-1), and Tgk represent the absolute value of each monomer constituting the specific (meth)acrylic-based polymer (A) as a homopolymer, respectively. The glass transition temperature expressed by temperature. m1, m2, ･･･, m(k-1), and mk represent the molar fraction of each monomer constituting the specific (meth)acrylic polymer (A), respectively, m1+m2+･･･+ m(k-1)+mk=1. In addition, the absolute temperature can be converted to the Celsius temperature by subtracting 273 from the absolute temperature, and the Celsius temperature can be converted to the absolute temperature by adding 273 to the Celsius temperature.

本說明書中，「製成均聚物時以絕對溫度表示之玻璃轉移溫度」，係指將該單體單獨聚合而製得之均聚物之以絕對溫度表示之玻璃轉移溫度。 就均聚物之玻璃轉移溫度而言，係使用差示掃描熱量測定裝置(DSC)[型號：EXSTAR6000、Seiko Instruments(股)]，於氮氣流中，以測定試樣10mg、升溫速度10℃/分鐘之條件進行測定，將獲得之DSC曲線之反曲點定義為均聚物之玻璃轉移溫度。In this specification, "glass transition temperature expressed as absolute temperature when a homopolymer is obtained" refers to the glass transition temperature expressed as absolute temperature of a homopolymer obtained by polymerizing the monomer alone. The glass transition temperature of the homopolymer was measured using a differential scanning calorimeter (DSC) [model: EXSTAR6000, Seiko Instruments Co., Ltd.] in a nitrogen stream at a temperature of 10 mg of a sample and a temperature increase rate of 10°C/°C. The measurement was carried out under the conditions of minutes, and the inflection point of the obtained DSC curve was defined as the glass transition temperature of the homopolymer.

代表性的單體之「製成均聚物時以攝氏溫度表示之玻璃轉移溫度」，丙烯酸2-乙基己酯(2EHA)為-76℃、甲基丙烯酸2-乙基己酯(2EHMA)為-10℃、丙烯酸正丁酯(n-BA)為-57℃、甲基丙烯酸正丁酯(n-BMA)為21℃、丙烯酸第三丁酯(t-BA)為41℃、甲基丙烯酸第三丁酯(t-BMA)為107℃、甲基丙烯酸異丁酯(i-BMA)為48℃、丙烯酸甲酯(MA)為5℃、甲基丙烯酸甲酯(MMA)為103℃、甲基丙烯酸異莰酯(IBXMA)為155℃、丙烯酸異莰酯(IBXA)為96℃、丙烯酸乙酯(EA)為-27℃、甲基丙烯酸(MAA)為185℃、丙烯酸4-羥基丁酯(4HBA)為-39℃、丙烯酸2-羥基乙酯(2HEA)為-15℃、甲基丙烯酸2-羥基乙酯(2HEMA)為55℃、丙烯酸2-羥基丙酯(2HPA)為-7℃、丙烯酸(AA)為163℃、丙烯酸酯異辛酯(i-OA)為-75℃、甲基丙烯酸二甲基胺基乙酯(DM)為18℃、ω-羧基-聚己內酯(n≒2)單丙烯酸酯為-30℃、及琥珀酸2-丙烯醯氧乙酯為-40℃。"Glass transition temperature expressed in degrees Celsius when a homopolymer is prepared" as a representative monomer, 2-ethylhexyl acrylate (2EHA) is -76°C, 2-ethylhexyl methacrylate (2EHMA) is -10℃, n-butyl acrylate (n-BA) is -57℃, n-butyl methacrylate (n-BMA) is 21℃, tertiary butyl acrylate (t-BA) is 41℃, methyl methacrylate (t-BA) is 107°C for tertiary butyl acrylate (t-BMA), 48°C for isobutyl methacrylate (i-BMA), 5°C for methyl acrylate (MA), and 103°C for methyl methacrylate (MMA) , 155°C for isocamphenyl methacrylate (IBXMA), 96°C for isocampylate acrylate (IBXA), -27°C for ethyl acrylate (EA), 185°C for methacrylic acid (MAA), 4-hydroxy acrylate Butyl ester (4HBA) is -39°C, 2-hydroxyethyl acrylate (2HEA) is -15°C, 2-hydroxyethyl methacrylate (2HEMA) is 55°C, 2-hydroxypropyl acrylate (2HPA) is - 7°C, acrylic acid (AA) is 163°C, isooctyl acrylate (i-OA) is -75°C, dimethylaminoethyl methacrylate (DM) is 18°C, ω-carboxy-polycaprolactone The ester (n≒2) monoacrylate was -30°C, and the 2-propenyloxyethyl succinate was -40°C.

特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度，例如可藉由使用2種以上之製成均聚物時之玻璃轉移溫度不同的單體來適當調整。The glass transition temperature of the specific (meth)acrylic polymer (A) can be appropriately adjusted, for example, by using two or more monomers having different glass transition temperatures when used as a homopolymer.

＜＜特定(甲基)丙烯酸系聚合物(A)之重量平均分子量＞＞ 特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(亦稱為「Mw」。)，為超過20萬且在200萬以下之範圍，宜為超過20萬且在180萬以下之範圍，為超過20萬且在160萬以下之範圍更佳，為超過20萬且在140萬以下之範圍尤佳，為超過20萬且在120萬以下之範圍特佳。 特定(甲基)丙烯酸系聚合物(A)之重量平均分子量超過20萬的話，會有所形成之黏著劑層容易獲得凝聚力的傾向。 特定(甲基)丙烯酸系聚合物(A)之重量平均分子量為200萬以下的話，會有黏著劑組成物之塗覆性容易變得良好的傾向。<<The weight average molecular weight of the specific (meth)acrylic polymer (A)>> The weight average molecular weight (also referred to as "Mw") of the specific (meth)acrylic polymer (A) is in the range of more than 200,000 and 2,000,000 or less, preferably in the range of more than 200,000 and 1,800,000 or less , more preferably in the range of more than 200,000 and below 1.6 million, more preferably in the range of more than 200,000 and below 1.4 million, and particularly preferably in the range of more than 200,000 and below 1.2 million. When the weight-average molecular weight of the specific (meth)acrylic polymer (A) exceeds 200,000, the formed adhesive layer tends to easily acquire cohesion. When the weight average molecular weight of the specific (meth)acrylic polymer (A) is 2,000,000 or less, the applicability of the adhesive composition tends to be favorable.

特定(甲基)丙烯酸系聚合物(A)之重量平均分子量，係利用下列方法測得的值。具體而言，依循下列(1)～(3)進行測定。 (1)將特定(甲基)丙烯酸系聚合物(A)之溶液塗布於剝離紙，於100℃乾燥1分鐘，獲得薄膜狀之特定(甲基)丙烯酸系聚合物(A)。 (2)使用上述(1)獲得之薄膜狀之特定(甲基)丙烯酸系聚合物(A)與四氫呋喃，獲得固體成分濃度為0.2質量%的試樣溶液。此外，此處所稱「固體成分濃度」，意指在試樣溶液中特定(甲基)丙烯酸系聚合物(A)所佔之質量比例。 (3)利用凝膠滲透層析法(GPC)，依下列條件以標準聚苯乙烯換算值的形式測定特定(甲基)丙烯酸系聚合物(A)之重量平均分子量。The weight average molecular weight of the specific (meth)acrylic polymer (A) is a value measured by the following method. Specifically, the measurement was performed according to the following (1) to (3). (1) The solution of the specific (meth)acrylic-type polymer (A) was apply|coated to a release paper, and it dried at 100 degreeC for 1 minute, and obtained the specific (meth)acrylic-type polymer (A) in the form of a film. (2) Using the film-like specific (meth)acrylic polymer (A) obtained in the above (1) and tetrahydrofuran, a sample solution having a solid content concentration of 0.2 mass % was obtained. In addition, "solid content concentration" as used here means the mass ratio which a specific (meth)acrylic-type polymer (A) occupies in a sample solution. (3) Using gel permeation chromatography (GPC), the weight average molecular weight of the specific (meth)acrylic polymer (A) was measured as a standard polystyrene-equivalent value under the following conditions.

～條件～ 測定裝置：高速GPC[型號：HLC-8220 GPC、東曹(股)製] 檢測器：差示折射率計(RI)[組裝於HLC-8220、東曹(股)製] 管柱：使用4支TSK-GEL GMHXL [東曹(股)製] 管柱溫度：40℃ 洗提液：四氫呋喃 試樣溶液之注入量：100μL 流量：0.8mL/分鐘～Condition～ Measuring device: High-speed GPC [Model: HLC-8220 GPC, manufactured by Tosoh Corporation] Detector: Differential Refractometer (RI) [Assembled in HLC-8220, manufactured by Tosoh Corporation] Column : Using 4 TSK-GEL GMH XL [manufactured by Tosoh Corporation] Column temperature: 40°C Eluent: Tetrahydrofuran Sample solution injection volume: 100 μL Flow rate: 0.8 mL/min

特定(甲基)丙烯酸系聚合物(A)之重量平均分子量，可藉由調整聚合溫度、聚合時間、有機溶劑的使用量、聚合引發劑的種類、聚合引發劑的使用量等而使其成為期望之值。The weight-average molecular weight of the specific (meth)acrylic polymer (A) can be adjusted to the polymerization temperature, the polymerization time, the amount of the organic solvent used, the type of the polymerization initiator, the amount of the polymerization initiator used, and the like. expected value.

＜＜特定(甲基)丙烯酸系聚合物(A)之羥值＞＞ 特定(甲基)丙烯酸系聚合物(A)具有羥基時，特定(甲基)丙烯酸系聚合物(A)之羥值並無特別限定，例如，宜為0.3mgKOH/g以上且40mgKOH/g以下之範圍，為0.5mgKOH/g以上且30mgKOH/g以下之範圍更佳，為1mgKOH/g以上且20mgKOH/g以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(A)之羥值為0.3mgKOH/g以上的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(A)之羥值為40mgKOH/g以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<Hydroxy value of specific (meth)acrylic polymer (A)>> When the specific (meth)acrylic polymer (A) has a hydroxyl group, the hydroxyl value of the specific (meth)acrylic polymer (A) is not particularly limited, but, for example, it is preferably 0.3 mgKOH/g or more and 40 mgKOH/g or less. The range is more preferably a range of 0.5 mgKOH/g or more and 30 mgKOH/g or less, and more preferably a range of 1 mgKOH/g or more and 20 mgKOH/g or less. When the hydroxyl value of the specific (meth)acrylic polymer (A) is 0.3 mgKOH/g or more, there is a tendency to form an adhesive layer with a better balance between the low-speed peeling force and the high-speed peeling force. If the hydroxyl value of the specific (meth)acrylic polymer (A) is 40 mgKOH/g or less, the zipper phenomenon will not easily occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(A)之羥值，係依下列計算式求出之值。此外，下列計算式中，56.1係KOH之分子量。 羥值(mgKOH/g) ＝[(A1/100)÷A2]×56.1×1000×A3 A1：特定(甲基)丙烯酸系聚合物(A)之製造所使用之全部單體中，具有羥基之單體所佔的比例(單位：質量%) A2：特定(甲基)丙烯酸系聚合物(A)之製造所使用之具有羥基之單體之分子量 A3：具有羥基之單體1分子中含有的羥基數The hydroxyl value of a specific (meth)acrylic-type polymer (A) is a value calculated|required by the following calculation formula. In addition, in the following formula, 56.1 is the molecular weight of KOH. Hydroxyl value (mgKOH/g) ＝[(A1/100)÷A2]×56.1×1000×A3 A1: The ratio (unit: mass %) of the monomer having a hydroxyl group in all the monomers used for the production of the specific (meth)acrylic polymer (A) A2: Molecular weight of the monomer having a hydroxyl group used for the production of the specific (meth)acrylic polymer (A) A3: The number of hydroxyl groups contained in 1 molecule of a monomer having a hydroxyl group

特定(甲基)丙烯酸系聚合物(A)之製造所使用之具有羥基之單體有2種以上時，針對各單體依上述計算式求出羥值後，將獲得之值予以合計而求出羥值。When there are two or more monomers having a hydroxyl group used for the production of the specific (meth)acrylic polymer (A), after obtaining the hydroxyl value for each monomer according to the above calculation formula, the obtained values are added up to obtain Hydroxyl value.

＜＜特定(甲基)丙烯酸系聚合物(A)之酸價＞＞ 特定(甲基)丙烯酸系聚合物(A)具有羧基時，特定(甲基)丙烯酸系聚合物(A)之酸價並無特別限定，例如，宜為0.7mgKOH/g以上且24mgKOH/g以下之範圍，為1mgKOH/g以上且20mgKOH/g以下之範圍更佳，為2mgKOH/g以上且10mgKOH/g以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(A)之酸價為0.7mgKOH/g以上的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(A)之酸價為24mgKOH/g以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<Acid value of specific (meth)acrylic polymer (A)>> When the specific (meth)acrylic polymer (A) has a carboxyl group, the acid value of the specific (meth)acrylic polymer (A) is not particularly limited, but, for example, it is preferably 0.7 mgKOH/g or more and 24 mgKOH/g or less. The range is more preferably a range of 1 mgKOH/g or more and 20 mgKOH/g or less, and more preferably a range of 2 mgKOH/g or more and 10 mgKOH/g or less. When the acid value of the specific (meth)acrylic polymer (A) is 0.7 mgKOH/g or more, there is a tendency to form an adhesive layer with a better balance between the low-speed peeling force and the high-speed peeling force. If the acid value of the specific (meth)acrylic polymer (A) is 24 mgKOH/g or less, there is a possibility that the zipper phenomenon will not easily occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(A)之酸價，係依下列計算式求出之值。此外，下列計算式中，56.1係KOH之分子量。 酸價(mgKOH/g) ＝[(a1/100)÷a2]×56.1×1000×a3 a1：特定(甲基)丙烯酸系聚合物(A)之製造所使用之全部單體中，具有羧基之單體所佔的比例(單位：質量%) a2：特定(甲基)丙烯酸系聚合物(A)之製造所使用之具有羧基之單體之分子量 a3：具有羧基之單體1分子中含有的羧基數The acid value of a specific (meth)acrylic-type polymer (A) is a value calculated|required by the following calculation formula. In addition, in the following formula, 56.1 is the molecular weight of KOH. Acid value (mgKOH/g) ＝[(a1/100)÷a2]×56.1×1000×a3 a1: The ratio (unit: mass %) of the monomer having a carboxyl group in all the monomers used for the production of the specific (meth)acrylic polymer (A) a2: Molecular weight of the monomer having a carboxyl group used for the production of the specific (meth)acrylic polymer (A) a3: The number of carboxyl groups contained in 1 molecule of a monomer having a carboxyl group

特定(甲基)丙烯酸系聚合物(A)之製造所使用之具有羧基之單體有2種以上時，針對各單體依上述計算式求出酸價後，將獲得之值予以合計而求出酸價。When there are two or more monomers having a carboxyl group used in the production of the specific (meth)acrylic polymer (A), the acid value is calculated for each monomer according to the above calculation formula, and the obtained values are added up to calculate out of acid value.

＜＜特定(甲基)丙烯酸系聚合物(A)的含有率＞＞ 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(A)的含有率並無特別限定，例如，相對於黏著劑組成物中之全部固體成分量，宜為55質量%以上且92質量%以下之範圍，為55質量%以上且90質量%以下之範圍更佳，為60質量%以上且90質量%以下之範圍尤佳，為60質量%以上且88質量%以下之範圍特佳。 本說明書中，「黏著劑組成物中之全部固體成分量」，當黏著劑組成物不含溶劑時，意指黏著劑組成物之總質量，當黏著劑組成物含有溶劑時，意指從黏著劑組成物除去溶劑後的殘渣之質量。 本說明書中，「溶劑」意指水及有機溶劑。<<Content rate of specific (meth)acrylic polymer (A)>> The content of the specific (meth)acrylic polymer (A) in the adhesive composition of the present invention is not particularly limited, but, for example, it is preferably 55% by mass or more with respect to the total solid content in the adhesive composition And the range of 92 mass % or less, the range of 55 mass % or more and 90 mass % or less is more preferable, the range of 60 mass % or more and 90 mass % or less is particularly preferable, and the range of 60 mass % or more and 88 mass % or less is more preferable. Excellent. In this specification, "the total solid content in the adhesive composition" means the total mass of the adhesive composition when the adhesive composition does not contain a solvent, and means the total mass of the adhesive composition when the adhesive composition contains a solvent. The mass of the residue after the solvent composition is removed. In this specification, "solvent" means water and an organic solvent.

[特定(甲基)丙烯酸系聚合物(B)] 本發明之黏著劑組成物含有具有羥基及羧基中之至少一者，玻璃轉移溫度為0℃以上且45℃以下之範圍，且重量平均分子量為6000以上且15萬以下之範圍的(甲基)丙烯酸系聚合物(B)[亦即，特定(甲基)丙烯酸系聚合物(B)]。又，本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(B)之含量，相對於上述特定(甲基)丙烯酸系聚合物(A)100質量份，為7質量份以上且70質量份以下之範圍。 本發明之黏著劑組成物可僅含有1種特定(甲基)丙烯酸系聚合物(B)，亦可含有2種以上。[Specific (meth)acrylic polymer (B)] The adhesive composition of the present invention contains (methyl) having at least one of a hydroxyl group and a carboxyl group, a glass transition temperature in the range of 0°C or higher and 45°C or lower, and a weight average molecular weight in the range of 6,000 or more and 150,000 or less. Acrylic polymer (B) [that is, specific (meth)acrylic polymer (B)]. Moreover, the content of the specific (meth)acrylic polymer (B) in the adhesive composition of the present invention is 7 parts by mass or more with respect to 100 parts by mass of the above-mentioned specific (meth)acrylic polymer (A). and 70 parts by mass or less. The adhesive composition of this invention may contain only 1 type of specific (meth)acrylic-type polymer (B), and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(B)，可為均聚物亦可為共聚物。又，特定(甲基)丙烯酸系聚合物(B)可為在羥基及羧基中僅具有羥基之聚合物，亦可為僅具有羧基之聚合物，也可為具有羥基及羧基之兩者之聚合物。 特定(甲基)丙烯酸系聚合物(B)，例如，可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體的均聚物，亦可為於不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體的均聚物中，藉由取代而導入羥基及羧基中之至少一者而得者，也可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體的共聚物，亦可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體、與不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體以外之單體的共聚物，也可為具有羥基及羧基中之至少一者之(甲基)丙烯酸系單體以外之單體、與不具有羥基及羧基中之任一者之(甲基)丙烯酸系單體的共聚物。 特定(甲基)丙烯酸系聚合物(B)之較佳態樣，係特定(甲基)丙烯酸系聚合物(B)藉由含有後述來自具有羥基之單體之構成單元及來自具有羧基之單體之構成單元中之至少一者，而具有羥基及羧基中之至少一者的態樣。The specific (meth)acrylic polymer (B) may be a homopolymer or a copolymer. Moreover, the specific (meth)acrylic polymer (B) may be a polymer having only a hydroxyl group among a hydroxyl group and a carboxyl group, a polymer having only a carboxyl group, or a polymer having both a hydroxyl group and a carboxyl group. thing. The specific (meth)acrylic polymer (B) may be, for example, a homopolymer of a (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, or may be a homopolymer that does not have a hydroxyl group and a carboxyl group In the homopolymer of any one of the (meth)acrylic monomers, at least one of a hydroxyl group and a carboxyl group is introduced by substitution, and it may be ( The copolymer of meth)acrylic monomer may be a (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, and a (meth)acrylic acid not having any one of a hydroxyl group and a carboxyl group A copolymer of a monomer other than a monomer may be a monomer other than a (meth)acrylic monomer having at least one of a hydroxyl group and a carboxyl group, and a monomer that does not have either a hydroxyl group or a carboxyl group ( Copolymers of meth)acrylic monomers. A preferable aspect of the specific (meth)acrylic polymer (B) is that the specific (meth)acrylic polymer (B) contains a structural unit derived from a monomer having a hydroxyl group described later and a monomer derived from a carboxyl group. At least one of the structural units of the body has a form of at least one of a hydroxyl group and a carboxyl group.

＜來自具有羥基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(B)宜含有來自具有羥基之單體之構成單元。 具有羥基之單體的種類並無特別限定。 特定(甲基)丙烯酸系聚合物(B)中之具有羥基之單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之具有羥基之單體之具體例同樣，故此處省略其說明。 具有羥基之單體宜為(甲基)丙烯酸羥基烷基酯，為具有碳數為1～5之羥基烷基之(甲基)丙烯酸羥基烷基酯更佳，為具有碳數為2～4之羥基烷基之(甲基)丙烯酸羥基烷基酯更佳，為丙烯酸4-羥基丁酯特佳。<Constituent unit derived from a monomer having a hydroxyl group> The specific (meth)acrylic polymer (B) preferably contains a structural unit derived from a monomer having a hydroxyl group. The kind of the monomer having a hydroxyl group is not particularly limited. Specific examples of the monomer having a hydroxyl group in the specific (meth)acrylic polymer (B) are the same as the specific examples of the monomer having a hydroxyl group in the specific (meth)acrylic polymer (A), so Its description is omitted here. The monomer having a hydroxyl group is preferably a hydroxyalkyl (meth)acrylate, more preferably a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group with a carbon number of 1 to 5, and a hydroxyalkyl (meth)acrylate with a carbon number of 2 to 4 The hydroxyalkyl (meth)acrylate is more preferably hydroxyalkyl, especially 4-hydroxybutyl acrylate.

特定(甲基)丙烯酸系聚合物(B)含有來自具有羥基之單體之構成單元時，可僅含有1種來自具有羥基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (B) contains the structural unit derived from the monomer which has a hydroxyl group, it may contain only 1 type of constitutional unit derived from the monomer which has a hydroxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(B)含有來自具有羥基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(B)中之來自具有羥基之單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元，宜為0.1質量%以上且10質量%以下之範圍，為0.5質量%以上且8質量%以下之範圍更佳，為1質量%以上且5質量%以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元為0.1質量%以上，意指特定(甲基)丙烯酸系聚合物(B)積極地含有來自具有羥基之單體之構成單元。 特定(甲基)丙烯酸系聚合物(B)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元為10質量%以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。When the specific (meth)acrylic polymer (B) contains a structural unit derived from a monomer having a hydroxyl group, the content rate of the structural unit derived from a monomer having a hydroxyl group in the specific (meth)acrylic polymer (B) Although not particularly limited, for example, it is preferably in the range of 0.1 mass % or more and 10 mass % or less, and preferably 0.5 mass % or more and 8 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (B). The range is more preferable, and the range of 1 mass % or more and 5 mass % or less is especially preferable. The content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (B) is 0.1 mass % or more with respect to all the structural units of the specific (meth)acrylic polymer (B), This means that the specific (meth)acrylic polymer (B) positively contains a structural unit derived from a monomer having a hydroxyl group. When the content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (B) is 10 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (B) , there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time.

＜來自具有羧基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(B)宜含有來自具有羧基之單體之構成單元。 具有羧基之單體的種類並無特別限定。 特定(甲基)丙烯酸系聚合物(B)中之具有羧基之單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之具有羧基之單體之具體例同樣，故此處省略其說明。 具有羧基之單體宜為丙烯酸。<Constituent unit derived from a monomer having a carboxyl group> The specific (meth)acrylic polymer (B) preferably contains a structural unit derived from a monomer having a carboxyl group. The kind of the monomer having a carboxyl group is not particularly limited. Specific examples of the monomer having a carboxyl group in the specific (meth)acrylic polymer (B) are the same as the specific examples of the monomer having a carboxyl group in the specific (meth)acrylic polymer (A), so Its description is omitted here. The monomer having a carboxyl group is preferably acrylic acid.

特定(甲基)丙烯酸系聚合物(B)含有來自具有羧基之單體之構成單元時，可僅含有1種來自具有羧基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (B) contains the structural unit derived from the monomer which has a carboxyl group, it may contain only 1 type of constitutional unit derived from the monomer which has a carboxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(B)含有來自具有羧基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(B)中之來自具有羧基之單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元，宜為0.1質量%以上且5質量%以下之範圍，為0.3質量%以上且3質量%以下之範圍更佳，為0.5質量%以上且1.5質量%以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)中之來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元為0.1質量%以上，意指特定(甲基)丙烯酸系聚合物(B)積極地含有來自具有羧基之單體之構成單元。 特定(甲基)丙烯酸系聚合物(B)中之來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元為5質量%以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。When the specific (meth)acrylic polymer (B) contains a structural unit derived from a monomer having a carboxyl group, the content rate of the structural unit derived from a monomer having a carboxyl group in the specific (meth)acrylic polymer (B) Although not particularly limited, for example, it is preferably in the range of 0.1 mass % or more and 5 mass % or less, and preferably 0.3 mass % or more and 3 mass % or less with respect to all the constituent units of the specific (meth)acrylic polymer (B). The range is more preferable, and the range of 0.5 mass % or more and 1.5 mass % or less is especially preferable. The content rate of the structural unit derived from the monomer which has a carboxyl group in the specific (meth)acrylic polymer (B) is 0.1 mass % or more with respect to all the structural units of the specific (meth)acrylic polymer (B), It means that the specific (meth)acrylic-type polymer (B) positively contains the structural unit derived from the monomer which has a carboxyl group. When the content rate of the structural unit derived from the monomer which has a carboxyl group in the specific (meth)acrylic polymer (B) is 5 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (B) , there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time.

＜來自(甲基)丙烯酸烷基酯單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(B)宜含有來自(甲基)丙烯酸烷基酯單體之構成單元。 (甲基)丙烯酸烷基酯單體的種類並無特別限定。 (甲基)丙烯酸烷基酯單體宜為無取代之(甲基)丙烯酸烷基酯單體。 (甲基)丙烯酸烷基酯單體之烷基可為直鏈狀、分支鏈狀、或環狀中之任一者。 就烷基之碳數而言，例如考量黏著力的觀點，宜為1以上且18以下之範圍，為1以上且12以下之範圍更佳，為1以上且8以下之範圍尤佳。<Constituent unit derived from alkyl (meth)acrylate monomer> The specific (meth)acrylic polymer (B) preferably contains a structural unit derived from an alkyl (meth)acrylate monomer. The type of the (meth)acrylic acid alkyl ester monomer is not particularly limited. The alkyl (meth)acrylate monomer is preferably an unsubstituted alkyl (meth)acrylate monomer. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably in the range of 1 or more and 18 or less, more preferably in the range of 1 or more and 12 or less, and particularly preferably in the range of 1 or more and 8 or less, from the viewpoint of, for example, adhesive force.

特定(甲基)丙烯酸系聚合物(B)中之(甲基)丙烯酸烷基酯單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之(甲基)丙烯酸烷基酯單體之具體例同樣，故此處省略其說明。 (甲基)丙烯酸烷基酯單體，宜為選自由丙烯酸甲酯、丙烯酸正丁酯、及甲基丙烯酸正丁酯構成之群組中之至少1種。Specific examples of the (meth)acrylic acid alkyl ester monomer in the specific (meth)acrylic polymer (B) are the same as the alkyl (meth)acrylate in the specific (meth)acrylic polymer (A). The specific example of the base ester monomer is the same, so the description is omitted here. The alkyl (meth)acrylate monomer is preferably at least one selected from the group consisting of methyl acrylate, n-butyl acrylate, and n-butyl methacrylate.

特定(甲基)丙烯酸系聚合物(B)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，可僅含有1種來自(甲基)丙烯酸烷基酯單體之構成單元，亦可含有2種以上。When the specific (meth)acrylic polymer (B) contains a structural unit derived from an alkyl (meth)acrylate monomer, it may contain only one structural unit derived from an alkyl (meth)acrylate monomer, and the Two or more types may be contained.

特定(甲基)丙烯酸系聚合物(B)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，特定(甲基)丙烯酸系聚合物(B)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元，宜為50質量%以上，為50質量%以上且99質量%以下之範圍更佳，為60質量%以上且99質量%以下之範圍尤佳，為70質量%以上且99質量%以下之範圍特佳。 此處，特定(甲基)丙烯酸系聚合物(B)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(B)之全部構成單元為50質量%以上，意指來自(甲基)丙烯酸烷基酯單體之構成單元係作為構成特定(甲基)丙烯酸系聚合物(B)之構成單元之主成分而含有。When the specific (meth)acrylic polymer (B) contains a structural unit derived from an alkyl (meth)acrylate monomer, the alkyl (meth)acrylate derived from the specific (meth)acrylic polymer (B) The content rate of the constituent unit of the base ester monomer is not particularly limited, but for example, it is preferably 50 mass % or more, 50 mass % or more and 99 mass % with respect to all the constituent units of the specific (meth)acrylic polymer (B). The range of mass % or less is more preferable, the range of 60 mass % or more and 99 mass % or less is particularly preferable, and the range of 70 mass % or more and 99 mass % or less is particularly preferable. Here, the content rate of the structural unit derived from the alkyl (meth)acrylate monomer in the specific (meth)acrylic polymer (B) is relative to the entire specific (meth)acrylic polymer (B) That the structural unit is 50 mass % or more means that the structural unit derived from the (meth)acrylic acid alkyl ester monomer is contained as the main component of the structural unit which comprises a specific (meth)acrylic-type polymer (B).

＜其他構成單元＞ 特定(甲基)丙烯酸系聚合物(B)，在發揮本發明之效果的範圍內，可含有上述構成單元以外的構成單元(所謂其他構成單元)。<Other components> A specific (meth)acrylic-type polymer (B) may contain the structural unit (so-called other structural unit) other than the said structural unit in the range which exhibits the effect of this invention.

構成特定(甲基)丙烯酸系聚合物(B)中之其他構成單元的單體之具體例，係與構成特定(甲基)丙烯酸系聚合物(A)中之其他構成單元的單體之具體例同樣，故此處省略其說明。Specific examples of monomers constituting other structural units in the specific (meth)acrylic polymer (B) are specific examples of monomers constituting other structural units in the specific (meth)acrylic polymer (A) The example is the same, so the description is omitted here.

特定(甲基)丙烯酸系聚合物(B)含有其他構成單元時，可僅含有1種其他構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (B) contains another structural unit, only 1 type of other structural unit may be contained, and 2 or more types may be contained.

特定(甲基)丙烯酸系聚合物(B)含有其他構成單元時，特定(甲基)丙烯酸系聚合物(B)中之其他構成單元的含有率並無特別限定，可因應目的適當設定。When a specific (meth)acrylic-type polymer (B) contains another structural unit, the content rate of the other structural unit in a specific (meth)acrylic-type polymer (B) is not specifically limited, According to the objective, it can set suitably.

＜＜特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度＞＞ 特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度為0℃以上且45℃以下之範圍，宜為5℃以上且43℃以下之範圍，為10℃以上且40℃以下之範圍更佳，為15℃以上且35℃以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度為0℃以上的話，會有可形成低速剝離力與高速剝離力之平衡良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度為45℃以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<The glass transition temperature of the specific (meth)acrylic polymer (B)>> The glass transition temperature of the specific (meth)acrylic polymer (B) is in the range of 0°C or higher and 45°C or lower, preferably 5°C or higher and 43°C or lower, more preferably 10°C or higher and 40°C or lower. Preferably, it is the range of 15 degreeC or more and 35 degrees C or less. When the glass transition temperature of a specific (meth)acrylic-type polymer (B) is 0 degreeC or more, there exists a tendency for the adhesive bond layer with the balance of a low-speed peeling force and a high-speed peeling force to be favorable. If the glass transition temperature of the specific (meth)acrylic polymer (B) is 45°C or lower, there is a possibility that even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed, the zipper phenomenon will not easily occur. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度，係利用與特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度同樣之方法求出之值。The glass transition temperature of the specific (meth)acrylic polymer (B) is a value determined by the same method as the glass transition temperature of the specific (meth)acrylic polymer (A).

特定(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度，例如可藉由使用2種以上之製成均聚物時之玻璃轉移溫度不同的單體來適當調整。The glass transition temperature of the specific (meth)acrylic polymer (B) can be appropriately adjusted, for example, by using two or more monomers having different glass transition temperatures when used as a homopolymer.

＜＜特定(甲基)丙烯酸系聚合物(B)之重量平均分子量＞＞ 特定(甲基)丙烯酸系聚合物(B)之重量平均分子量為6000以上且15萬以下之範圍，宜為1萬以上且15萬以下之範圍，為1.5萬以上且15萬以下之範圍更佳，為2萬以上且10萬以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)之重量平均分子量為6000以上的話，會有可形成低速剝離力與高速剝離力之平衡良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(B)之重量平均分子量為15萬以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<The weight average molecular weight of the specific (meth)acrylic polymer (B)>> The weight average molecular weight of the specific (meth)acrylic polymer (B) is in the range of 6,000 or more and 150,000 or less, preferably 10,000 or more and 150,000 or less, more preferably 15,000 or more and 150,000 or less , the range of more than 20,000 and less than 100,000 is particularly preferred. When the weight average molecular weight of the specific (meth)acrylic polymer (B) is 6,000 or more, there is a tendency to form an adhesive layer with a good balance between low-speed peeling force and high-speed peeling force. If the weight-average molecular weight of the specific (meth)acrylic polymer (B) is 150,000 or less, there is a possibility that even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed, the zipper phenomenon does not easily occur. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(B)之重量平均分子量，係利用與特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)同樣之方法測得之值。The weight average molecular weight of the specific (meth)acrylic polymer (B) is a value measured by the same method as the weight average molecular weight (Mw) of the specific (meth)acrylic polymer (A).

特定(甲基)丙烯酸系聚合物(B)之重量平均分子量，可藉由調整聚合溫度、聚合時間、有機溶劑的使用量、聚合引發劑的種類、聚合引發劑的使用量等而使其成為期望之值。The weight-average molecular weight of the specific (meth)acrylic polymer (B) can be adjusted to the polymerization temperature, the polymerization time, the amount of the organic solvent used, the type of the polymerization initiator, the amount of the polymerization initiator used, and the like. expected value.

＜＜特定(甲基)丙烯酸系聚合物(B)之羥值＞＞ 特定(甲基)丙烯酸系聚合物(B)具有羥基時，特定(甲基)丙烯酸系聚合物(B)之羥值並無特別限定，例如，宜為0.3mgKOH/g以上且40mgKOH/g以下之範圍，為0.5mgKOH/g以上且30mgKOH/g以下之範圍更佳，為1mgKOH/g以上且20mgKOH/g以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)之羥值為0.3mgKOH/g以上的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(B)之羥值為40mgKOH/g以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<Hydroxy value of specific (meth)acrylic polymer (B)>> When the specific (meth)acrylic polymer (B) has a hydroxyl group, the hydroxyl value of the specific (meth)acrylic polymer (B) is not particularly limited, but, for example, it is preferably 0.3 mgKOH/g or more and 40 mgKOH/g or less. The range is more preferably a range of 0.5 mgKOH/g or more and 30 mgKOH/g or less, and more preferably a range of 1 mgKOH/g or more and 20 mgKOH/g or less. When the hydroxyl value of the specific (meth)acrylic polymer (B) is 0.3 mgKOH/g or more, there is a tendency to form an adhesive layer with a better balance between the low-speed peeling force and the high-speed peeling force. If the hydroxyl value of the specific (meth)acrylic polymer (B) is 40 mgKOH/g or less, the zipper phenomenon will not easily occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(B)之羥值，係利用與特定(甲基)丙烯酸系聚合物(A)之羥值同樣之方法算出之值。The hydroxyl value of the specific (meth)acrylic polymer (B) is a value calculated by the same method as the hydroxyl value of the specific (meth)acrylic polymer (A).

＜＜特定(甲基)丙烯酸系聚合物(B)之酸價＞＞ 特定(甲基)丙烯酸系聚合物(B)具有羧基時，特定(甲基)丙烯酸系聚合物(B)之酸價並無特別限定，例如，宜為0.7mgKOH/g以上且24mgKOH/g以下之範圍，為1mgKOH/g以上且20mgKOH/g以下之範圍更佳，為2mgKOH/g以上且10mgKOH/g以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(B)之酸價為0.7mgKOH/g以上的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(B)之酸價為24mgKOH/g以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。就理由而言，據推測係因為所形成之黏著劑層對於被黏體之潤濕不會被過度抑制所致。<<Acid value of specific (meth)acrylic polymer (B)>> When the specific (meth)acrylic polymer (B) has a carboxyl group, the acid value of the specific (meth)acrylic polymer (B) is not particularly limited, but, for example, it is preferably 0.7 mgKOH/g or more and 24 mgKOH/g or less. The range is more preferably a range of 1 mgKOH/g or more and 20 mgKOH/g or less, and more preferably a range of 2 mgKOH/g or more and 10 mgKOH/g or less. When the acid value of the specific (meth)acrylic polymer (B) is 0.7 mgKOH/g or more, there is a tendency to form an adhesive layer with a better balance between the low-speed peeling force and the high-speed peeling force. If the acid value of the specific (meth)acrylic polymer (B) is 24 mgKOH/g or less, there is a possibility that the zipper phenomenon will not easily occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. the tendency of the adhesive layer. For the reason, it is presumed that the formed adhesive layer is not excessively inhibited from the wetting of the adherend.

特定(甲基)丙烯酸系聚合物(B)之酸價，係利用與特定(甲基)丙烯酸系聚合物(A)之酸價同樣之方法算出之值。The acid value of the specific (meth)acrylic polymer (B) is a value calculated by the same method as the acid value of the specific (meth)acrylic polymer (A).

＜＜特定(甲基)丙烯酸系聚合物(B)之含量＞＞ 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(B)之含量，相對於特定(甲基)丙烯酸系聚合物(A)100質量份，為7質量份以上且70質量份以下之範圍，宜為10質量份以上60質量份以下之範圍，為15質量份以上且55質量份以下之範圍更佳，為20質量份以上且50質量份以下之範圍尤佳。 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(B)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為7質量份以上的話，會有可形成低速剝離力與高速剝離力之平衡良好的黏著劑層的傾向。 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(B)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為70質量份以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<Content of specific (meth)acrylic polymer (B)>> The content of the specific (meth)acrylic polymer (B) in the adhesive composition of the present invention is 7 parts by mass or more and 70 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer (A). The range of not more than 10 parts by mass is preferably not less than 10 parts by mass and not more than 60 parts by mass, more preferably not less than 15 parts by mass and not more than 55 parts by mass, and particularly preferably not less than 20 parts by mass and not more than 50 parts by mass. When the content of the specific (meth)acrylic polymer (B) in the adhesive composition of the present invention is 7 parts by mass or more with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), there may be a possibility that The tendency to form an adhesive layer with a good balance between low-speed peel force and high-speed peel force. If the content of the specific (meth)acrylic polymer (B) in the adhesive composition of the present invention is 70 parts by mass or less with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), there may be a possibility that There is a tendency to form an adhesive layer in which a zipper phenomenon hardly occurs even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time.

[特定(甲基)丙烯酸系聚合物(C)] 本發明之黏著劑組成物含有玻璃轉移溫度為-30℃以下，且重量平均分子量為6000以上且15萬以下之範圍的(甲基)丙烯酸系聚合物(C)[亦即，特定(甲基)丙烯酸系聚合物(C)]。又，本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(C)之含量，相對於上述特定(甲基)丙烯酸系聚合物(A)100質量份，為0.5質量份以上且5質量份以下之範圍。 本發明之黏著劑組成物可僅含有1種特定(甲基)丙烯酸系聚合物(C)，亦可含有2種以上。[Specific (meth)acrylic polymer (C)] The adhesive composition of the present invention contains a (meth)acrylic polymer (C) [that is, a specific (methyl) ) acrylic polymer (C)]. Moreover, content of the specific (meth)acrylic-type polymer (C) in the adhesive composition of this invention is 0.5 mass part or more with respect to 100 mass parts of the said specific (meth)acrylic-type polymer (A) and 5 parts by mass or less. The adhesive composition of this invention may contain only 1 type of specific (meth)acrylic-type polymer (C), and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(C)，可為均聚物亦可為共聚物。 以下，針對特定(甲基)丙烯酸系聚合物(C)中含有的較佳構成單元進行詳細地說明。The specific (meth)acrylic polymer (C) may be a homopolymer or a copolymer. Hereinafter, the preferable structural unit contained in a specific (meth)acrylic-type polymer (C) is demonstrated in detail.

＜來自(甲基)丙烯酸烷基酯單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(C)宜含有來自(甲基)丙烯酸烷基酯單體之構成單元。 (甲基)丙烯酸烷基酯單體的種類並無特別限定。 (甲基)丙烯酸烷基酯單體宜為無取代之(甲基)丙烯酸烷基酯單體。 (甲基)丙烯酸烷基酯單體之烷基可為直鏈狀、分支鏈狀、或環狀中之任一者。 就烷基之碳數而言，例如考量黏著力的觀點，宜為1以上且18以下之範圍，為1以上且12以下之範圍更佳，為1以上且8以下之範圍尤佳。<Constituent unit derived from alkyl (meth)acrylate monomer> The specific (meth)acrylic polymer (C) preferably contains a structural unit derived from an alkyl (meth)acrylate monomer. The type of the (meth)acrylic acid alkyl ester monomer is not particularly limited. The alkyl (meth)acrylate monomer is preferably an unsubstituted alkyl (meth)acrylate monomer. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably in the range of 1 or more and 18 or less, more preferably in the range of 1 or more and 12 or less, and particularly preferably in the range of 1 or more and 8 or less, from the viewpoint of, for example, adhesive force.

特定(甲基)丙烯酸系聚合物(C)中之(甲基)丙烯酸烷基酯單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之(甲基)丙烯酸烷基酯單體之具體例同樣，故此處省略其說明。 (甲基)丙烯酸烷基酯單體宜為選自丙烯酸甲酯及丙烯酸正丁酯中之至少1種。Specific examples of the (meth)acrylic acid alkyl ester monomer in the specific (meth)acrylic polymer (C) are the same as the alkyl (meth)acrylate in the specific (meth)acrylic polymer (A) The specific example of the base ester monomer is the same, so the description is omitted here. The alkyl (meth)acrylate monomer is preferably at least one selected from methyl acrylate and n-butyl acrylate.

特定(甲基)丙烯酸系聚合物(C)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，可僅含有1種來自(甲基)丙烯酸烷基酯單體之構成單元，亦可含有2種以上。When the specific (meth)acrylic polymer (C) contains a structural unit derived from an alkyl (meth)acrylate monomer, it may contain only one structural unit derived from an alkyl (meth)acrylate monomer, and the Two or more types may be contained.

特定(甲基)丙烯酸系聚合物(C)含有來自(甲基)丙烯酸烷基酯單體之構成單元時，特定(甲基)丙烯酸系聚合物(C)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元，宜為50質量%以上且100質量%以下之範圍，為60質量%以上且100質量%以下之範圍更佳，為70質量%以上且100質量%以下之範圍尤佳。 此處，特定(甲基)丙烯酸系聚合物(C)中之來自(甲基)丙烯酸烷基酯單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為50質量%以上，意指來自(甲基)丙烯酸烷基酯單體之構成單元係作為構成特定(甲基)丙烯酸系聚合物(C)之構成單元之主成分而含有。When the specific (meth)acrylic polymer (C) contains a structural unit derived from an alkyl (meth)acrylate monomer, the alkyl (meth)acrylate derived from the specific (meth)acrylic polymer (C) The content rate of the structural unit of the base ester monomer is not particularly limited, but for example, it is preferably in the range of 50 mass % or more and 100 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (C). The range of 60 mass % or more and 100 mass % or less is more preferable, and the range of 70 mass % or more and 100 mass % or less is especially preferable. Here, the content rate of the structural unit derived from the alkyl (meth)acrylate monomer in the specific (meth)acrylic polymer (C) is relative to the total of the specific (meth)acrylic polymer (C) That the structural unit is 50 mass % or more means that the structural unit derived from the (meth)acrylic acid alkylester monomer is contained as the main component of the structural unit which comprises a specific (meth)acrylic-type polymer (C).

＜來自具有羥基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(C)宜含有來自具有羥基之單體之構成單元。 具有羥基之單體的種類並無特別限定。 特定(甲基)丙烯酸系聚合物(C)中之具有羥基之單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之具有羥基之單體之具體例同樣，故此處省略其說明。 具有羥基之單體宜為(甲基)丙烯酸羥基烷基酯，為具有碳數為1～5之羥基烷基之(甲基)丙烯酸羥基烷基酯更佳，為具有碳數為2～4之羥基烷基之(甲基)丙烯酸羥基烷基酯更佳，為丙烯酸4-羥基丁酯特佳。<Constituent unit derived from a monomer having a hydroxyl group> The specific (meth)acrylic polymer (C) preferably contains a structural unit derived from a monomer having a hydroxyl group. The kind of the monomer having a hydroxyl group is not particularly limited. The specific example of the monomer having a hydroxyl group in the specific (meth)acrylic polymer (C) is the same as the specific example of the monomer having a hydroxyl group in the specific (meth)acrylic polymer (A), so Its description is omitted here. The monomer having a hydroxyl group is preferably a hydroxyalkyl (meth)acrylate, more preferably a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group with a carbon number of 1 to 5, and a hydroxyalkyl (meth)acrylate with a carbon number of 2 to 4 The hydroxyalkyl (meth)acrylate is more preferably hydroxyalkyl, especially 4-hydroxybutyl acrylate.

特定(甲基)丙烯酸系聚合物(C)含有來自具有羥基之單體之構成單元時，可僅含有1種來自具有羥基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (C) contains the structural unit derived from the monomer which has a hydroxyl group, it may contain only 1 type of structural unit derived from the monomer which has a hydroxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(C)含有來自具有羥基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(C)中之來自具有羥基之單體之構成單元的含有率並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元，宜為0.1質量%以上且10質量%以下之範圍，為0.5質量%以上且10質量%以下之範圍更佳，為1質量%以上且8質量%以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(C)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為0.1質量%以上的話，適度地形成交聯結構，故會有剝離時黏著劑層成分朝被黏體之轉移黏附受到抑制的傾向。 特定(甲基)丙烯酸系聚合物(C)中之來自具有羥基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為10質量%以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。When the specific (meth)acrylic polymer (C) contains a structural unit derived from a monomer having a hydroxyl group, the content rate of the structural unit derived from a monomer having a hydroxyl group in the specific (meth)acrylic polymer (C) Although not particularly limited, for example, it is preferably in the range of 0.1 mass % or more and 10 mass % or less, and preferably 0.5 mass % or more and 10 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (C). The range is more preferable, and the range of 1 mass % or more and 8 mass % or less is especially preferable. When the content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (C) is 0.1 mass % or more with respect to all the structural units of the specific (meth)acrylic polymer (C) , a moderately cross-linked structure is formed, so the transfer and adhesion of the adhesive layer components to the adherend tends to be inhibited during peeling. When the content rate of the structural unit derived from the monomer which has a hydroxyl group in the specific (meth)acrylic polymer (C) is 10 mass % or less with respect to all the structural units of the specific (meth)acrylic polymer (C) , there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time.

＜來自具有羧基之單體之構成單元＞ 特定(甲基)丙烯酸系聚合物(C)亦可含有來自具有羧基之單體之構成單元。 具有羧基之單體的種類並無特別限定。 特定(甲基)丙烯酸系聚合物(C)中之具有羧基之單體之具體例，係與特定(甲基)丙烯酸系聚合物(A)中之具有羧基之單體之具體例同樣，故此處省略其說明。<Constituent unit derived from a monomer having a carboxyl group> The specific (meth)acrylic-type polymer (C) may contain the structural unit derived from the monomer which has a carboxyl group. The kind of the monomer having a carboxyl group is not particularly limited. Specific examples of the monomer having a carboxyl group in the specific (meth)acrylic polymer (C) are the same as the specific examples of the monomer having a carboxyl group in the specific (meth)acrylic polymer (A), so Its description is omitted here.

特定(甲基)丙烯酸系聚合物(C)含有來自具有羧基之單體之構成單元時，可僅含有1種來自具有羧基之單體之構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (C) contains the structural unit derived from the monomer which has a carboxyl group, it may contain only 1 type of structural unit derived from the monomer which has a carboxyl group, and may contain 2 or more types.

特定(甲基)丙烯酸系聚合物(C)含有來自具有羧基之單體之構成單元時，特定(甲基)丙烯酸系聚合物(C)中之來自具有羧基之單體之構成單元的含有率並無特別限定。 特定(甲基)丙烯酸系聚合物(C)，例如考量會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向的觀點，宜不含來自具有羧基之單體之構成單元，或來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為超過0質量%且在1質量%以下之範圍較佳，不含來自具有羧基之單體之構成單元，或來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為超過0質量%且在0.5質量%以下之範圍更佳，不含來自具有羧基之單體之構成單元，或來自具有羧基之單體之構成單元的含有率相對於特定(甲基)丙烯酸系聚合物(C)之全部構成單元為超過0質量%且在0.1質量%以下之範圍尤佳，不含來自具有羧基之單體之構成單元特佳。When the specific (meth)acrylic polymer (C) contains a structural unit derived from a monomer having a carboxyl group, the content rate of the structural unit derived from a monomer having a carboxyl group in the specific (meth)acrylic polymer (C) There is no particular limitation. The specific (meth)acrylic polymer (C), for example, is considered to have a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. From a viewpoint, it is preferable not to contain a structural unit derived from a monomer having a carboxyl group, or the content rate of a structural unit derived from a monomer having a carboxyl group is more than 0 mass relative to all the structural units of the specific (meth)acrylic polymer (C). % and the range of 1 mass % or less is preferable, and the content of the structural unit derived from the monomer having a carboxyl group is not contained, or the content rate of the structural unit derived from the monomer having a carboxyl group is relative to the specific (meth)acrylic polymer (C ) is more preferably in the range of more than 0 mass % and 0.5 mass % or less of all constituent units, does not contain constituent units derived from a monomer having a carboxyl group, or the content rate of constituent units derived from a monomer having a carboxyl group is relative to the specific ( It is especially preferable that all the structural units of a meth)acrylic-type polymer (C) are more than 0 mass % and the range of 0.1 mass % or less, and it is especially preferable not to contain the structural unit derived from the monomer which has a carboxyl group.

＜其他構成單元＞ 特定(甲基)丙烯酸系聚合物(C)，在發揮本發明之效果的範圍內，可含有上述構成單元以外的構成單元(所謂其他構成單元)。<Other components> The specific (meth)acrylic polymer (C) may contain structural units other than the above-mentioned structural units (so-called other structural units) within the range in which the effects of the present invention are exhibited.

構成特定(甲基)丙烯酸系聚合物(C)中之其他構成單元的單體之具體例，係與構成特定(甲基)丙烯酸系聚合物(A)中之其他構成單元的單體之具體例同樣，故此處省略其說明。Specific examples of monomers constituting other structural units in the specific (meth)acrylic polymer (C) are specific examples of monomers constituting other structural units in the specific (meth)acrylic polymer (A) The example is the same, so the description is omitted here.

特定(甲基)丙烯酸系聚合物(C)含有其他構成單元時，可僅含有1種其他構成單元，亦可含有2種以上。When a specific (meth)acrylic-type polymer (C) contains other structural unit, only 1 type of other structural unit may be contained, and 2 or more types may be contained.

特定(甲基)丙烯酸系聚合物(C)含有其他構成單元時，特定(甲基)丙烯酸系聚合物(C)中之其他構成單元的含有率並無特別限定，可因應目的適當設定。When a specific (meth)acrylic-type polymer (C) contains another structural unit, the content rate of the other structural unit in a specific (meth)acrylic-type polymer (C) is not specifically limited, According to the objective, it can set suitably.

＜＜特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度＞＞ 特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度為-30℃以下，宜為-65℃以上且-30℃以下之範圍，為-65℃以上且-40℃以下之範圍更佳，為-65℃以上且-45℃以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度為-30℃以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<The glass transition temperature of the specific (meth)acrylic polymer (C)>> The glass transition temperature of the specific (meth)acrylic polymer (C) is -30°C or lower, preferably -65°C or higher and -30°C or lower, more preferably -65°C or higher and -40°C or lower , the range of -65°C or higher and -45°C or lower is particularly preferable. If the glass transition temperature of the specific (meth)acrylic polymer (C) is -30°C or lower, a zipper will not easily occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. phenomenon of the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度，係利用與特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度同樣之方法求出之值。The glass transition temperature of the specific (meth)acrylic polymer (C) is a value determined by the same method as the glass transition temperature of the specific (meth)acrylic polymer (A).

特定(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度，例如可藉由使用2種以上之製成均聚物時之玻璃轉移溫度不同的單體來適當調整。The glass transition temperature of the specific (meth)acrylic polymer (C) can be appropriately adjusted by using, for example, two or more monomers having different glass transition temperatures when used as a homopolymer.

＜＜特定(甲基)丙烯酸系聚合物(C)之重量平均分子量＞＞ 特定(甲基)丙烯酸系聚合物(C)之重量平均分子量為6000以上且15萬以下之範圍，宜為7000以上且13萬以下之範圍，為8000以上且10萬以下之範圍更佳，為9000以上且8萬以下之範圍尤佳。 特定(甲基)丙烯酸系聚合物(C)之重量平均分子量為6000以上的話，會有可形成低速剝離力與高速剝離力之平衡良好的黏著劑層的傾向。 特定(甲基)丙烯酸系聚合物(C)之重量平均分子量為15萬以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<The weight average molecular weight of the specific (meth)acrylic polymer (C)>> The weight average molecular weight of the specific (meth)acrylic polymer (C) is in the range of 6,000 or more and 150,000 or less, preferably in the range of 7,000 or more and 130,000 or less, more preferably in the range of 8,000 or more and 100,000 or less, The range above 9,000 and below 80,000 is preferred. When the weight-average molecular weight of the specific (meth)acrylic polymer (C) is 6,000 or more, there is a tendency to form an adhesive layer with a good balance between the low-speed peeling force and the high-speed peeling force. If the weight-average molecular weight of the specific (meth)acrylic polymer (C) is 150,000 or less, there is a possibility that even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed, the zipper phenomenon does not easily occur. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(C)之重量平均分子量，係利用與特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)同樣之方法測得之值。The weight average molecular weight of the specific (meth)acrylic polymer (C) is a value measured by the same method as the weight average molecular weight (Mw) of the specific (meth)acrylic polymer (A).

特定(甲基)丙烯酸系聚合物(C)之重量平均分子量，可藉由調整聚合溫度、聚合時間、有機溶劑的使用量、聚合引發劑的種類、聚合引發劑的使用量等而使其成為期望之值。The weight-average molecular weight of the specific (meth)acrylic polymer (C) can be adjusted by adjusting the polymerization temperature, the polymerization time, the amount of the organic solvent used, the type of the polymerization initiator, the amount of the polymerization initiator used, and the like. expected value.

特定(甲基)丙烯酸系聚合物(C)之重量平均分子量，宜比上述特定(甲基)丙烯酸系聚合物(B)之重量平均分子量小較佳。 特定(甲基)丙烯酸系聚合物(C)之重量平均分子量比特定(甲基)丙烯酸系聚合物(B)之重量平均分子量小的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。The weight average molecular weight of the specific (meth)acrylic polymer (C) is preferably smaller than the weight average molecular weight of the specific (meth)acrylic polymer (B). If the weight-average molecular weight of the specific (meth)acrylic polymer (C) is smaller than the weight-average molecular weight of the specific (meth)acrylic polymer (B), it may be formed even after being attached to the adherend for a long time. Even when peeled from the adherend at high speed, the adhesive layer of the zipper phenomenon is less likely to occur.

＜＜特定(甲基)丙烯酸系聚合物(C)之羥值＞＞ 特定(甲基)丙烯酸系聚合物(C)之羥值並無特別限定，例如，宜為40mgKOH/g以下，為0mgKOH/g以上且40mgKOH/g以下之範圍更佳，為0.3mgKOH/g以上且40mgKOH/g以下之範圍尤佳，為0.5mgKOH/g以上且30mgKOH/g以下之範圍特佳。 本說明書中，特定(甲基)丙烯酸系聚合物(C)之羥值為0mgKOH/g，意指特定(甲基)丙烯酸系聚合物(C)不含羥基。 特定(甲基)丙烯酸系聚合物(C)之羥值為40mgKOH/g以下的話，會有所形成之黏著劑層展現更適當的高速剝離力的傾向。<<Hydroxy value of specific (meth)acrylic polymer (C)>> The hydroxyl value of the specific (meth)acrylic polymer (C) is not particularly limited. For example, it is preferably 40 mgKOH/g or less, more preferably 0 mgKOH/g or more and 40 mgKOH/g or less, and 0.3 mgKOH/g or more. And the range of 40 mgKOH/g or less is especially preferable, and the range of 0.5 mgKOH/g or more and 30 mgKOH/g or less is especially preferable. In this specification, the hydroxyl value of the specific (meth)acrylic polymer (C) is 0 mgKOH/g, which means that the specific (meth)acrylic polymer (C) does not contain a hydroxyl group. When the hydroxyl value of the specific (meth)acrylic polymer (C) is 40 mgKOH/g or less, the formed adhesive layer tends to exhibit a more suitable high-speed peeling force.

特定(甲基)丙烯酸系聚合物(C)之羥值，係利用與特定(甲基)丙烯酸系聚合物(A)之羥值同樣之方法而算出之值。The hydroxyl value of the specific (meth)acrylic polymer (C) is a value calculated by the same method as the hydroxyl value of the specific (meth)acrylic polymer (A).

＜＜特定(甲基)丙烯酸系聚合物(C)之酸價＞＞ 特定(甲基)丙烯酸系聚合物(C)之酸價並無特別限定，例如，宜為7mgKOH/g以下，為0mgKOH/g以上且7mgKOH/g以下之範圍更佳，為0mgKOH/g以上且3.5mgKOH/g以下之範圍尤佳，為0mgKOH/g特佳。 本說明書中，特定(甲基)丙烯酸系聚合物(C)之酸價為0mgKOH/g，意指特定(甲基)丙烯酸系聚合物(C)不含羧基。 特定(甲基)丙烯酸系聚合物(C)之酸價為7mgKOH/g以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。<<Acid value of specific (meth)acrylic polymer (C)>> The acid value of the specific (meth)acrylic polymer (C) is not particularly limited. For example, it is preferably 7 mgKOH/g or less, more preferably 0 mgKOH/g or more and 7 mgKOH/g or less, more preferably 0 mgKOH/g or more and The range below 3.5 mgKOH/g is particularly preferred, and 0 mgKOH/g is particularly preferred. In this specification, the acid value of the specific (meth)acrylic polymer (C) is 0 mgKOH/g, which means that the specific (meth)acrylic polymer (C) does not contain a carboxyl group. If the acid value of the specific (meth)acrylic polymer (C) is 7 mgKOH/g or less, the zipper phenomenon is unlikely to occur even if it is attached to the adherend for a long time and then peeled off from the adherend at a high speed. the tendency of the adhesive layer.

特定(甲基)丙烯酸系聚合物(C)之酸價，係利用與特定(甲基)丙烯酸系聚合物(A)之酸價同樣之方法而算出之值。The acid value of the specific (meth)acrylic polymer (C) is a value calculated by the same method as the acid value of the specific (meth)acrylic polymer (A).

特定(甲基)丙烯酸系聚合物(C)可使用市售品。 特定(甲基)丙烯酸系聚合物(C)之市售品之示例，可列舉：UP-1080[商品名、玻璃轉移溫度：-61℃、重量平均分子量：6000、東亞合成(股)製]、UP-1170[商品名、玻璃轉移溫度：-57℃、重量平均分子量：8000、東亞合成(股)製]、UH-2000[商品名、具有羥基之(甲基)丙烯酸系聚合物、玻璃轉移溫度：-55℃、重量平均分子量：11000、東亞合成(股)製]、UH-2190[商品名、具有羥基之(甲基)丙烯酸系聚合物、玻璃轉移溫度：-47℃、重量平均分子量：6000、東亞合成(股)製]等。A commercial item can be used for a specific (meth)acrylic-type polymer (C). Examples of commercial products of the specific (meth)acrylic polymer (C) include: UP-1080 [trade name, glass transition temperature: -61°C, weight average molecular weight: 6000, manufactured by Toagosei Co., Ltd.] , UP-1170 [trade name, glass transition temperature: -57°C, weight average molecular weight: 8000, manufactured by Toagosei Co., Ltd.], UH-2000 [trade name, (meth)acrylic polymer with hydroxyl group, glass Transition temperature: -55°C, weight average molecular weight: 11000, manufactured by Toagosei Co., Ltd.], UH-2190 [trade name, (meth)acrylic polymer having a hydroxyl group, glass transition temperature: -47°C, weight average Molecular weight: 6000, manufactured by Toagosei (stock)] and so on.

＜＜特定(甲基)丙烯酸系聚合物(C)之含量＞＞ 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(C)之含量，相對於特定(甲基)丙烯酸系聚合物(A)100質量份，為0.5質量份以上且5質量份以下之範圍，宜為0.5質量份以上且4.5質量份以下之範圍，為1質量份以上且4質量份以下之範圍更佳，為1.5質量份以上且3質量份以下之範圍尤佳。 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(C)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為0.5質量份以上的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。 本發明之黏著劑組成物中之特定(甲基)丙烯酸系聚合物(C)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為5質量份以下的話，會有可形成低速剝離力與高速剝離力之平衡良好的黏著劑層的傾向。＜＜Content of specific (meth)acrylic polymer (C)＞ The content of the specific (meth)acrylic polymer (C) in the adhesive composition of the present invention is 0.5 parts by mass or more and 5 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer (A). The range of 0.5 parts by mass or more and 4.5 parts by mass or less is preferable, the range of 1 part by mass or more and 4 parts by mass or less is more preferable, and the range of 1.5 parts by mass or more and 3 parts by mass or less is particularly preferable. When the content of the specific (meth)acrylic polymer (C) in the adhesive composition of the present invention is 0.5 parts by mass or more with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), there may be a possibility that There is a tendency to form an adhesive layer in which a zipper phenomenon hardly occurs even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time. When the content of the specific (meth)acrylic polymer (C) in the adhesive composition of the present invention is 5 parts by mass or less with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), there may be a possibility that The tendency to form an adhesive layer with a good balance between low-speed peel force and high-speed peel force.

本發明之黏著劑組成物之較佳態樣，可列舉特定(甲基)丙烯酸系聚合物(C)之重量平均分子量比特定(甲基)丙烯酸系聚合物(B)之重量平均分子量小，且特定(甲基)丙烯酸系聚合物(C)之含量比特定(甲基)丙烯酸系聚合物(B)之含量少的態樣。 依上述態樣，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。A preferred aspect of the adhesive composition of the present invention is that the weight average molecular weight of the specific (meth)acrylic polymer (C) is smaller than the weight average molecular weight of the specific (meth)acrylic polymer (B), And the aspect in which content of a specific (meth)acrylic-type polymer (C) is smaller than content of a specific (meth)acrylic-type polymer (B). According to the above aspect, there is a tendency to form an adhesive layer that does not easily cause a zipper phenomenon even when it is peeled off from the adherend at a high speed after being attached to the adherend for a long period of time.

[特定(甲基)丙烯酸系聚合物之製造方法] 特定(甲基)丙烯酸系聚合物(A)、特定(甲基)丙烯酸系聚合物(B)、及特定(甲基)丙烯酸系聚合物(C)[亦即，特定(甲基)丙烯酸系聚合物]之製造方法並無特別限定。 特定(甲基)丙烯酸系聚合物，例如可藉由利用以溶液聚合法、乳化聚合法、懸浮聚合法、及塊狀聚合法為代表的公知聚合方法，將上述單體進行聚合而製造。又，特定(甲基)丙烯酸系聚合物，例如可藉由利用以溶液聚合法、乳化聚合法、懸浮聚合法、及塊狀聚合法為代表的公知聚合方法，將不具有羥基及羧基中之任一者之單體進行聚合而製造(甲基)丙烯酸系聚合物後，於製得之(甲基)丙烯酸系聚合物中，藉由取代而導入羥基及羧基中之至少一者來製造。 就聚合方法而言，考量製造後製備本發明之黏著劑組成物時，處理步驟較簡單，且能於短時間進行的觀點，宜為溶液聚合法。[Manufacturing method of specific (meth)acrylic polymer] Specific (meth)acrylic polymer (A), specific (meth)acrylic polymer (B), and specific (meth)acrylic polymer (C) [that is, specific (meth)acrylic The production method of the polymer] is not particularly limited. The specific (meth)acrylic polymer can be produced by polymerizing the above-mentioned monomers by, for example, a known polymerization method represented by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method. In addition, the specific (meth)acrylic polymer can be obtained by using, for example, a well-known polymerization method represented by solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. After polymerizing any one of the monomers to produce a (meth)acrylic polymer, at least one of a hydroxyl group and a carboxyl group is introduced into the produced (meth)acrylic polymer by substitution, and the production is produced. As for the polymerization method, when the adhesive composition of the present invention is prepared after production, the processing steps are relatively simple and can be carried out in a short time, so the solution polymerization method is suitable.

溶液聚合法中，一般係於聚合槽內加入預定的有機溶劑、單體、聚合引發劑、及視需要使用之鏈轉移劑，於氮氣流中，在有機溶劑之回流溫度邊攪拌邊加熱反應數小時。此時，亦可逐次添加有機溶劑、單體、聚合引發劑及/或鏈轉移劑中之至少一部分。In the solution polymerization method, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent as needed are generally added to the polymerization tank, and the reaction mixture is heated at the reflux temperature of the organic solvent while stirring in a nitrogen stream. Hour. At this time, at least a part of the organic solvent, monomer, polymerization initiator and/or chain transfer agent may be added sequentially.

聚合反應時使用之有機溶劑，可列舉：芳香族烴化合物、脂肪族系或脂環族系烴化合物、酯化合物、酮化合物、二醇醚化合物、醇化合物等。 聚合反應時使用之有機溶劑，更具體而言，例如可列舉：以苯、甲苯、乙苯、正丙苯、第三丁苯、鄰二甲苯、間二甲苯、對二甲苯、四氫萘、十氫萘、及芳香族石油腦為代表的芳香族烴化合物；以正己烷、正庚烷、正辛烷、異辛烷、正癸烷、二戊烯、石油精、石油腦、及松節油為代表的脂肪族系或脂環族系烴化合物；以乙酸乙酯、乙酸正丁酯、乙酸正戊酯、乙酸2-羥基乙酯、乙酸2-丁氧基乙酯、乙酸3-甲氧基丁酯、及苯甲酸甲酯為代表的酯化合物；以丙酮、甲乙酮、甲基異丁基酮、異佛酮、環己酮、及甲基環己酮為代表的酮化合物；以乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、及二乙二醇單丁醚為代表的二醇醚化合物；及以甲醇、乙基醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、及第三丁醇為代表的醇化合物。The organic solvent used in the polymerization reaction includes aromatic hydrocarbon compounds, aliphatic or alicyclic hydrocarbon compounds, ester compounds, ketone compounds, glycol ether compounds, alcohol compounds, and the like. More specifically, the organic solvent used in the polymerization reaction includes, for example, benzene, toluene, ethylbenzene, n-propylbenzene, tertiary butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, Aromatic hydrocarbon compounds represented by decalin and aromatic naphtha; n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit, naphtha, and turpentine are Representative aliphatic or alicyclic hydrocarbon compounds; with ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxy acetate Ester compounds represented by butyl ester and methyl benzoate; ketone compounds represented by acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methyl cyclohexanone; ethylene glycol Glycol ether compounds represented by monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and Alcohol compounds represented by methanol, ethyl alcohol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol.

特定(甲基)丙烯酸系聚合物之製造時，宜使用芳香族烴化合物、酯化合物、酮化合物等在聚合反應中不易發生鏈轉移的有機溶劑，尤其考量特定(甲基)丙烯酸系聚合物之溶解性、聚合反應之容易度等的觀點，宜使用選自由乙酸乙酯、甲苯、及甲乙酮構成之群組中之至少1種。In the production of specific (meth)acrylic polymers, organic solvents such as aromatic hydrocarbon compounds, ester compounds, ketone compounds, etc., which do not easily undergo chain transfer during polymerization, are preferably used, especially considering the properties of specific (meth)acrylic polymers. From the viewpoints of solubility and ease of polymerization reaction, at least one selected from the group consisting of ethyl acetate, toluene, and methyl ethyl ketone is preferably used.

聚合反應時可僅使用1種有機溶劑，亦可使用2種以上。In the polymerization reaction, only one type of organic solvent may be used, or two or more types may be used.

聚合引發劑可列舉通常的溶液聚合法中使用之有機過氧化物、偶氮化合物等。 作為有機過氧化物，例如可列舉：第三丁基過氧化氫、異丙苯過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化月桂醯、過氧化己醯、過氧化二碳酸二異丙酯、過氧化二碳酸二-2-乙基己酯、過氧化三甲基乙酸第三丁酯、2,2-雙(4,4-二-第三丁基過氧化環己基)丙烷、2,2-雙(4,4-二-第三戊基過氧化環己基)丙烷、2,2-雙(4,4-二-第三辛基過氧化環己基)丙烷、2,2-雙(4,4-二-α-異丙苯基過氧化環己基)丙烷、2,2-雙(4,4-二-第三丁基過氧化環己基)丁烷、及2,2-雙(4,4-二-第三辛基過氧化環己基)丁烷。 作為偶氮化合物，例如可列舉：2,2’-偶氮雙異丁腈[AIBN]、2,2’-偶氮雙(2,4-二甲基戊腈)[ABVN]、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、1,1’-偶氮雙(環己烷-1-甲腈)、及2,2’-偶氮雙(異丁酸)二甲酯。 特定(甲基)丙烯酸系聚合物之製造時，宜使用不會在聚合反應中引起接枝反應的聚合引發劑，尤其宜使用偶氮化合物。Examples of the polymerization initiator include organic peroxides, azo compounds, and the like used in a general solution polymerization method. Examples of organic peroxides include tert-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzyl peroxide, lauryl peroxide, hexamethylene peroxide, peroxide Diisopropyl dicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxytrimethylacetate, 2,2-bis(4,4-di-tert-butylperoxide) Hexyl)propane, 2,2-bis(4,4-di-tert-pentylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-isopropylphenylcyclohexylperoxide)propane, 2,2-bis(4,4-di-tert-butylcyclohexylperoxide)butane, and 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)butane. Examples of the azo compound include 2,2'-azobisisobutyronitrile [AIBN], 2,2'-azobis(2,4-dimethylvaleronitrile) [ABVN], 2,2 '-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azo Dimethyl bis(isobutyrate). When producing a specific (meth)acrylic polymer, it is preferable to use a polymerization initiator that does not cause a graft reaction in the polymerization reaction, and particularly an azo compound is preferably used.

聚合反應時可僅使用1種聚合引發劑，亦可使用2種以上。In the polymerization reaction, only one type of polymerization initiator may be used, or two or more types may be used.

聚合引發劑的使用量並無特別限定，例如可因應作為目的之特定(甲基)丙烯酸系聚合物之分子量適當設定。The usage-amount of a polymerization initiator is not specifically limited, For example, it can set suitably according to the molecular weight of the specific (meth)acrylic-type polymer which is an objective.

特定(甲基)丙烯酸系聚合物之製造時，亦可視需要使用鏈轉移劑。 作為鏈轉移劑，例如可列舉：氰乙酸、氰乙酸之碳數1～8之烷基酯化合物、溴乙酸、溴乙酸之碳數1～8之烷基酯化合物；以α-甲基苯乙烯、蒽、菲、茀、及9-苯基茀為代表的芳香族化合物；以對硝基苯胺、硝基苯、二硝基苯、對硝基苯甲酸、對硝基苯酚、及對硝基甲苯為代表的芳香族硝基化合物；以苯醌及2,3,5,6-四甲基-對苯醌為代表的苯醌衍生物；以三丁基硼烷為代表的硼烷衍生物；以四溴化碳、四氯化碳、1,1,2,2-四溴乙烷、三溴乙烯、三氯乙烯、溴三氯甲烷、三溴甲烷、及3-氯-1-丙烯為代表的鹵化烴化合物；以氯醛及呋喃甲醛為代表的醛化合物；以碳數1～18之烷基硫醇化合物、硫苯酚及甲苯硫醇為代表的芳香族硫醇化合物；巰基乙酸、巰基乙酸之碳數1～10之烷基酯化合物、碳數1～12之羥基烷基硫醇化合物；及以蒎烯及萜品油烯(terpinolene)為代表的萜烯化合物。When producing a specific (meth)acrylic polymer, a chain transfer agent may be used as needed. Examples of the chain transfer agent include: cyanoacetic acid, alkyl ester compounds with 1 to 8 carbon atoms of cyanoacetic acid, bromoacetic acid, and alkyl ester compounds of 1 to 8 carbon atoms of bromoacetic acid; α-methylstyrene Aromatic compounds represented by , anthracene, phenanthrene, phenanthrene, and 9-phenyl fluoride; p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, and p-nitro Aromatic nitro compounds represented by toluene; benzoquinone derivatives represented by benzoquinone and 2,3,5,6-tetramethyl-p-benzoquinone; borane derivatives represented by tributylborane ; take carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, and 3-chloro-1-propene as Representative halogenated hydrocarbon compounds; Aldehyde compounds represented by chloral and furancarboxaldehyde; Aromatic thiol compounds represented by alkylthiol compounds with carbon number 1 to 18, thiophenol and toluenethiol; thioglycolic acid, mercapto An alkyl ester compound having 1 to 10 carbon atoms of acetic acid, a hydroxyalkylthiol compound having 1 to 12 carbon atoms, and a terpene compound represented by pinene and terpinolene.

特定(甲基)丙烯酸系聚合物之製造時，使用鏈轉移劑的情況下，鏈轉移劑的使用量並無特別限定，例如可因應作為目的之特定(甲基)丙烯酸系聚合物之分子量適當設定。When a chain transfer agent is used in the production of a specific (meth)acrylic polymer, the amount of the chain transfer agent to be used is not particularly limited. For example, it may be appropriate according to the molecular weight of the specific (meth)acrylic polymer intended for use. set up.

聚合溫度並無特別限定，例如可因應作為目的之特定(甲基)丙烯酸系聚合物之分子量適當設定。The polymerization temperature is not particularly limited, and can be appropriately set, for example, according to the molecular weight of the specific (meth)acrylic polymer to be used.

[異氰酸酯系交聯劑(D)] 本發明之黏著劑組成物含有異氰酸酯系交聯劑(D)。 本說明書中，「異氰酸酯系交聯劑(D)」，係指分子內具有2個以上之異氰酸酯基的化合物(所謂多異氰酸酯化合物)。[Isocyanate-based crosslinking agent (D)] The adhesive composition of the present invention contains an isocyanate-based crosslinking agent (D). In this specification, "isocyanate type crosslinking agent (D)" means the compound (so-called polyisocyanate compound) which has two or more isocyanate groups in a molecule|numerator.

異氰酸酯系交聯劑(D)並無特別限定。 作為異氰酸酯系交聯劑(D)，例如可列舉：二甲苯二異氰酸酯(XDI)、二苯基甲烷二異氰酸酯、三苯基甲烷三異氰酸酯、及甲苯二異氰酸酯(TDI)等芳香族多異氰酸酯化合物；六亞甲基二異氰酸酯(HMDI)、五亞甲基二異氰酸酯(PDI)、異佛酮二異氰酸酯、及芳香族多異氰酸酯化合物之氫化物等脂肪族或脂環族多異氰酸酯化合物。 又，作為異氰酸酯系交聯劑(D)，例如亦可列舉：上述多異氰酸酯化合物之2聚物、3聚物、或5聚物、上述多異氰酸酯化合物與三羥甲基丙烷等多元醇化合物之加成體、及上述多異氰酸酯化合物之雙脲體。 又，作為異氰酸酯系交聯劑(D)，亦可列舉分子內具有2個以上之異氰酸酯基、與聚矽氧烷結構及環氧烷結構的化合物(所謂聚矽氧系多異氰酸酯化合物)。 聚矽氧系多異氰酸酯化合物之具體例，例如可列舉日本特開2019-35066號公報之段落[0102]～段落[0118]記載之聚矽氧系異氰酸酯化合物(C)之例示化合物。The isocyanate-based crosslinking agent (D) is not particularly limited. Examples of the isocyanate-based crosslinking agent (D) include aromatic polyisocyanate compounds such as xylene diisocyanate (XDI), diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate (TDI); Aliphatic or alicyclic polyisocyanate compounds such as hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate, and hydrogenated products of aromatic polyisocyanate compounds. Moreover, as an isocyanate type crosslinking agent (D), the dimer, trimer, or pentamer of the above-mentioned polyisocyanate compound, the compound of the polyol compound such as the above-mentioned polyisocyanate compound and trimethylolpropane can also be mentioned, for example. An adduct, and a diurea body of the above-mentioned polyisocyanate compound. Moreover, as an isocyanate type crosslinking agent (D), the compound (so-called polysiloxane type polyisocyanate compound) which has two or more isocyanate groups, a polysiloxane structure, and an alkylene oxide structure in a molecule|numerator can also be mentioned. Specific examples of the polysiloxane-based polyisocyanate compound include, for example, exemplary compounds of the polysiloxane-based isocyanate compound (C) described in paragraphs [0102] to [0118] of JP-A No. 2019-35066.

該等之中，異氰酸酯系交聯劑(D)宜為六亞甲基二異氰酸酯。 異氰酸酯系交聯劑(D)為六亞甲基二異氰酸酯的話，會有可形成具有更適合於保護薄膜之用途之剝離力的黏著劑層的傾向。Among these, the isocyanate-based crosslinking agent (D) is preferably hexamethylene diisocyanate. When the isocyanate-based crosslinking agent (D) is hexamethylene diisocyanate, there is a tendency that an adhesive layer having a peeling force more suitable for the use of a protective film can be formed.

異氰酸酯系交聯劑(D)可使用市售品。 異氰酸酯系交聯劑(D)之市售品之示例，可列舉：「CORONATE(註冊商標)HX」、「CORONATE(註冊商標)HL-S」、「CORONATE(註冊商標)L」、「CORONATE(註冊商標)L-45E」、「CORONATE(註冊商標)2031」、「CORONATE(註冊商標)2030」、「CORONATE(註冊商標)2234」、「CORONATE(註冊商標)2785」、「AQUANATE(註冊商標)200」、及「AQUANATE(註冊商標)210」[以上為東曹(股)製]、「SUMIDUR(註冊商標)N3300」、「DESMODUR(註冊商標)N3400」、及「SUMIDUR(註冊商標)N75」[以上為Sumika Covestro Urethane(股)製]、「DURANATE(註冊商標)E-405-80T」、「DURANATE(註冊商標)AE700-100」、「DURANATE(註冊商標)24A-100」、及「DURANATE(註冊商標)TSE-100」[以上為旭化成(股)製]、以及、「TAKENATE(註冊商標)D-110N」、「TAKENATE(註冊商標)D-120N」、「TAKENATE(註冊商標)M-631N」、「MT-OLESTER(註冊商標)NP1200」、及「STABiO(註冊商標)XD-340N」[以上為三井化學(股)製]。As the isocyanate-based crosslinking agent (D), a commercial item can be used. Examples of commercially available isocyanate-based crosslinking agents (D) include "CORONATE (registered trademark) HX", "CORONATE (registered trademark) HL-S", "CORONATE (registered trademark) L", "CORONATE (registered trademark) Registered trademark) L-45E", "CORONATE (registered trademark) 2031", "CORONATE (registered trademark) 2030", "CORONATE (registered trademark) 2234", "CORONATE (registered trademark) 2785", "AQUANATE (registered trademark)" 200", and "AQUANATE (registered trademark) 210" [the above are manufactured by Tosoh Corporation], "SUMIDUR (registered trademark) N3300", "DESMODUR (registered trademark) N3400", and "SUMIDUR (registered trademark) N75" [The above are manufactured by Sumika Covestro Urethane Co., Ltd.], "DURANATE (registered trademark) E-405-80T", "DURANATE (registered trademark) AE700-100", "DURANATE (registered trademark) 24A-100", and "DURANATE (registered trademark) 24A-100" (registered trademark) TSE-100” [the above are manufactured by Asahi Kasei Corporation], and, “TAKENATE (registered trademark) D-110N”, “TAKENATE (registered trademark) D-120N”, “TAKENATE (registered trademark) M- 631N", "MT-OLESTER (registered trademark) NP1200", and "STABiO (registered trademark) XD-340N" [the above are manufactured by Mitsui Chemicals Co., Ltd.].

本發明之黏著劑組成物可僅含有1種異氰酸酯系交聯劑(D)，亦可含有2種以上。The adhesive composition of this invention may contain only 1 type of isocyanate type crosslinking agent (D), and may contain 2 or more types.

本發明之黏著劑組成物中之異氰酸酯系交聯劑(D)之含量，並無特別限定，例如相對於特定(甲基)丙烯酸系聚合物(A)100質量份，宜為0.1質量份以上且7.0質量份以下之範圍，為0.3質量份以上且7.0質量份以下之範圍更佳，為0.5質量份以上且5.0質量份以下之範圍尤佳，為0.5質量份以上且3.0質量份以下之範圍特佳。 本發明之黏著劑組成物中之異氰酸酯系交聯劑(D)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為0.1質量份以上的話，會有可形成低速剝離力與高速剝離力之平衡更良好的黏著劑層的傾向。 本發明之黏著劑組成物中之異氰酸酯系交聯劑(D)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份為7.0質量份以下的話，會有可形成即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層的傾向。The content of the isocyanate-based crosslinking agent (D) in the adhesive composition of the present invention is not particularly limited. For example, it is preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific (meth)acrylic polymer (A). And the range of 7.0 parts by mass or less is more preferably the range of 0.3 parts by mass or more and 7.0 parts by mass or less, the range of 0.5 parts by mass or more and 5.0 parts by mass or less is particularly preferable, and the range of 0.5 parts by mass or more and 3.0 parts by mass or less is more preferable. Excellent. When the content of the isocyanate-based crosslinking agent (D) in the adhesive composition of the present invention is 0.1 part by mass or more with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), a low-speed peeling force can be formed. The tendency of the adhesive layer to be better balanced with the high-speed peel force. If the content of the isocyanate-based crosslinking agent (D) in the adhesive composition of the present invention is 7.0 parts by mass or less with respect to 100 parts by mass of the specific (meth)acrylic polymer (A), there is a possibility that it can be formed even for a long period of time. The adhesive layer of the zipper phenomenon also tends to be less likely to occur when it is peeled off from the adherend at a high speed after being attached to the adherend.

[有機溶劑] 本發明之黏著劑組成物亦可含有有機溶劑。 本發明之黏著劑組成物含有有機溶劑的話，可改善塗布性。 就有機溶劑而言，例如可列舉與上述特定(甲基)丙烯酸系聚合物之聚合反應時使用之有機溶劑同樣者。[Organic solvents] The adhesive composition of the present invention may also contain an organic solvent. When the adhesive composition of the present invention contains an organic solvent, coatability can be improved. As an organic solvent, the thing similar to the organic solvent used at the time of the polymerization reaction of the above-mentioned specific (meth)acrylic-type polymer is mentioned, for example.

本發明之黏著劑組成物含有有機溶劑時，可僅含有1種有機溶劑，亦可含有2種以上。When the adhesive composition of the present invention contains an organic solvent, only one type of organic solvent may be contained, or two or more types may be contained.

本發明之黏著劑組成物含有有機溶劑時，有機溶劑之含量並無特別限定，可因應目的適當設定。When the adhesive composition of the present invention contains an organic solvent, the content of the organic solvent is not particularly limited, and can be appropriately set according to the purpose.

[抗靜電劑] 本發明之黏著劑組成物亦可含有抗靜電劑。 抗靜電劑並無特別限定，例如可列舉離子性化合物。 離子性化合物可列舉鹼金屬鹽、有機鹽等。 該等之中，離子性化合物宜為鹼金屬鹽。 鹼金屬鹽只要是以鋰離子(Li+ )、鈉離子(Na+ )、鉀離子(K+ )、銣離子(Rb+ )等作為陽離子的金屬鹽，則無特別限定。 鹼金屬鹽宜為由選自由Li+ 、Na+ 、及K+ 構成之群組中之至少1種陽離子、與選自由Cl- 、Br- 、I- 、BF4 - 、PF6 - 、SCN- 、ClO4 - 、CF3 SO3 - 、(FSO2 )2 N- 、(CF3 SO2 )2 N- 、(C2 F5 SO2 )2 N- 、及(CF3 SO2 )3 C- 構成之群組中之至少1種陰離子構成的金屬鹽較佳，為LiBr、LiI、LiBF4 、LiPF6 、LiSCN、LiClO4 、LiCF3 SO3 (所謂LiTFS)、Li(FSO2 )2 N、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(CF3 SO2 )3 C等鋰鹽更佳，為選自由LiClO4 、LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、及Li(CF3 SO2 )3 C構成之群組中之至少1種鋰鹽尤佳。[Antistatic Agent] The adhesive composition of the present invention may contain an antistatic agent. Although an antistatic agent is not specifically limited, For example, an ionic compound is mentioned. Examples of the ionic compound include alkali metal salts, organic salts, and the like. Among these, the ionic compound is preferably an alkali metal salt. The alkali metal salt is not particularly limited as long as it is a metal salt whose cation is lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), or the like. The alkali metal salt is preferably at least one cation selected from the group consisting of Li + , Na + , and K + , and at least one cation selected from Cl − , Br − , I − , BF 4 − , PF 6 − , SCN − , ClO 4 - , CF 3 SO 3 - , (FSO 2 ) 2 N - , (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , and (CF 3 SO 2 ) 3 C - The metal salt composed of at least one anion in the group is preferably LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 (so-called LiTFS), Li(FSO 2 ) 2 N , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C and other lithium salts are more preferable, and are selected from LiClO 4 , LiCF 3 SO 3 , Li At least one lithium salt selected from the group consisting of (CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, and Li(CF 3 SO 2 ) 3 C is particularly preferred.

本發明之黏著劑組成物含有抗靜電劑時，可僅含有1種抗靜電劑，亦可含有2種以上。When the adhesive composition of the present invention contains an antistatic agent, only one type of antistatic agent may be contained, or two or more types may be contained.

本發明之黏著劑組成物含有抗靜電劑時，抗靜電劑之含量並無特別限定，可因應目的適當設定。When the adhesive composition of the present invention contains an antistatic agent, the content of the antistatic agent is not particularly limited, and can be appropriately set according to the purpose.

[聚醚改性聚矽氧化合物] 本發明之黏著劑組成物亦可含有聚醚改性聚矽氧化合物。 此外，本說明書中之「聚醚改性聚矽氧化合物」不包括上述聚矽氧系多異氰酸酯化合物。 本發明之黏著劑組成物中，聚醚改性聚矽氧化合物可作為剝離調整劑而發揮功能。 又，本發明之黏著劑組成物中，聚醚改性聚矽氧化合物可作為抗靜電助劑而發揮功能。因此，本發明之黏著劑組成物宜含有聚醚改性聚矽氧化合物與抗靜電劑之組合。 聚醚改性聚矽氧化合物並無特別限定，例如，宜為選自由於係主鏈之聚矽氧烷鏈之側鏈之一部分鍵結末端具有羥基之環氧烷結構而得的聚矽氧化合物、鍵結末端具有乙醯基之環氧烷結構而得的聚矽氧化合物、及於係主鏈之聚矽氧烷鏈之兩末端鍵結末端具有羥基之環氧烷結構而得的聚矽氧化合物構成之群組中之至少1種聚矽氧化合物[以下，亦稱為「特定聚醚改性聚矽氧化合物」。]較佳。[Polyether modified polysiloxane] The adhesive composition of the present invention may also contain a polyether-modified polysiloxane compound. In addition, the "polyether-modified polysiloxane compound" in this specification does not include the above-mentioned polysiloxane-based polyisocyanate compound. In the adhesive composition of the present invention, the polyether-modified polysiloxane can function as a peeling regulator. In addition, in the adhesive composition of the present invention, the polyether-modified polysiloxane can function as an antistatic auxiliary. Therefore, the adhesive composition of the present invention preferably contains a combination of a polyether-modified polysiloxane compound and an antistatic agent. The polyether-modified polysiloxane compound is not particularly limited, for example, it is preferably selected from polysiloxanes derived from an alkylene oxide structure having a hydroxyl group at the end of a part of the side chain of the polysiloxane chain of the main chain. Compounds, polysiloxane compounds having an alkylene oxide structure having an acetyl group at the bonding terminal, and a polysiloxane compound having an alkylene oxide structure having a hydroxyl group at the bonding terminal at both ends of the polysiloxane chain of the main chain At least one polysiloxane in the group consisting of silicone compounds [hereinafter, also referred to as "specific polyether-modified polysiloxane". ] is better.

特定聚醚改性聚矽氧化合物，宜為含有來自二烷基矽氧烷之構成單元、與來自鍵結有末端具有羥基之環氧烷結構的烷基矽氧烷之構成單元的聚矽氧烷化合物。 二烷基矽氧烷中之烷基之碳數宜為1～4，為1更佳。 鍵結有末端具有羥基之環氧烷結構的烷基矽氧烷中的環氧烷鏈之碳數，宜為2～4，為2或3更佳。 鍵結有末端具有羥基之環氧烷結構的烷基矽氧烷中之烷基之碳數，宜為1～4。 鍵結有末端具有羥基之環氧烷結構的烷基矽氧烷中之環氧烷鏈之含有數，宜為1～100，為10～100更佳。The specific polyether-modified polysiloxane compound is preferably a polysiloxane containing a structural unit derived from a dialkylsiloxane and a structural unit derived from an alkylsiloxane bonded with an alkylene oxide structure having a hydroxyl group at the terminal. Alkane compounds. The carbon number of the alkyl group in the dialkylsiloxane is preferably 1 to 4, more preferably 1. The number of carbon atoms in the alkylene oxide chain in the alkylsiloxane to which the alkylene oxide structure having a hydroxyl group at the end is bonded is preferably 2 to 4, more preferably 2 or 3. The number of carbon atoms in the alkyl group in the alkylsiloxane having an alkylene oxide structure having a hydroxyl group at the end is preferably 1-4. The content number of the alkylene oxide chain in the alkylsiloxane to which the alkylene oxide structure having a hydroxyl group at the end is bonded is preferably 1 to 100, more preferably 10 to 100.

特定聚醚改性聚矽氧化合物含有來自二烷基矽氧烷之構成單元、與來自鍵結有末端具有羥基之環氧烷結構之烷基矽氧烷的構成單元時，來自二烷基矽氧烷之構成單元之含有數，宜為100以下，為1～80更佳。 又，來自鍵結有末端具有羥基之環氧烷結構之烷基矽氧烷的構成單元之含有數，宜為2～100，為2～80更佳。When a specific polyether-modified polysiloxane compound contains a structural unit derived from dialkylsiloxane and a structural unit derived from an alkylsiloxane bonded with an alkylene oxide structure having a hydroxyl group at the terminal, the The number of the constituent units of the oxane is preferably 100 or less, more preferably 1 to 80. Moreover, the content number of the structural unit derived from the alkylsiloxane to which the alkylene oxide structure which has a hydroxyl group at a terminal couple|bonded is preferably 2-100, More preferably, it is 2-80.

特定聚醚改性聚矽氧化合物宜為下列式(A)或式(B)表示之化合物。The specific polyether-modified polysiloxane compound is preferably a compound represented by the following formula (A) or formula (B).

[化1]

Figure 02_image001
[hua 1]
Figure 02_image001

式(A)中，p為二甲基矽氧烷結構單元之重複數，表示0～100之整數，q為具有聚環氧乙烷鏈之甲基伸丙基矽氧烷結構單元之重複數，表示2～100之整數，a為環氧乙烷結構單元之重複數，表示1～100之整數。 式(A)表示之化合物為多數化合物之集合體時，p、q、及a係作為化合物之集合體之平均值，為有理數。In formula (A), p is the repeating number of the dimethylsiloxane structural unit, representing an integer from 0 to 100, and q is the repeating number of the methylidenesiloxane structural unit having a polyethylene oxide chain , represents an integer from 2 to 100, a is the repeating number of the ethylene oxide structural unit, and represents an integer from 1 to 100. When the compound represented by the formula (A) is an aggregate of many compounds, p, q, and a are the average values of the aggregate of the compounds, and are rational numbers.

式(A)中，a表示之環氧乙烷結構單元之重複數，宜為10～100之整數。 式(A)中，p表示之二甲基矽氧烷結構單元之重複數，宜為1～80之整數。 式(A)中，q表示之甲基伸丙基矽氧烷結構單元之重複數，宜為2～80之整數。In the formula (A), the repeating number of the ethylene oxide structural unit represented by a is preferably an integer of 10-100. In formula (A), the repeating number of the dimethylsiloxane structural unit represented by p is preferably an integer of 1-80. In formula (A), the repeating number of the methylidene siloxane structural unit represented by q is preferably an integer of 2-80.

式(A)表示之化合物可使用市售品。 式(A)表示之化合物之市售品之示例，可列舉：「DOWSIL(註冊商標)SF-8428」、「DOWSIL(註冊商標)FZ-2162」、「DOWSIL(註冊商標)SH-3773M」、「DOWSIL(註冊商標)FZ-77」、「DOWSIL(註冊商標)FZ-2104」、「DOWSIL(註冊商標)FZ-2110」、「DOWSIL(註冊商標)L-7001」、「DOWSIL(註冊商標)L-7002」、及「DOWSIL(註冊商標)SH-3749」[以上為東麗道康寧(股)製]。A commercial item can be used for the compound represented by formula (A). Examples of commercial products of the compound represented by the formula (A) include "DOWSIL (registered trademark) SF-8428", "DOWSIL (registered trademark) FZ-2162", "DOWSIL (registered trademark) SH-3773M", "DOWSIL (registered trademark) FZ-77", "DOWSIL (registered trademark) FZ-2104", "DOWSIL (registered trademark) FZ-2110", "DOWSIL (registered trademark) L-7001", "DOWSIL (registered trademark) L-7002", and "DOWSIL (registered trademark) SH-3749" [the above are manufactured by Toray Dow Corning Corporation].

[化2]

Figure 02_image003
[hua 2]
Figure 02_image003

式(B)中，R1 及R2 各自獨立地表示碳數1～6之伸烷基，c為二甲基矽氧烷結構單元之重複數，表示10～80之整數，d為環氧乙烷結構單元之重複數，表示1以上之整數，e為環氧丙烷結構單元之重複數，表示0以上之整數，d+e表示1～30之整數。環氧乙烷結構單元及環氧丙烷結構單元之順序亦可為無規。In formula (B), R 1 and R 2 each independently represent an alkylene group having 1 to 6 carbon atoms, c is the repeating number of a dimethylsiloxane structural unit, and represents an integer of 10 to 80, and d is an epoxy The repeating number of the ethane structural unit represents an integer of 1 or more, e is the repeating number of the propylene oxide structural unit, and represents an integer of 0 or more, and d+e represents an integer of 1-30. The order of the ethylene oxide structural units and the propylene oxide structural units may also be random.

式(B)表示之化合物可使用市售品。 式(B)表示之化合物之市售品之示例，可列舉「DOWSIL(註冊商標)BY-16-201」、及「DOWSIL(註冊商標)SF-8427」[以上為東麗道康寧(股)製]。A commercial item can be used for the compound represented by formula (B). Examples of commercial products of the compound represented by the formula (B) include "DOWSIL (registered trademark) BY-16-201" and "DOWSIL (registered trademark) SF-8427" [the above are manufactured by Toray Dow Corning Co., Ltd. ].

聚醚改性聚矽氧化合物之重量平均分子量並無特別限定，例如，宜為1萬以上且2萬以下之範圍，為0.3萬以上且1.5萬以下之範圍更佳。 聚醚改性聚矽氧化合物之重量平均分子量，係利用與上述特定(甲基)丙烯酸系聚合物(A)之重量平均分子量的測定方法同樣之方法測得的值。The weight-average molecular weight of the polyether-modified polysiloxane compound is not particularly limited. The weight average molecular weight of the polyether-modified polysiloxane is a value measured by the same method as the method for measuring the weight average molecular weight of the above-mentioned specific (meth)acrylic polymer (A).

本發明之黏著劑組成物含有聚醚改性聚矽氧化合物時，可僅含有1種聚醚改性聚矽氧化合物，亦可含有2種以上。When the adhesive composition of the present invention contains a polyether-modified polysiloxane compound, only one kind of polyether-modified polysiloxane compound may be contained, or two or more kinds thereof may be contained.

本發明之黏著劑組成物含有聚醚改性聚矽氧化合物時，本發明之黏著劑組成物中之聚醚改性聚矽氧化合物之含量，並無特別限定，例如，相對於特定(甲基)丙烯酸系聚合物(A)100質量份，宜為0.1質量份以上且3.0質量份以下之範圍，為0.1質量份以上且1.5質量份以下之範圍更佳，為0.1質量份以上且1.0質量份以下之範圍尤佳。When the adhesive composition of the present invention contains a polyether-modified polysiloxane compound, the content of the polyether-modified polysiloxane compound in the adhesive composition of the present invention is not particularly limited. Base) 100 parts by mass of acrylic polymer (A), preferably in the range of 0.1 part by mass or more and 3.0 parts by mass or less, more preferably in the range of 0.1 part by mass or more and 1.5 parts by mass or less, and more preferably in the range of 0.1 part by mass or more and 1.0 parts by mass The range below the number of copies is preferred.

[交聯觸媒] 本發明之黏著劑組成物亦可含有交聯觸媒。 交聯觸媒並無特別限定，可使用公知者。 就交聯觸媒而言，例如可列舉以二月桂酸二辛基錫(DOTDL)及1,3-二乙醯氧基四丁基錫氧烷為代表的有機金屬化合物、及以三乙二胺及N-甲基𠰌啉為代表的3級胺化合物。[Cross-linking catalyst] The adhesive composition of the present invention may also contain a cross-linking catalyst. The crosslinking catalyst is not particularly limited, and a known one can be used. As a crosslinking catalyst, for example, organometallic compounds represented by dioctyltin dilaurate (DOTDL) and 1,3-diacetoxytetrabutylstannoxane, and triethylenediamine and A tertiary amine compound represented by N-methylpyridine.

本發明之黏著劑組成物含有交聯觸媒時，可僅含有1種交聯觸媒，亦可含有2種以上。When the adhesive composition of the present invention contains a cross-linking catalyst, only one type of cross-linking catalyst may be contained, or two or more types may be contained.

本發明之黏著劑組成物含有交聯觸媒時，交聯觸媒之含量並無特別限定，可因應目的適當設定。When the adhesive composition of the present invention contains a cross-linking catalyst, the content of the cross-linking catalyst is not particularly limited, and can be appropriately set according to the purpose.

[其他成分] 本發明之黏著劑組成物，在不損及本發明之效果的範圍內，亦可視需要含有上述成分以外的成分(所謂其他成分)。 就其他成分而言，可列舉異氰酸酯系交聯劑以外的交聯劑(例如，金屬螯合物系交聯劑)、抗氧化劑、著色劑(例如，染料及顏料)、光穩定劑(例如，紫外線吸收劑)等。[other ingredients] The adhesive composition of the present invention may contain components other than the above-mentioned components (so-called other components) as necessary within a range that does not impair the effects of the present invention. Other components include crosslinking agents other than isocyanate-based crosslinking agents (eg, metal chelate-based crosslinking agents), antioxidants, colorants (eg, dyes and pigments), light stabilizers (eg, UV absorbers) etc.

本發明之黏著劑組成物含有其他成分時，其他成分之含量，在發揮本發明之效果的範圍內，可適當設定。When the adhesive composition of the present invention contains other components, the content of the other components can be appropriately set within the range in which the effects of the present invention are exhibited.

[用途] 本發明之黏著劑組成物可形成低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層，故可理想地使用於用以保護光學構件之薄膜(所謂光學構件保護薄膜)。亦即，本發明之黏著劑組成物適合於將保護薄膜貼附於光學構件之用途。[use] The adhesive composition of the present invention can form an adhesive layer with a good balance between low-speed peeling force and high-speed peeling force, and even if it is adhered to the adherend for a long time and then peeled off from the adherend at high speed, the zipper phenomenon is not easy to occur. Therefore, it can be preferably used for a film for protecting an optical member (so-called optical member protective film). That is, the adhesive composition of the present invention is suitable for the purpose of attaching a protective film to an optical member.

光學構件並無特別限定，例如可列舉構成影像顯示裝置、輸入裝置等設備(所謂光學設備)的構件或該等設備所使用的構件。 光學構件之具體例，可列舉：偏光板、AG(Anti-Glare)偏光板、包含波長板、1/2、1/4等波長板的相位差板、視角補償薄膜、光學補償薄膜、增亮薄膜、導光板、反射薄膜、抗反射薄膜、ITO(Indium-Tin Oxide)薄膜等透明導電薄膜、稜鏡片、透鏡片、散射板等。 光學構件的材質可列舉：聚乙烯系樹脂、聚酯系樹脂、乙酸酯系樹脂(例如，三乙醯基纖維素樹脂)、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、丙烯酸系樹脂、氯乙烯系樹脂、ABS(Acrylonitrile Butadiene Styrene)樹脂、氟系樹脂等樹脂。The optical member is not particularly limited, and examples thereof include members constituting devices (so-called optical devices) such as image display devices and input devices, or members used for these devices. Specific examples of optical members include polarizing plates, AG (Anti-Glare) polarizing plates, retardation plates including wavelength plates, 1/2, 1/4 and other wavelength plates, viewing angle compensation films, optical compensation films, brightness enhancement films Films, light guide plates, reflective films, anti-reflection films, ITO (Indium-Tin Oxide) films and other transparent conductive films, crystal sheets, lens sheets, diffuser plates, etc. Examples of the material of the optical member include polyethylene-based resins, polyester-based resins, acetate-based resins (for example, triacetin-based cellulose resins), polyether-based resins, polycarbonate-based resins, and polyamide-based resins. Resins such as resins, polyimide-based resins, polyolefin-based resins, acrylic resins, vinyl chloride-based resins, ABS (Acrylonitrile Butadiene Styrene) resins, and fluorine-based resins.

[光學構件保護薄膜] 本發明之光學構件保護薄膜(以下，亦簡稱為「保護薄膜」。)具備：基材：及設置於上述基材上，且由上述本發明之黏著劑組成物形成之黏著劑層。亦即，本發明之保護薄膜，係基材、與由本發明之黏著劑組成物形成之黏著劑層疊層而成。 本發明之保護薄膜具有由本發明之黏著劑組成物形成之黏著劑層，故貼附於被黏體之表面後，在需要保護的期間，不易發生從被黏體剝落、偏移等不良情況，且在不需要保護，從被黏體剝離時，可有效地剝離。換言之，低速剝離力與高速剝離力之平衡良好。 本發明之保護薄膜具備由本發明之黏著劑組成物形成之黏著劑層，故即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象。[Optical member protective film] The optical member protective film of the present invention (hereinafter, also abbreviated as "protective film") includes: a base material: and an adhesive layer provided on the above-mentioned base material and formed of the above-mentioned adhesive composition of the present invention. That is, the protective film of the present invention is formed by laminating a substrate and an adhesive layer formed from the adhesive composition of the present invention. The protective film of the present invention has an adhesive layer formed of the adhesive composition of the present invention, so after being attached to the surface of the adherend, in the period of time when protection is required, it is not easy to peel off and offset from the adherend. And when it is peeled off from the adherend without protection, it can be effectively peeled off. In other words, the low-speed peeling force and the high-speed peeling force are well balanced. The protective film of the present invention is provided with an adhesive layer formed of the adhesive composition of the present invention, so even if it is adhered to the adherend for a long time and then peeled off from the adherend at a high speed, the zipper phenomenon is unlikely to occur.

就基材而言，只要可於該基材上形成黏著劑層，則無特別限定。 基材例如可列舉含有聚烯烴系樹脂(例如，聚乙烯及聚丙烯)、聚酯系樹脂[例如，聚對苯二甲酸乙二醇酯(PET)]、乙酸酯系樹脂(例如，三乙醯基纖維素樹脂)、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、丙烯酸系樹脂、氯乙烯系樹脂、ABS(Acrylonitrile Butadiene Styrene)樹脂、氟系樹脂等樹脂的薄膜。 例如考量考慮利用透視所為之光學構件的檢查及管理的觀點，基材宜為含有選自由聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、及丙烯酸系樹脂構成之群組中之至少1種樹脂的薄膜較佳。 又，例如考量表面保護性能的觀點，宜為含有聚酯系樹脂的薄膜，考慮實用性的話，為含有聚對苯二甲酸乙二醇酯(PET)的薄膜特佳。The base material is not particularly limited as long as an adhesive layer can be formed on the base material. Examples of the base material include polyolefin-based resins (for example, polyethylene and polypropylene), polyester-based resins [for example, polyethylene terephthalate (PET)], acetate-based resins (for example, Acetyl cellulose resin), polyether resin, polycarbonate resin, polyamide resin, polyimide resin, acrylic resin, vinyl chloride resin, ABS (Acrylonitrile Butadiene Styrene) resin, Films of resins such as fluorine-based resins. For example, from the viewpoint of inspection and management of optical members by means of fluoroscopy, the base material is preferably a material selected from the group consisting of polyester-based resins, acetate-based resins, polyether-based resins, polycarbonate-based resins, and polyamide-based resins. A film of at least one resin selected from the group consisting of a resin, a polyimide-based resin, a polyolefin-based resin, and an acrylic resin is preferable. In addition, for example, from the viewpoint of surface protection performance, a film containing a polyester-based resin is preferable, and a film containing polyethylene terephthalate (PET) is particularly preferable in view of practicality.

基材亦可含有塑化劑、著色劑(例如，染料及顏料)、熱穩定劑、光穩定劑、抗靜電劑、阻燃劑、抗氧化劑等各種添加劑。 基材也可在一部分或整體施加花紋。The substrate may also contain various additives such as plasticizers, colorants (eg, dyes and pigments), heat stabilizers, light stabilizers, antistatic agents, flame retardants, antioxidants, and the like. The substrate may also be patterned in part or in its entirety.

基材的厚度並無特別限定，一般為500μm以下，宜為300μm以下，為200μm以下更佳。 基材的厚度的下限，例如考量保護薄膜之強度的觀點，宜為5μm以上，為10μm以上更佳。The thickness of the base material is not particularly limited, but is generally 500 μm or less, preferably 300 μm or less, and more preferably 200 μm or less. The lower limit of the thickness of the base material is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of, for example, considering the strength of the protective film.

亦可於基材之單面或兩面設置抗靜電層。又，基材之設置有黏著劑層之側之表面，考量改善基材與黏著劑層之密接性的觀點，亦可施以電暈放電處理、電漿放電處理等表面處理。An antistatic layer can also be provided on one or both sides of the substrate. In addition, the surface of the base material on the side where the adhesive layer is provided may be subjected to surface treatment such as corona discharge treatment and plasma discharge treatment from the viewpoint of improving the adhesion between the base material and the adhesive layer.

黏著劑層之形成方法並無特別限定，可採用通常使用的方法。 作為於基材上形成黏著劑層的方法，例如可採用下列方法。 將本發明之黏著劑組成物以其本身的狀態或視需要利用溶劑稀釋後的狀態，塗布於基材上，形成塗布膜。然後，將形成的塗布膜進行乾燥，藉此於基材上形成黏著膜。然後，藉由將基材上所形成之黏著膜進行熟化，於基材上形成黏著劑層。The formation method of an adhesive bond layer is not specifically limited, A commonly used method can be used. As a method of forming the adhesive layer on the substrate, for example, the following method can be adopted. The adhesive composition of the present invention is applied to a substrate in its own state or, if necessary, diluted with a solvent to form a coating film. Then, the formed coating film is dried to form an adhesive film on the base material. Then, an adhesive layer is formed on the substrate by curing the adhesive film formed on the substrate.

本發明之保護薄膜中，露出的黏著劑層亦可利用剝離薄膜予以保護。剝離薄膜只要是可輕易地從黏著劑層剝離者，則無特別限定，例如可列舉於單面或兩面施以利用剝離處理劑所為之表面處理(所謂易剝離處理)的樹脂薄膜。樹脂薄膜例如可列舉以聚對苯二甲酸乙二醇酯(PET)薄膜為代表的聚酯薄膜。 就剝離處理劑而言，例如可列舉氟系剝離處理劑(例如，氟系樹脂)、蠟系剝離處理劑(例如，石蠟)、聚矽氧系剝離處理劑(例如，聚矽氧)、及長鏈烷基化合物。 剝離薄膜係在將保護薄膜供於實際使用前的期間內保護黏著劑層的表面，並於使用時予以剝離。In the protective film of the present invention, the exposed adhesive layer may be protected by a release film. The release film is not particularly limited as long as it can be easily peeled from the pressure-sensitive adhesive layer, and examples thereof include a resin film that is surface-treated with a release agent (so-called easy-peel treatment) on one side or both sides. The resin film includes, for example, a polyester film typified by a polyethylene terephthalate (PET) film. As the release treatment agent, for example, fluorine-based release treatment agent (for example, fluorine-based resin), wax-based release treatment agent (for example, paraffin), polysiloxane-based release treatment agent (for example, polysiloxane), and Long chain alkyl compounds. The peeling film protects the surface of the pressure-sensitive adhesive layer until the protective film is actually used, and is peeled off at the time of use.

於基材上形成黏著劑層的另一方法，例如可採用下列方法。 將本發明之黏著劑組成物以其本身的狀態或視需要利用溶劑稀釋後的狀態，塗布於經施以利用剝離劑所為之表面處理的紙、樹脂薄膜等剝離薄膜上，於剝離薄膜形成塗布膜。然後，將形成的塗布膜進行乾燥，藉此於剝離薄膜上形成黏著膜。然後，使所形成的黏著膜之露出面與基材接觸並加壓，將黏著膜轉印至基材，藉此於基材上形成黏著膜。然後，藉由將所形成的黏著膜進行熟化，而於基材上形成黏著劑層。As another method of forming the adhesive layer on the substrate, for example, the following method can be used. The adhesive composition of the present invention is applied in its own state or in a state diluted with a solvent if necessary, on a release film such as paper and a resin film that has been surface-treated with a release agent, and the release film is formed. membrane. Then, the formed coating film is dried to form an adhesive film on the release film. Then, the exposed surface of the formed adhesive film is brought into contact with the substrate and pressurized, and the adhesive film is transferred to the substrate, thereby forming an adhesive film on the substrate. Then, an adhesive layer is formed on the base material by aging the formed adhesive film.

於基材上或剝離薄膜上塗布黏著劑組成物的方法並無特別限定，例如可列舉使用凹版輥塗機、逆式輥塗機、吻合式輥塗機、浸漬式輥塗機、刀塗機、噴塗機、塗布棒、塗抹機等的公知方法。 塗布到基材上或剝離薄膜上之黏著劑組成物的塗布量，係因應所形成之黏著劑層之厚度而適當地設定。The method of coating the adhesive composition on the substrate or on the release film is not particularly limited, and examples thereof include the use of a gravure roll coater, a reverse roll coater, a dosing roll coater, a dip roll coater, and a knife coater. , sprayers, applicators, applicators, etc. known methods. The coating amount of the adhesive composition applied to the substrate or the release film is appropriately set according to the thickness of the adhesive layer to be formed.

黏著劑層的厚度可因應保護薄膜所要求之黏著力、被黏體的種類(例如，材質及形狀)、被黏體之表面粗糙度等而適當設定。 黏著劑層的厚度並無特別限定，一般為1μm以上且100μm以下之範圍，宜為5μm以上且50μm以下之範圍，為10μm以上且30μm以下之範圍更佳。The thickness of the adhesive layer can be appropriately set according to the adhesive force required by the protective film, the type (eg, material and shape) of the adherend, and the surface roughness of the adherend. The thickness of the adhesive layer is not particularly limited, but is generally in the range of 1 μm or more and 100 μm or less, preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 30 μm or less.

將基材上或剝離薄膜上所形成之塗布膜進行乾燥的方法並無特別限定，例如可列舉自然乾燥、加熱乾燥、熱風乾燥、真空乾燥等方法。 塗布膜之乾燥溫度及乾燥時間並無特別限定，係因應塗布膜的厚度、塗布膜中之有機溶劑的量等而適當設定。 作為乾燥條件之一例，可列舉使用熱風乾燥機於70℃～120℃乾燥1分鐘～3分鐘之條件。The method of drying the coating film formed on the base material or the release film is not particularly limited, and examples thereof include methods such as natural drying, heat drying, hot air drying, and vacuum drying. The drying temperature and drying time of the coating film are not particularly limited, and are appropriately set according to the thickness of the coating film, the amount of the organic solvent in the coating film, and the like. As an example of drying conditions, the conditions of drying at 70 degreeC - 120 degreeC for 1 minute - 3 minutes using a hot air dryer can be mentioned.

熟化例如於20℃～35℃之環境下進行4天～7天。 藉由熟化，黏著劑組成物之交聯反應結束並形成黏著劑層。The aging is performed, for example, in an environment of 20°C to 35°C for 4 to 7 days. By aging, the cross-linking reaction of the adhesive composition is completed and an adhesive layer is formed.

將貼附於被黏體之保護薄膜進行180°剝離時之黏著劑層之黏著力(所謂剝離力)，當剝離速度為0.3m/分鐘(亦即，低速剝離)時，宜為0.09N/25mm以上，為0.13N/25mm以上更佳，為0.18N/25mm以上尤佳。The adhesive force (so-called peeling force) of the adhesive layer when the protective film attached to the adherend is peeled off at 180° is preferably 0.09N/minute when the peeling speed is 0.3m/min (ie, low-speed peeling). 25mm or more, more preferably 0.13N/25mm or more, more preferably 0.18N/25mm or more.

將貼附於被黏體之保護薄膜進行180°剝離時之黏著劑層之黏著力(所謂剝離力)，當剝離速度為30m/分鐘(亦即，高速剝離)時，宜未達1.00N/25mm，未達0.75N/25mm更佳，未達0.50N/25mm尤佳。When the protective film attached to the adherend is peeled off at 180°, the adhesive force of the adhesive layer (so-called peeling force), when the peeling speed is 30m/min (that is, high-speed peeling), should be less than 1.00N/ 25mm, less than 0.75N/25mm is better, less than 0.50N/25mm is better.

本說明書中，低速剝離力與高速剝離力之平衡良好的黏著劑層，意指根據低速剝離力之值除以高速剝離力之值而得的值(亦即，「低速剝離力/高速剝離力」)進行評價。 「低速剝離力/高速剝離力」宜為0.10以上，為0.20以上更佳，為0.30以上尤佳。 [實施例]In this specification, an adhesive layer with a good balance between the low-speed peeling force and the high-speed peeling force means the value obtained by dividing the value of the low-speed peeling force by the value of the high-speed peeling force (that is, "low-speed peeling force/high-speed peeling force" ”) to evaluate. "Low-speed peeling force/high-speed peeling force" is preferably 0.10 or more, more preferably 0.20 or more, and particularly preferably 0.30 or more. [Example]

以下，藉由實施例更具體地說明本發明。本發明只要不超出其要旨，不限定於下列實施例。Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples as long as the gist is not exceeded.

[(甲基)丙烯酸系聚合物A之製造] [製造例A-1] 於配備有溫度計、攪拌機、氮氣導入管、回流冷卻器、及逐次滴加裝置之反應容器內，加入乙酸乙酯[有機溶劑]70.0質量份。 又，在另外的容器中加入丙烯酸正丁酯[n-BA；丙烯酸烷基酯單體]60.0質量份、丙烯酸2-乙基己酯[2EHA；丙烯酸烷基酯單體]36.3質量份、丙烯酸4-羥基丁酯[4HBA；具有羥基之單體]3.0質量份、及丙烯酸[AA；具有羧基之單體]0.7質量份，混合而製成單體混合物。 將該單體混合物中之25.0質量%添加至上述反應容器內。然後，將該反應容器內之空氣置換為氮氣後，添加2,2’-偶氮雙異丁腈[AIBN；聚合引發劑]0.01質量份，邊於氮氣環境下攪拌，邊將反應容器內之內容物溫度升溫至85℃，使初始反應開始。 在初始反應基本結束後之反應容器內，邊歷時約2小時逐次添加剩餘的單體混合物75.0質量%、乙酸乙酯20.0質量份及AIBN 0.02質量份之混合物，邊使反應容器內之內容物反應，添加結束後進一步反應2小時，得到反應產物(a1)。 之後，於反應容器內之反應產物(a1)中，歷時1小時滴加於乙酸乙酯25.0質量份中溶解過氧化三甲基乙酸第三丁酯(聚合引發劑)0.25質量份而製得的溶液，滴加結束後進一步反應1.5小時，得到反應產物(a2)。將獲得之反應產物(a2)利用乙酸乙酯稀釋，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物A-1之溶液。[Production of (meth)acrylic polymer A] [Production Example A-1] In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube, a reflux cooler, and a sequential dropwise addition device, 70.0 parts by mass of ethyl acetate [organic solvent] was added. In addition, 60.0 parts by mass of n-butyl acrylate [n-BA; alkyl acrylate monomer], 36.3 parts by mass of 2-ethylhexyl acrylate [2EHA; alkyl acrylate monomer], and acrylic acid were placed in a separate container. 3.0 parts by mass of 4-hydroxybutyl ester [4HBA; a monomer having a hydroxyl group] and 0.7 part by mass of acrylic acid [AA; a monomer having a carboxyl group] were mixed to prepare a monomer mixture. 25.0 mass % of this monomer mixture was added in the said reaction container. Then, after replacing the air in the reaction container with nitrogen, 0.01 part by mass of 2,2'-azobisisobutyronitrile [AIBN; polymerization initiator] was added, and the air in the reaction container was stirred under a nitrogen atmosphere. The temperature of the contents was raised to 85°C to start the initial reaction. In the reaction vessel after the initial reaction was substantially completed, the remaining mixture of 75.0 mass % of the monomer mixture, 20.0 mass parts of ethyl acetate and 0.02 mass parts of AIBN was gradually added over a period of about 2 hours, and the contents of the reaction vessel were reacted. , and further reacted for 2 hours after the addition was completed to obtain the reaction product (a1). Then, the reaction product (a1) in the reaction vessel was added dropwise to 25.0 parts by mass of ethyl acetate to dissolve 0.25 part by mass of tert-butyl peroxytrimethyl acetate (polymerization initiator) over 1 hour. The solution was further reacted for 1.5 hours after the dropwise addition to obtain a reaction product (a2). The obtained reaction product (a2) was diluted with ethyl acetate, and the solution of (meth)acrylic-type polymer A-1 whose solid content concentration was 45 mass % was obtained.

此處所稱「固體成分濃度」，意指(甲基)丙烯酸系聚合物A-1之溶液中，(甲基)丙烯酸系聚合物A-1所佔的質量比例。 下列(甲基)丙烯酸系聚合物A-2～A-6之各溶液亦同樣。The "solid content concentration" as used herein means the mass ratio of the (meth)acrylic polymer A-1 in the solution of the (meth)acrylic polymer A-1. The same applies to each solution of the following (meth)acrylic polymers A-2 to A-6.

[製造例A-2及A-4～A-6] 製造例A-2及A-4～A-6中，藉由將(甲基)丙烯酸系聚合物A之單體組成變更為表1所示之單體組成，以及調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物A之重量平均分子量(Mw)調整為表1所示之重量平均分子量(Mw)，除此以外，進行與製造例A-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物A-2及A-4～A-6之各溶液。[Production Examples A-2 and A-4 to A-6] In Production Examples A-2 and A-4 to A-6, by changing the monomer composition of the (meth)acrylic polymer A to the monomer composition shown in Table 1, and adjusting the usage amount of the organic solvent and In addition to adjusting the weight average molecular weight (Mw) of the (meth)acrylic polymer A to the weight average molecular weight (Mw) shown in Table 1, at least one of the usage amounts of the polymerization initiators was used with In the same manner as in Production Example A-1, each solution of (meth)acrylic polymer A-2 and A-4 to A-6 having a solid content concentration of 45% by mass was obtained.

[製造例A-3] 製造例A-3中，藉由調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物A之重量平均分子量(Mw)調整為表1所示之重量平均分子量(Mw)，除此以外，進行與製造例A-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物A-3之溶液。[Production Example A-3] In Production Example A-3, the weight average molecular weight (Mw) of the (meth)acrylic polymer A was adjusted to Table 1 by adjusting at least one of the amount of the organic solvent used and the amount of the polymerization initiator used. Except having shown the weight average molecular weight (Mw), it carried out similarly to manufacture example A-1, and obtained the solution of (meth)acrylic-type polymer A-3 whose solid content concentration is 45 mass %.

(甲基)丙烯酸系聚合物A-1～A-6之單體組成(單位：質量%)、羥值(單位：mgKOH/g)、酸價(單位：mgKOH/g)、重量平均分子量[Mw、單位：萬(表中記載為「×104 )]、及玻璃轉移溫度(Tg、單位：℃)示於表1。Monomer composition (unit: mass %), hydroxyl value (unit: mgKOH/g), acid value (unit: mgKOH/g), weight average molecular weight of (meth)acrylic polymers A-1 to A-6 [ Mw, unit: 10,000 (represented in the table as "×10 4 )], and glass transition temperature (Tg, unit: °C) are shown in Table 1.

(甲基)丙烯酸系聚合物A-1～A-6之重量平均分子量(Mw)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)的測定方法同樣之方法進行測定。 (甲基)丙烯酸系聚合物A-1～A-6之玻璃轉移溫度(Tg)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度(Tg)之計算方法同樣之方法進行計算。The weight average molecular weights (Mw) of the (meth)acrylic polymers A-1 to A-6 were measured in the same manner as the weight average molecular weight (Mw) of the above-mentioned specific (meth)acrylic polymers (A). method to measure. The glass transition temperatures (Tg) of the (meth)acrylic polymers A-1 to A-6 were calculated using the same method as the glass transition temperature (Tg) of the specific (meth)acrylic polymers (A) described above. method to calculate.

(甲基)丙烯酸系聚合物A-1～A-6之羥值及酸價，分別利用與上述特定(甲基)丙烯酸系聚合物(A)之羥值及酸價的計算方法同樣之方法進行計算。The hydroxyl values and acid values of the (meth)acrylic polymers A-1 to A-6 were calculated using the same methods as the calculation methods for the hydroxyl values and acid values of the specific (meth)acrylic polymers (A) described above, respectively. Calculation.

例如，(甲基)丙烯酸系聚合物A-1之羥值係如下述般進行計算。此外，(甲基)丙烯酸系聚合物A-1中之4HBA的含有率(A1)為3.0質量%，4HBA之分子量(A2)為144.17。又，4HBA之1分子中含有的羥基數(A3)為1。 (甲基)丙烯酸系聚合物A-1之羥值(mgKOH/g)＝[(A1/100)÷A2]×56.1×1000×A3＝[(3.0/100)÷144.17]×56.1×1000×1＝11.67･･･≒11.7For example, the hydroxyl value of the (meth)acrylic polymer A-1 is calculated as follows. Moreover, the content rate (A1) of 4HBA in (meth)acrylic-type polymer A-1 was 3.0 mass %, and the molecular weight (A2) of 4HBA was 144.17. In addition, the number of hydroxyl groups (A3) contained in one molecule of 4HBA is 1. Hydroxyl value (mgKOH/g) of (meth)acrylic polymer A-1=[(A1/100)÷A2]×56.1×1000×A3=[(3.0/100)÷144.17]×56.1×1000× 1＝11.67･･･≒11.7

又，(甲基)丙烯酸系聚合物A-1之酸價係如下述般進行計算。此外，(甲基)丙烯酸系聚合物A-1中之AA的含有率(a1)為0.7質量%，AA之分子量(a2)為72.06。又，AA之1分子中含有的羧基數(a3)為1。 (甲基)丙烯酸系聚合物A-1之酸價(mgKOH/g)＝[(a1/100)÷a2]×56.1×1000×a3＝[(0.7/100)÷72.06]×56.1×1000×1＝5.44･･･≒5.4In addition, the acid value of (meth)acrylic-type polymer A-1 was calculated as follows. Moreover, the content rate (a1) of AA in (meth)acrylic-type polymer A-1 was 0.7 mass %, and the molecular weight (a2) of AA was 72.06. In addition, the number of carboxyl groups (a3) contained in one molecule of AA is 1. Acid value (mgKOH/g) of (meth)acrylic polymer A-1=[(a1/100)÷a2]×56.1×1000×a3=[(0.7/100)÷72.06]×56.1×1000× 1＝5.44･･･≒5.4

上述獲得之(甲基)丙烯酸系聚合物A-1～A-6中，(甲基)丙烯酸系聚合物A-1～A-5相當於本發明中之特定(甲基)丙烯酸系聚合物(A)。Among the (meth)acrylic polymers A-1 to A-6 obtained above, the (meth)acrylic polymers A-1 to A-5 correspond to the specific (meth)acrylic polymers in the present invention (A).

[表1]

Figure 02_image005
[Table 1]
Figure 02_image005

表1記載之各單體詳細如下所示。 「n-BA」：丙烯酸正丁酯[丙烯酸烷基酯單體] 「2EHA」：丙烯酸2-乙基己酯[丙烯酸烷基酯單體] 「4HBA」：丙烯酸4-羥基丁酯[具有羥基之單體] 「AA」：丙烯酸[具有羧基之單體]The details of each monomer described in Table 1 are shown below. "n-BA": n-butyl acrylate [alkyl acrylate monomer] "2EHA": 2-ethylhexyl acrylate [alkyl acrylate monomer] "4HBA": 4-hydroxybutyl acrylate [monomer with hydroxyl group] "AA": Acrylic acid [monomer with carboxyl group]

表1中，單體組成之欄記載之「-」，意指不含該當於該欄之單體。 表1中，將「重量平均分子量」記載為「Mw」，「玻璃轉移溫度」記載為「Tg」。In Table 1, "-" described in the column of monomer composition means that the monomer corresponding to this column is not contained. In Table 1, the "weight average molecular weight" is described as "Mw", and the "glass transition temperature" is described as "Tg".

[(甲基)丙烯酸系聚合物B之製造] [製造例B-1] 於配備有溫度計、攪拌機、氮氣導入管、回流冷卻器、及逐次滴加裝置之反應容器內，加入乙酸乙酯[有機溶劑]70.0質量份。 又，在另外的容器中加入甲基丙烯酸正丁酯[n-BMA；甲基丙烯酸烷基酯單體]96.3質量份、丙烯酸4-羥基丁酯[4HBA；具有羥基之單體]3.0質量份、及丙烯酸[AA；具有羧基之單體]0.7質量份，混合以製成單體混合物。 將該單體混合物中之25.0質量%添加至上述反應容器內。然後，將該反應容器內之空氣置換為氮氣後，添加2,2’-偶氮雙異丁腈[AIBN；聚合引發劑]1.80質量份，邊於氮氣環境下攪拌，邊將反應容器內之內容物溫度升溫至85℃，使初始反應開始。 在初始反應基本結束後之反應容器內，邊歷時約2小時逐次添加剩餘的單體混合物75.0質量%、乙酸乙酯20.0質量份及AIBN 2.0質量份之混合物，邊使反應容器內之內容物反應，添加結束後進一步反應約1小時，得到反應產物(b1)。 之後，於反應容器內之反應產物(b1)中，歷時1小時滴加於乙酸乙酯25.0質量份中溶解過氧化三甲基乙酸第三丁酯(聚合引發劑)0.25質量份而製得的溶液，滴加結束後進一步反應2小時間，得到反應產物(b2)。將獲得之反應產物(b2)利用乙酸乙酯稀釋，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物B-1之溶液。[Production of (meth)acrylic polymer B] [Production Example B-1] In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube, a reflux cooler, and a sequential dropwise addition device, 70.0 parts by mass of ethyl acetate [organic solvent] was added. In addition, 96.3 parts by mass of n-butyl methacrylate [n-BMA; an alkyl methacrylate monomer] and 3.0 parts by mass of 4-hydroxybutyl acrylate [4HBA; a monomer having a hydroxyl group] were placed in a separate container , and 0.7 parts by mass of acrylic acid [AA; monomer having a carboxyl group], and mixed to prepare a monomer mixture. 25.0 mass % of this monomer mixture was added in the said reaction container. Then, after replacing the air in the reaction container with nitrogen, 1.80 parts by mass of 2,2'-azobisisobutyronitrile [AIBN; polymerization initiator] was added, and the air in the reaction container was stirred under a nitrogen atmosphere. The temperature of the contents was raised to 85°C to start the initial reaction. In the reaction vessel after the initial reaction was substantially completed, the remaining mixture of 75.0 mass % of the monomer mixture, 20.0 mass parts of ethyl acetate and 2.0 mass parts of AIBN was gradually added over a period of about 2 hours, and the contents of the reaction vessel were reacted. , and further reacted for about 1 hour after the addition was completed to obtain the reaction product (b1). Then, the reaction product (b1) in the reaction vessel was added dropwise to 25.0 parts by mass of ethyl acetate to dissolve 0.25 parts by mass of tert-butyl peroxytrimethyl acetate (polymerization initiator) over 1 hour. The solution was further reacted for 2 hours after the dropwise addition to obtain a reaction product (b2). The obtained reaction product (b2) was diluted with ethyl acetate, and the solution of (meth)acrylic-type polymer B-1 whose solid content concentration was 45 mass % was obtained.

此處所稱「固體成分濃度」，意指(甲基)丙烯酸系聚合物B-1之溶液中，(甲基)丙烯酸系聚合物B-1所佔的質量比例。 下列(甲基)丙烯酸系聚合物B-2～B-12之各溶液亦同樣。"Solid content concentration" as used here means the mass ratio of (meth)acrylic-type polymer B-1 in the solution of (meth)acrylic-type polymer B-1. The same applies to each solution of the following (meth)acrylic polymers B-2 to B-12.

[製造例B-2～B-5及B-8～B-10] 製造例B-2～B-5及B-8～B-10中，藉由將(甲基)丙烯酸系聚合物B之單體組成變更為表2所示之單體組成，以及調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物B之重量平均分子量(Mw)調整為表2所示之重量平均分子量(Mw)，除此以外，進行與製造例B-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物B-2～B-5及B-8～B-10之各溶液。[Production Examples B-2 to B-5 and B-8 to B-10] In Production Examples B-2 to B-5 and B-8 to B-10, by changing the monomer composition of (meth)acrylic polymer B to the monomer composition shown in Table 2, and adjusting the organic solvent At least one of the usage amount and the usage amount of the polymerization initiator to adjust the weight average molecular weight (Mw) of the (meth)acrylic polymer B to the weight average molecular weight (Mw) shown in Table 2, in addition to Other than that, it carried out similarly to manufacture example B-1, and obtained each solution of (meth)acrylic-type polymer B-2-B-5 and B-8-B-10 whose solid content concentration is 45 mass %.

[製造例B-6、B-7、B-11、及B-12] 製造例B-6、B-7、B-11、及B-12中，藉由調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物B之重量平均分子量(Mw)調整為表2所示之重量平均分子量(Mw)，除此以外，進行與製造例B-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物B-6、B-7、B-11、及B-12之各溶液。[Production Examples B-6, B-7, B-11, and B-12] In Production Examples B-6, B-7, B-11, and B-12, by adjusting at least one of the usage amount of the organic solvent and the usage amount of the polymerization initiator, the (meth)acrylic polymer was polymerized Except having adjusted the weight average molecular weight (Mw) of material B to the weight average molecular weight (Mw) shown in Table 2, the same operation as that of Production Example B-1 was carried out to obtain (methyl) having a solid content concentration of 45% by mass. ) Each solution of acrylic polymer B-6, B-7, B-11, and B-12.

(甲基)丙烯酸系聚合物B-1～B-12之單體組成(單位：質量%)、羥值(單位：mgKOH/g)、酸價(單位：mgKOH/g)、重量平均分子量[Mw、單位：萬(表中記載為「×104 )]、及玻璃轉移溫度(Tg、單位：℃)示於表2。Monomer composition (unit: mass %), hydroxyl value (unit: mgKOH/g), acid value (unit: mgKOH/g), weight average molecular weight of (meth)acrylic polymers B-1 to B-12 [ Mw, unit: ten thousand (represented in the table as "×10 4 )], and glass transition temperature (Tg, unit: °C) are shown in Table 2.

(甲基)丙烯酸系聚合物B-1～B-12之重量平均分子量(Mw)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)的測定方法同樣之方法進行測定。 (甲基)丙烯酸系聚合物B-1～B-12之玻璃轉移溫度(Tg)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度(Tg)之計算方法同樣之方法進行計算。The weight average molecular weights (Mw) of the (meth)acrylic polymers B-1 to B-12 were measured in the same manner as the weight average molecular weights (Mw) of the specific (meth)acrylic polymers (A) described above. method to measure. The glass transition temperature (Tg) of the (meth)acrylic polymers B-1 to B-12 was calculated in the same manner as the glass transition temperature (Tg) of the specific (meth)acrylic polymer (A) described above. method to calculate.

(甲基)丙烯酸系聚合物B-1～B-12之羥值及酸價，分別利用與上述特定(甲基)丙烯酸系聚合物(A)之羥值及酸價的計算方法同樣之方法進行計算。The hydroxyl value and acid value of the (meth)acrylic polymers B-1 to B-12 were calculated using the same method as the calculation method of the hydroxyl value and acid value of the above-mentioned specific (meth)acrylic polymer (A). Calculation.

上述獲得之(甲基)丙烯酸系聚合物B-1～B-12中，(甲基)丙烯酸系聚合物B-1～B-7相當於本發明中之特定(甲基)丙烯酸系聚合物(B)。Among the (meth)acrylic polymers B-1 to B-12 obtained above, the (meth)acrylic polymers B-1 to B-7 correspond to the specific (meth)acrylic polymers in the present invention (B).

[表2]

Figure 02_image007
[Table 2]
Figure 02_image007

表2記載之各單體詳細如下所示。 「n-BA」：丙烯酸正丁酯[丙烯酸烷基酯單體] 「n-BMA」：甲基丙烯酸正丁酯[甲基丙烯酸烷基酯單體] 「MA」：丙烯酸甲酯[丙烯酸烷基酯單體] 「MMA」：甲基丙烯酸甲酯[甲基丙烯酸烷基酯單體] 「2EHMA」：甲基丙烯酸2-乙基己酯[甲基丙烯酸烷基酯單體] 「4HBA」：丙烯酸4-羥基丁酯[具有羥基之單體] 「AA」：丙烯酸[具有羧基之單體]The details of each monomer described in Table 2 are shown below. "n-BA": n-butyl acrylate [alkyl acrylate monomer] "n-BMA": n-butyl methacrylate [alkyl methacrylate monomer] "MA": methyl acrylate [alkyl acrylate monomer] "MMA": methyl methacrylate [alkyl methacrylate monomer] "2EHMA": 2-ethylhexyl methacrylate [alkyl methacrylate monomer] "4HBA": 4-hydroxybutyl acrylate [monomer with hydroxyl group] "AA": Acrylic acid [monomer with carboxyl group]

表2中，單體組成之欄記載之「-」，意指不含該等於該欄之單體。 表2中，將「重量平均分子量」記載為「Mw」，「玻璃轉移溫度」記載為「Tg」。In Table 2, "-" described in the column of monomer composition means that the monomer equivalent to this column is not contained. In Table 2, the "weight average molecular weight" is described as "Mw", and the "glass transition temperature" is described as "Tg".

[(甲基)丙烯酸系聚合物C之製造] [製造例C-1] 於配備有溫度計、攪拌機、氮氣導入管、及回流冷卻器之反應容器內，加入甲乙酮[有機溶劑]100.0質量份。 將反應容器內之空氣置換為氮氣後，將反應容器內之溫度升溫至87℃。然後，於將反應容器內之溫度保持在87℃之狀態攪拌甲乙酮，於攪拌下之甲乙酮中，邊分別歷時約2小時逐次添加丙烯酸正丁酯[n-BA；丙烯酸烷基酯單體]95.0質量份及丙烯酸4-羥基丁酯[4HBA；具有羥基之單體]5.0質量份之單體混合物、與甲乙酮100.0質量份及2,2’-偶氮雙異丁腈[AIBN；聚合引發劑]5.0質量份之混合物，邊使反應容器內之內容物反應，添加結束後進一步反應約4小時，得到反應產物(c1)。將獲得之反應產物(c1)利用甲乙酮稀釋，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物C-1之溶液。[Production of (meth)acrylic polymer C] [Production Example C-1] In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux cooler, 100.0 parts by mass of methyl ethyl ketone [organic solvent] was added. After replacing the air in the reaction container with nitrogen, the temperature in the reaction container was raised to 87°C. Then, methyl ethyl ketone was stirred while the temperature in the reaction vessel was kept at 87°C, and n-butyl acrylate [n-BA; acrylic acid alkyl ester monomer] 95.0 was gradually added to the stirred methyl ethyl ketone over a period of about 2 hours. Parts by mass and a monomer mixture of 5.0 parts by mass of 4-hydroxybutyl acrylate [4HBA; monomer having a hydroxyl group], 100.0 parts by mass of methyl ethyl ketone, and 2,2'-azobisisobutyronitrile [AIBN; polymerization initiator] 5.0 parts by mass of the mixture was reacted with the contents in the reaction vessel, and the reaction was further performed for about 4 hours after completion of the addition to obtain a reaction product (c1). The obtained reaction product (c1) was diluted with methyl ethyl ketone to obtain a solution of (meth)acrylic polymer C-1 having a solid content concentration of 45% by mass.

此處所稱「固體成分濃度」，意指(甲基)丙烯酸系聚合物C-1之溶液中，(甲基)丙烯酸系聚合物C-1所佔的質量比例。 下列(甲基)丙烯酸系聚合物C-2～C-8之各溶液亦同樣。The "solid content concentration" as used herein means the mass ratio of the (meth)acrylic polymer C-1 in the solution of the (meth)acrylic polymer C-1. The same applies to each solution of the following (meth)acrylic polymers C-2 to C-8.

[製造例C-2、C-5、及C-6] 製造例C-2、C-5、及C-6中，藉由將(甲基)丙烯酸系聚合物C之單體組成變更為表3所示之單體組成，以及調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物C之重量平均分子量(Mw)調整為表3所示之重量平均分子量(Mw)，除此以外，進行與製造例C-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物C-2、C-5、及C-6之各溶液。[Production Examples C-2, C-5, and C-6] In Production Examples C-2, C-5, and C-6, the monomer composition of (meth)acrylic polymer C was changed to the monomer composition shown in Table 3, and the amount of organic solvent used was adjusted and at least one of the amount of polymerization initiator used to adjust the weight-average molecular weight (Mw) of the (meth)acrylic polymer C to the weight-average molecular weight (Mw) shown in Table 3, in addition to In the same manner as in Production Example C-1, solutions of (meth)acrylic polymers C-2, C-5, and C-6 having a solid content concentration of 45% by mass were obtained.

[製造例C-3、C-4、C-7、及C-8] 製造例C-3、C-4、C-7、及C-8中，藉由調整有機溶劑的使用量及聚合引發劑的使用量中之至少一者，以將(甲基)丙烯酸系聚合物C之重量平均分子量(Mw)調整為表3所示之重量平均分子量(Mw)，除此以外，進行與製造例C-1同樣之操作，得到固體成分濃度為45質量%的(甲基)丙烯酸系聚合物C-3、C-4、C-7、及C-8之各溶液。[Production Examples C-3, C-4, C-7, and C-8] In Production Examples C-3, C-4, C-7, and C-8, by adjusting at least one of the usage amount of the organic solvent and the usage amount of the polymerization initiator, the (meth)acrylic-based polymer was polymerized Except that the weight average molecular weight (Mw) of substance C was adjusted to the weight average molecular weight (Mw) shown in Table 3, the same operation as in Production Example C-1 was carried out to obtain (methyl) having a solid content concentration of 45% by mass. ) Each solution of acrylic polymer C-3, C-4, C-7, and C-8.

(甲基)丙烯酸系聚合物C-1～C-8之單體組成(單位：質量%)、羥值(單位：mgKOH/g)、酸價(單位：mgKOH/g)、重量平均分子量[Mw、單位：萬(表中記載為「×104 )]、及玻璃轉移溫度(Tg、單位：℃)示於表3。Monomer composition (unit: mass %), hydroxyl value (unit: mgKOH/g), acid value (unit: mgKOH/g), weight average molecular weight of (meth)acrylic polymers C-1 to C-8 [ Mw, unit: 10,000 (represented in the table as "×10 4 )], and glass transition temperature (Tg, unit: °C) are shown in Table 3.

(甲基)丙烯酸系聚合物C-1～C-8之重量平均分子量(Mw)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)的測定方法同樣之方法進行測定。 (甲基)丙烯酸系聚合物C-1～C-8之玻璃轉移溫度(Tg)，係利用與上述特定(甲基)丙烯酸系聚合物(A)之玻璃轉移溫度(Tg)之計算方法同樣之方法進行計算。The weight average molecular weights (Mw) of the (meth)acrylic polymers C-1 to C-8 were measured in the same manner as the weight average molecular weights (Mw) of the specific (meth)acrylic polymers (A) described above. method to measure. The glass transition temperatures (Tg) of the (meth)acrylic polymers C-1 to C-8 are calculated using the same method as the glass transition temperature (Tg) of the specific (meth)acrylic polymer (A) described above. method to calculate.

(甲基)丙烯酸系聚合物C-1～C-8之羥值及酸價，分別利用與上述特定(甲基)丙烯酸系聚合物(A)之羥值及酸價的計算方法同樣之方法進行計算。The hydroxyl values and acid values of the (meth)acrylic polymers C-1 to C-8 were calculated using the same methods as the calculation methods for the hydroxyl values and acid values of the specific (meth)acrylic polymer (A) described above, respectively. Calculation.

上述獲得之(甲基)丙烯酸系聚合物C-1～C-8中，(甲基)丙烯酸系聚合物C-1～C-5相當於本發明中之特定(甲基)丙烯酸系聚合物(C)。Among the (meth)acrylic polymers C-1 to C-8 obtained above, the (meth)acrylic polymers C-1 to C-5 correspond to the specific (meth)acrylic polymers in the present invention (C).

[表3]

Figure 02_image009
[table 3]
Figure 02_image009

表3記載之各單體詳細如下所示。 「n-BA」：丙烯酸正丁酯[丙烯酸烷基酯單體] 「MA」：丙烯酸甲酯[丙烯酸烷基酯單體] 「4HBA」：丙烯酸4-羥基丁酯[具有羥基之單體]The details of each monomer described in Table 3 are shown below. "n-BA": n-butyl acrylate [alkyl acrylate monomer] "MA": methyl acrylate [alkyl acrylate monomer] "4HBA": 4-hydroxybutyl acrylate [monomer with hydroxyl group]

表3中，單體組成之欄記載之「-」，意指不含該等於該欄之單體。 表3中，將「重量平均分子量」記載為「Mw」，「玻璃轉移溫度」記載為「Tg」。In Table 3, "-" described in the column of monomer composition means that the monomer equivalent to this column is not contained. In Table 3, the "weight average molecular weight" is described as "Mw", and the "glass transition temperature" is described as "Tg".

[聚矽氧系多異氰酸酯化合物X之製造] 於配備有攪拌葉片、溫度計、氮氣導入管、回流冷卻器、及滴加漏斗之四口燒瓶中，加入TAKENATE(註冊商標)500[商品名、二甲苯二異氰酸酯(XDI)、三井化學(股)製]118.0質量份、DOWSIL(註冊商標)SH-3773M[商品名、聚醚改性聚矽氧化合物、東麗道康寧(股)製]82.0質量份，將燒瓶內之空氣置換為氮氣後，將燒瓶內之溫度升溫至50℃。然後，於將燒瓶內之溫度保持在50℃之狀態，將燒瓶內之內容物攪拌6小時，得到係異氰酸酯系交聯劑之聚矽氧系多異氰酸酯化合物X。[Production of polysiloxane-based polyisocyanate compound X] In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a reflux cooler, and a dropping funnel, TAKENATE (registered trademark) 500 [trade name, xylene diisocyanate (XDI), Mitsui Chemicals Co., Ltd. manufactured] 118.0 parts by mass, DOWSIL (registered trademark) SH-3773M [trade name, polyether-modified polysiloxane, manufactured by Toray Dow Corning Co., Ltd.] 82.0 parts by mass, the air in the flask was replaced with nitrogen, and the The temperature in the flask was raised to 50°C. Then, while maintaining the temperature in the flask at 50° C., the content in the flask was stirred for 6 hours to obtain a polysiloxane-based polyisocyanate compound X which is an isocyanate-based crosslinking agent.

[黏著劑組成物之製備] [實施例1] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液3.0質量份(固體成分為1質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物6.0質量份(固體成分為2.0質量份)，充分攪拌，得到實施例1之黏著劑組成物。[Preparation of adhesive composition] [Example 1] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 3.0 parts by mass (solid content is 1 part by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 6.0 parts by mass of the substance (solid content: 2.0 parts by mass) was sufficiently stirred to obtain the adhesive composition of Example 1.

[實施例2及3] 實施例2及3中，將係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1的摻合量變更為表4所示之摻合量，除此以外，進行與實施例1同樣之操作，得到實施例2及3之各黏著劑組成物。[Examples 2 and 3] In Examples 2 and 3, except that the blending amount of the (meth)acrylic polymer C-1 which is the specific (meth)acrylic polymer (C) was changed to the blending amount shown in Table 4 Other than that, it carried out the same operation as Example 1, and each adhesive composition of Examples 2 and 3 was obtained.

[實施例4～7] 實施例4～7中，將特定(甲基)丙烯酸系聚合物(C)的種類變更為表4所示之種類，除此以外，進行與實施例2同樣之操作，得到實施例4～7之各黏著劑組成物。[Examples 4 to 7] In Examples 4-7, except having changed the kind of specific (meth)acrylic-type polymer (C) to the kind shown in Table 4, the same operation as Example 2 was performed, and Examples 4-7 were obtained. each adhesive composition.

[實施例8及9] 實施例8及9中，將特定(甲基)丙烯酸系聚合物(A)的種類變更為表4所示之種類，除此以外，進行與實施例2同樣之操作，得到實施例8及9之各黏著劑組成物。[Examples 8 and 9] In Examples 8 and 9, except that the type of the specific (meth)acrylic polymer (A) was changed to the type shown in Table 4, the same operations as in Example 2 were performed to obtain Examples 8 and 9. each adhesive composition.

[實施例10] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-4之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物15.0質量份(固體成分為5.0質量份)、係交聯觸媒之二月桂酸二辛基錫(DOTDL)0.02質量份，充分攪拌，得到實施例10之黏著劑組成物。[Example 10] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-4 that is the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 15.0 parts by mass (solid content: 5.0 parts by mass) and 0.02 parts by mass of dioctyltin dilaurate (DOTDL) as a cross-linking catalyst were mixed thoroughly, and the adhesive composition of Example 10 was obtained.

[實施例11] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-5之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物15.0質量份(固體成分為5.0質量份)，充分攪拌，得到實施例11之黏著劑組成物。[Example 11] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-5 that is the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 15.0 parts by mass of the substance (solid content: 5.0 parts by mass) was sufficiently stirred to obtain the adhesive composition of Example 11.

[實施例12] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-2之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物15.0質量份(固體成分為5.0質量份)、係交聯觸媒之二月桂酸二辛基錫(DOTDL)0.02質量份，充分攪拌，得到實施例12之黏著劑組成物。[Example 12] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-2 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 15.0 parts by mass (solid content is 5.0 parts by mass) and 0.02 parts by mass of dioctyltin dilaurate (DOTDL), which is a crosslinking catalyst, were thoroughly stirred to obtain the adhesive composition of Example 12.

[實施例13] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-3之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物15.0質量份(固體成分為5.0質量份)，充分攪拌，得到實施例13之黏著劑組成物。[Example 13] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-3 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 15.0 parts by mass of the substance (solid content: 5.0 parts by mass) was sufficiently stirred to obtain the adhesive composition of Example 13.

[實施例14及15] 實施例14及15中，將特定(甲基)丙烯酸系聚合物B-1的摻合量變更為表4所示之摻合量，除此以外，進行與實施例2同樣之操作，得到實施例14及15之各黏著劑組成物。[Examples 14 and 15] In Examples 14 and 15, except having changed the blending amount of the specific (meth)acrylic polymer B-1 to the blending amount shown in Table 4, the same operation as in Example 2 was carried out, and the implementation was carried out. Each of the adhesive compositions of Examples 14 and 15.

[實施例16～19] 實施例16～19中，將特定(甲基)丙烯酸系聚合物(B)的種類變更為表5所示之種類，除此以外，進行與實施例2同樣之操作，得到實施例16～19之各黏著劑組成物。[Examples 16 to 19] In Examples 16-19, except having changed the kind of specific (meth)acrylic-type polymer (B) to the kind shown in Table 5, it carried out the same operation as Example 2, and obtained Examples 16-19 each adhesive composition.

[實施例20及21] 實施例20及21中，將係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400的摻合量變更為表5所示之摻合量，除此以外，進行與實施例2同樣之操作，得到實施例20及21之各黏著劑組成物。[Examples 20 and 21] In Examples 20 and 21, the same procedure as in Example 2 was carried out, except that the blending amount of DESMODUR (registered trademark) N3400, which is an isocyanate-based crosslinking agent (D), was changed to the blending amount shown in Table 5. Through the operation, the adhesive compositions of Examples 20 and 21 were obtained.

[實施例22及23] 實施例22及23中，將異氰酸酯系交聯劑(D)的種類變更為表5所示之種類，除此以外，進行與實施例2同樣之操作，得到實施例22及23之各黏著劑組成物。[Examples 22 and 23] In Examples 22 and 23, except that the type of the isocyanate-based crosslinking agent (D) was changed to the type shown in Table 5, the same operations as in Example 2 were performed to obtain the respective adhesives of Examples 22 and 23. composition.

[實施例24] 實施例24中，將異氰酸酯系交聯劑(D)的種類及摻合量變更為表5所示之種類及摻合量，除此以外，進行與實施例2同樣之操作，得到實施例24之黏著劑組成物。[Example 24] In Example 24, except having changed the kind and blending amount of the isocyanate-based crosslinking agent (D) to those shown in Table 5, the same operation as in Example 2 was carried out to obtain Example 24 The adhesive composition.

[實施例25] 實施例25中，不摻合係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M，除此以外，進行與實施例2同樣之操作，得到實施例25之黏著劑組成物。[Example 25] In Example 25, except that DOWSIL (registered trademark) SH-3773M, which is a polyether-modified polysiloxane compound, was not blended, the same operations as in Example 2 were performed to obtain the adhesive composition of Example 25.

[實施例26] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物6.0質量份(固體成分為2.0質量份)、作為其他交聯劑之係金屬螯合物系交聯劑之鋁螯合物A[商品名、參乙醯丙酮鋁、川研精細化學(股)製]0.1質量份，充分攪拌，得到實施例26之黏著劑組成物。[Example 26] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 6.0 parts by mass (solid content is 2.0 parts by mass), aluminum chelate A [trade name, acetonitrile aluminum acetonitrile, Chuanken Fine Chemicals (stock) as another crosslinking agent )] 0.1 parts by mass, fully stirred to obtain the adhesive composition of Example 26.

[實施例27] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份、係抗靜電劑之LiTFS[LiCF3 SO3 (三氟甲磺酸鋰)、森田化學工業(股)製]0.25質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物6.0質量份(固體成分為2.0質量份)，充分攪拌，得到實施例27之黏著劑組成物。[Example 27] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, a (meth)acrylic polymer A which is a specific (meth)acrylic polymer (A) was added 222.2 parts by mass of a solution of -1 (solid content: 100 parts by mass), and 66.7 parts by mass of a solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B) (solid content: 30 parts by mass), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), polyether-modified polymer DOWSIL (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass of silicon oxide compound, LiTFS [LiCF 3 SO 3 (trifluorocarbon) as an antistatic agent Lithium methanesulfonate), Morita Chemical Industry Co., Ltd.] 0.25 parts by mass, and stirred for 4 hours while maintaining the liquid temperature of the contents in the flask at around 25°C. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 6.0 parts by mass of the substance (solid content: 2.0 parts by mass) was sufficiently stirred to obtain the adhesive composition of Example 27.

[實施例28] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物6.0質量份(固體成分為2.0質量份)、係異氰酸酯系交聯劑(D)之聚矽氧系多異氰酸酯化合物X 0.25質量份，充分攪拌，得到實施例28之黏著劑組成物。[Example 28] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 6.0 parts by mass (solid content is 2.0 parts by mass) and 0.25 parts by mass of the polysiloxane-based polyisocyanate compound which is an isocyanate-based crosslinking agent (D), and fully stirred to obtain the adhesive composition of Example 28.

[實施例29] 於配備有攪拌葉片、溫度計、冷卻器、及滴加漏斗之四口燒瓶中，加入係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1之溶液222.2質量份(固體成分為100質量份)、係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1之溶液66.7質量份(固體成分為30質量份)、係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1之溶液6.0質量份(固體成分為2質量份)、係聚醚改性聚矽氧化合物之DOWSIL(註冊商標)SH-3773M[商品名、式(A)表示之化合物、東麗道康寧(股)製]0.36質量份，於將燒瓶內之內容物之液溫保持在25℃附近之狀態攪拌4小時。 然後，在燒瓶內添加係異氰酸酯系交聯劑(D)之DESMODUR(註冊商標)N3400[商品名、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製]之稀釋物6.0質量份(固體成分為2.0質量份)、係交聯觸媒之二月桂酸二辛基錫(DOTDL)0.02質量份，充分攪拌，得到實施例29之黏著劑組成物。[Example 29] In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, add the solution 222.2 of the (meth)acrylic polymer A-1 of the specific (meth)acrylic polymer (A). parts by mass (solid content: 100 parts by mass), 66.7 parts by mass (solid content: 30 parts by mass) of the solution of (meth)acrylic polymer B-1 of the specific (meth)acrylic polymer (B), 6.0 parts by mass (solid content: 2 parts by mass) of a solution of (meth)acrylic polymer C-1 of the specific (meth)acrylic polymer (C), DOWSIL which is a polyether-modified polysiloxane compound (registered trademark) SH-3773M [trade name, compound represented by formula (A), manufactured by Toray Dow Corning Co., Ltd.] 0.36 parts by mass, and stirred for 4 Hour. Then, a dilution of DESMODUR (registered trademark) N3400 [trade name, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.], which is an isocyanate-based crosslinking agent (D), was added to the flask. 6.0 parts by mass (solid content is 2.0 parts by mass) and 0.02 parts by mass of dioctyltin dilaurate (DOTDL), which is a crosslinking catalyst, were thoroughly stirred to obtain the adhesive composition of Example 29.

[比較例1] 比較例1中，摻合100質量份之作為比較聚合物之(甲基)丙烯酸系聚合物A-6以替代摻合100質量份之係特定(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸系聚合物A-1，除此以外，進行與實施例2同樣之操作，得到比較例1之黏著劑組成物。[Comparative Example 1] In Comparative Example 1, 100 parts by mass of (meth)acrylic polymer A-6 as a comparative polymer was blended in place of blending 100 parts by mass of (meth)acrylic polymer (A) ( Except the meth)acrylic-type polymer A-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 1 was obtained.

[比較例2] 比較例2中，摻合30質量份之作為比較聚合物之(甲基)丙烯酸系聚合物B-8以替代摻合30質量份之係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1，除此以外，進行與實施例2同樣之操作，得到比較例2之黏著劑組成物。[Comparative Example 2] In Comparative Example 2, 30 parts by mass of (meth)acrylic polymer B-8 as a comparative polymer was blended in place of blending 30 parts by mass of (meth)acrylic polymer (B) based on ( Except the meth)acrylic-type polymer B-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 2 was obtained.

[比較例3] 比較例3中，不摻合特定(甲基)丙烯酸系聚合物(B)，除此以外，進行與實施例2同樣之操作，得到比較例3之黏著劑組成物。[Comparative Example 3] In Comparative Example 3, except that the specific (meth)acrylic polymer (B) was not blended, the same operations as in Example 2 were performed to obtain an adhesive composition of Comparative Example 3.

[比較例4及5] 比較例4及5中，將特定(甲基)丙烯酸系聚合物B-1的摻合量變更為表6所示之摻合量，除此以外，進行與實施例2同樣之操作，得到比較例4及5之各黏著劑組成物。[Comparative Examples 4 and 5] In Comparative Examples 4 and 5, except having changed the blending amount of the specific (meth)acrylic polymer B-1 to the blending amount shown in Table 6, the same operations as in Example 2 were performed to obtain a comparison. Each of the adhesive compositions of Examples 4 and 5.

[比較例6] 比較例6中，摻合30質量份之作為比較聚合物之(甲基)丙烯酸系聚合物B-9以替代摻合30質量份之係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1，除此以外，進行與實施例2同樣之操作，得到比較例6之黏著劑組成物。[Comparative Example 6] In Comparative Example 6, 30 parts by mass of (meth)acrylic polymer B-9 as a comparative polymer was blended in place of blending 30 parts by mass of (meth)acrylic polymer (B) of ( Except the meth)acrylic-type polymer B-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 6 was obtained.

[比較例7] 比較例7中，摻合30質量份之作為比較聚合物之(甲基)丙烯酸系聚合物B-10以替代摻合30質量份之係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1，除此以外，進行與實施例2同樣之操作，得到比較例7之黏著劑組成物。[Comparative Example 7] In Comparative Example 7, instead of blending 30 parts by mass of (meth)acrylic polymer B-10 as a comparative polymer, 30 parts by mass of the specific (meth)acrylic polymer (B) ( Except the meth)acrylic-type polymer B-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 7 was obtained.

[比較例8] 比較例8中，摻合30質量份之作為比較聚合物之(甲基)丙烯酸系聚合物B-11以替代摻合30質量份之係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1，除此以外，進行與實施例2同樣之操作，得到比較例8之黏著劑組成物。[Comparative Example 8] In Comparative Example 8, 30 parts by mass of (meth)acrylic polymer B-11 as a comparative polymer was blended in place of blending 30 parts by mass of (meth)acrylic polymer (B) ( Except the meth)acrylic-type polymer B-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 8 was obtained.

[比較例9] 比較例9中，摻合30質量份之作為比較聚合物之(甲基)丙烯酸系聚合物B-12以替代摻合30質量份之係特定(甲基)丙烯酸系聚合物(B)之(甲基)丙烯酸系聚合物B-1，除此以外，進行與實施例2同樣之操作，得到比較例9之黏著劑組成物。[Comparative Example 9] In Comparative Example 9, 30 parts by mass of (meth)acrylic polymer B-12 as a comparative polymer was blended in place of blending 30 parts by mass of (meth)acrylic polymer (B) ( Except the meth)acrylic-type polymer B-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 9 was obtained.

[比較例10] 比較例10中，不摻合特定(甲基)丙烯酸系聚合物(C)，除此以外，進行與實施例2同樣之操作，得到比較例10之黏著劑組成物。[Comparative Example 10] In Comparative Example 10, except that the specific (meth)acrylic polymer (C) was not blended, the same operations as in Example 2 were performed to obtain an adhesive composition of Comparative Example 10.

[比較例11及12] 比較例11及12中，將特定(甲基)丙烯酸系聚合物C-1的摻合量變更為表6所示之摻合量，除此以外，進行與實施例2同樣之操作，得到比較例11及12之各黏著劑組成物。[Comparative Examples 11 and 12] In Comparative Examples 11 and 12, except having changed the blending amount of the specific (meth)acrylic polymer C-1 to the blending amount shown in Table 6, the same operations as in Example 2 were performed to obtain a comparison. Each of the adhesive compositions of Examples 11 and 12.

[比較例13] 比較例13中，摻合2質量份之作為比較聚合物之(甲基)丙烯酸系聚合物C-6以替代摻合2質量份之係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1，除此以外，進行與實施例2同樣之操作，得到比較例13之黏著劑組成物。[Comparative Example 13] In Comparative Example 13, instead of blending 2 parts by mass of (meth)acrylic polymer C-6 as a comparative polymer, 2 parts by mass of the specific (meth)acrylic polymer (C) ( Except the meth)acrylic-type polymer C-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 13 was obtained.

[比較例14] 比較例14中，摻合2質量份之作為比較聚合物之(甲基)丙烯酸系聚合物C-7以替代摻合2質量份之係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1，除此以外，進行與實施例2同樣之操作，得到比較例14之黏著劑組成物。[Comparative Example 14] In Comparative Example 14, instead of blending 2 parts by mass of (meth)acrylic polymer C-7 as a comparative polymer, 2 parts by mass of the specific (meth)acrylic polymer (C) ( Except the meth)acrylic-type polymer C-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 14 was obtained.

[比較例15] 比較例15中，摻合2質量份之作為比較聚合物之(甲基)丙烯酸系聚合物C-8以替代摻合2質量份之係特定(甲基)丙烯酸系聚合物(C)之(甲基)丙烯酸系聚合物C-1，除此以外，進行與實施例2同樣之操作，得到比較例15之黏著劑組成物。[Comparative Example 15] In Comparative Example 15, instead of blending 2 parts by mass of (meth)acrylic polymer C-8 as a comparative polymer, 2 parts by mass of the specific (meth)acrylic polymer (C) ( Except the meth)acrylic-type polymer C-1, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 15 was obtained.

[比較例16] 比較例16中，摻合係環氧系交聯劑之TETRAD(註冊商標)-X[商品名、三菱瓦斯化學(股)製]作為比較交聯劑以替代異氰酸酯系交聯劑(D)，除此以外，進行與實施例2同樣之操作，得到比較例16之黏著劑組成物。[Comparative Example 16] In Comparative Example 16, TETRAD (registered trademark)-X [trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.] blended with an epoxy-based cross-linking agent was used as a comparative cross-linking agent instead of the isocyanate-based cross-linking agent (D), Except for this, the same operation as Example 2 was performed, and the adhesive composition of the comparative example 16 was obtained.

[表4]

Figure 02_image011
[Table 4]
Figure 02_image011

[表5]

Figure 02_image013
[table 5]
Figure 02_image013

[表6]

Figure 02_image015
[Table 6]
Figure 02_image015

表4～6中，「-」意指不含該當之成分。 表4～6中之摻合量均為固體成分換算值。 表5中，將「聚矽氧系多異氰酸酯化合物X」記載為「化合物X」。In Tables 4 to 6, "-" means that the corresponding component is not contained. The blending amounts in Tables 4 to 6 are all solid content conversion values. In Table 5, "polysiloxane-based polyisocyanate compound X" is described as "compound X".

表4～6記載之各交聯劑詳細如下所示。 ＜異氰酸酯系交聯劑(D)＞ 「N3400」[商品名：DESMODUR(註冊商標)N3400、六亞甲基二異氰酸酯(HMDI)之2聚物、Sumika Covestro Urethane(股)製] 「N3300」[商品名：SUMIDUR(註冊商標)N3300、六亞甲基二異氰酸酯(HMDI)之3聚物、Sumika Covestro Urethane(股)製] 「L-45E」[商品名：CORONATE(註冊商標)L-45E、甲苯二異氰酸酯(TDI)與三羥甲基丙烷(TMP)之加成體、東曹(股)製] 「D-120」[商品名：TAKENATE(註冊商標)D-120、二甲苯二異氰酸酯(XDI)與三羥甲基丙烷(TMP)之加成體、三井化學(股)製] 「化合物X」：聚矽氧系多異氰酸酯化合物XThe details of each crosslinking agent described in Tables 4 to 6 are shown below. <Isocyanate-based crosslinking agent (D)> "N3400" [trade name: DESMODUR (registered trademark) N3400, dimer of hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane Co., Ltd.] "N3300" [trade name: SUMIDUR (registered trademark) N3300, hexamethylene diisocyanate (HMDI) terpolymer, manufactured by Sumika Covestro Urethane Co., Ltd.] "L-45E" [trade name: CORONATE (registered trademark) L-45E, adduct of toluene diisocyanate (TDI) and trimethylolpropane (TMP), manufactured by Tosoh Corporation] "D-120" [trade name: TAKENATE (registered trademark) D-120, adduct of xylene diisocyanate (XDI) and trimethylolpropane (TMP), manufactured by Mitsui Chemicals Co., Ltd.] "Compound X": polysiloxane-based polyisocyanate compound X

＜其他交聯劑＞ 「鋁螯合物A」[商品名、參乙醯丙酮鋁、川研精細化學(股)製]：金屬螯合物系交聯劑 ＜比較交聯劑＞ 「TETRAD-X」[商品名：TETRAD(註冊商標)-X、三菱瓦斯化學(股)製]：環氧系交聯劑<Other crosslinking agents> "Aluminum chelate A" [trade name, acetonitrile aluminum acetone, manufactured by Kawaken Fine Chemical Co., Ltd.]: metal chelate-based crosslinking agent <Comparative crosslinking agents> "TETRAD-X" [trade name: TETRAD (registered trademark)-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.]: epoxy-based crosslinking agent

[評價] 使用上述製備得到之黏著劑組成物實施下列評價。 結果示於表7～9。[Evaluation] The following evaluation was carried out using the adhesive composition prepared above. The results are shown in Tables 7 to 9.

1.剝離力 ＜剝離力評價用保護薄膜的製作＞ 於作為基材之聚對苯二甲酸乙二醇酯(PET)薄膜[商品名：Teijin(註冊商標)Tetoron(註冊商標)薄膜、型號：G2、厚度：38μm、Teijin Film Solutions(股)製]上，以使乾燥後之塗布量成為15g/m2 的方式，塗布黏著劑組成物，形成塗布膜。然後，將所形成的塗布膜使用熱風循環型乾燥機於100℃乾燥60秒，藉此於基材上形成黏著膜。 然後，將基材上所形成之黏著膜之露出面，重疊於經以聚矽氧系剝離處理劑進行表面處理的剝離薄膜[商品名：FILMBYNA(註冊商標)100E-0010 No.23、厚度：100μm、藤森工業(股)製]之表面處理面，然後通過加壓夾輥，藉此將黏著膜與剝離薄膜進行壓接並貼合。然後，於環境溫度23℃、50%RH之環境下將黏著膜熟化96小時，藉此得到具有基材/黏著劑層/剝離薄膜之疊層結構的剝離力評價用保護薄膜。1. Peeling force <Preparation of protective film for peeling force evaluation> Polyethylene terephthalate (PET) film [trade name: Teijin (registered trademark) Tetoron (registered trademark) film, model number: G2, thickness: 38 μm, manufactured by Teijin Film Solutions Co., Ltd.], the adhesive composition was applied so that the coating weight after drying was 15 g/m 2 to form a coating film. Then, the formed coating film was dried at 100° C. for 60 seconds using a hot air circulation type dryer to form an adhesive film on the substrate. Then, the exposed surface of the adhesive film formed on the substrate was superimposed on the release film [trade name: FILMBYNA (registered trademark) 100E-0010 No. 23, thickness: The surface-treated surface of 100 μm, Fujimori Kogyo Co., Ltd.] was passed through a pressure nip roll, whereby the adhesive film and the release film were crimped and bonded together. Then, the adhesive film was aged for 96 hours in an environment with an ambient temperature of 23° C. and 50% RH, thereby obtaining a protective film for evaluation of peeling force having a laminate structure of substrate/adhesive layer/release film.

＜評價試驗＞ (1)初始 (1-1)低速剝離力 將上述製得之剝離力評價用保護薄膜裁切成25mm×150mm之大小，準備剝離力評價用保護薄膜片。 然後，從所準備的剝離力評價用保護薄膜片將剝離薄膜予以剝離，將因剝離而露出的黏著劑層之面重疊於作為被黏體之聚對苯二甲酸乙二醇酯(PET)薄膜[商品名：COSMOSHINE(註冊商標)A4300、厚度：300μm、東洋紡(股)製]之面，然後使用桌上型層合機進行壓接而製成試驗樣品。 將該試驗樣品於環境溫度23℃、50%RH之環境下放置24小時。然後，使用單柱式材料試驗機[型號：STA-1225、A&D(股)製]作為測定裝置，以環境溫度23℃、50%RH之環境下、剝離速度0.3m/分鐘之條件，測定從PET薄膜將剝離力評價用保護薄膜片(構成：黏著劑層/基材)於長邊(150mm)方向進行180°剝離時的剝離力(單位：N/25mm)。另外，依下列評價基準評價低速剝離力。 評價結果若為「AA」、「A」、或「B」，則判斷為係展現適當之低速剝離力的黏著劑層。<Evaluation test> (1) Initial (1-1) Low speed peeling force The protective film for evaluation of peeling force obtained above was cut into a size of 25 mm×150 mm to prepare a protective film sheet for evaluation of peeling force. Then, the peeling film was peeled off from the prepared protective film sheet for peeling force evaluation, and the surface of the adhesive layer exposed by peeling was superimposed on the polyethylene terephthalate (PET) film as the adherend [trade name: COSMOSHINE (registered trademark) A4300, thickness: 300 μm, manufactured by Toyobo Co., Ltd.], and then press-bonded using a desktop laminator to prepare a test sample. The test sample was placed in an environment with an ambient temperature of 23° C. and 50% RH for 24 hours. Then, using a single-column material testing machine [model: STA-1225, manufactured by A&D Corporation] as a measuring device, under the conditions of an ambient temperature of 23°C, 50% RH, and a peeling speed of 0.3 m/min, the PET film Peeling force (unit: N/25mm) when peeling the protective film sheet for peeling force evaluation (configuration: adhesive layer/substrate) at 180° in the long-side (150 mm) direction. In addition, the low-speed peel force was evaluated according to the following evaluation criteria. If the evaluation result is "AA", "A", or "B", it is judged that it is an adhesive layer which exhibits an appropriate low-speed peeling force.

-評價基準- AA：剝離力為0.18N/25mm以上。 A：剝離力為0.13N/25mm以上且未達0.18N/25mm。 B：剝離力為0.09N/25mm以上且未達0.13N/25mm。 C：剝離力未達0.09N/25mm。-Evaluation criteria- AA: The peeling force is 0.18N/25mm or more. A: The peeling force is 0.13 N/25 mm or more and less than 0.18 N/25 mm. B: The peeling force is 0.09 N/25 mm or more and less than 0.13 N/25 mm. C: The peeling force was less than 0.09N/25mm.

(1-2)高速剝離力 以與上述「(1-1)低速剝離力」同樣之程序獲得試驗樣品。 將該試驗樣品於環境溫度23℃、50%RH之環境下放置24小時。然後，使用剝離試驗機[型號：橫向型TE-720、Tester sangyo(股)製]作為測定裝置，以環境溫度23℃、50%RH之環境下、剝離速度30m/分鐘之條件，測定從PET薄膜將剝離力評價用保護薄膜片(構成：黏著劑層/基材)於長邊(150mm)方向進行180°剝離時的剝離力(單位：N/25mm)。另外，依下列評價基準評價高速剝離力。 評價結果若為「AA」、「A」、或「B」，則判斷為係展現適當之高速剝離力的黏著劑層。(1-2) High-speed peeling force A test sample was obtained by the same procedure as the above-mentioned "(1-1) Peeling force at low speed". The test sample was placed in an environment with an ambient temperature of 23° C. and 50% RH for 24 hours. Then, using a peeling tester [model: horizontal type TE-720, manufactured by Tester Sangyo Co., Ltd.] as a measuring device, under the conditions of an ambient temperature of 23° C., 50% RH, and a peeling speed of 30 m/min. Film Peeling force (unit: N/25mm) when the protective film sheet for peeling force evaluation (configuration: adhesive layer/substrate) was peeled at 180° in the longitudinal (150 mm) direction. In addition, the high-speed peel force was evaluated according to the following evaluation criteria. If the evaluation result is "AA", "A", or "B", it will be judged that it is an adhesive bond layer which exhibits an appropriate high-speed peeling force.

-評價基準- AA：剝離力未達0.50N/25mm。 A：剝離力為0.50N/25mm以上且未達0.75N/25mm。 B：剝離力為0.75N/25mm以上且未達1.00N/25mm。 C：剝離力為1.00N/25mm以上。-Evaluation criteria- AA: The peeling force was less than 0.50N/25mm. A: The peeling force is 0.50 N/25 mm or more and less than 0.75 N/25 mm. B: The peeling force is 0.75 N/25 mm or more and less than 1.00 N/25 mm. C: The peeling force is 1.00 N/25 mm or more.

(1-3)低速剝離力與高速剝離力之平衡 根據上述「(1-1)低速剝離力」測得之低速剝離力之值、與上述「(1-2)高速剝離力」測得之高速剝離力之值，評價低速剝離力與高速剝離力之平衡。 具體而言，根據將低速剝離力之值除以高速剝離力之值，並將小數點以下第3位數四捨五入而得之值，依循下述評價基準評價低速剝離力與高速剝離力之平衡。 評價結果若為「AA」、「A」、或「B」，則判斷為係低速剝離力與高速剝離力之平衡良好的黏著劑層。(1-3) Balance between low-speed peeling force and high-speed peeling force According to the value of the low-speed peeling force measured in the above "(1-1) Low-speed peeling force" and the value of the high-speed peeling force measured in the above "(1-2) High-speed peeling force", evaluate the low-speed peeling force and the high-speed peeling force balance. Specifically, the balance between the low-speed peeling force and the high-speed peeling force was evaluated according to the following evaluation criteria according to the value obtained by dividing the value of the low-speed peeling force by the value of the high-speed peeling force and rounding off the third decimal place. When the evaluation result is "AA", "A", or "B", it is judged that it is an adhesive layer with a good balance between the low-speed peeling force and the high-speed peeling force.

-評價基準- AA：「低速剝離力/高速剝離力」為0.30以上。 A：「低速剝離力/高速剝離力」為0.20以上且未達0.30。 B：「低速剝離力/高速剝離力」為0.10以上且未達0.20。 C：「低速剝離力/高速剝離力」未達0.10。-Evaluation criteria- AA: "Low-speed peeling force/high-speed peeling force" is 0.30 or more. A: "Low-speed peeling force/high-speed peeling force" is 0.20 or more and less than 0.30. B: "Low-speed peeling force/high-speed peeling force" is 0.10 or more and less than 0.20. C: "Low-speed peeling force/high-speed peeling force" is less than 0.10.

(2)加速試驗後 (2-1)拉鍊現象的抑制 利用與上述「(1-1)低速剝離力」同樣之程序獲得試驗樣品。 對於該試驗樣品，實施於設定為80℃之熱風循環型乾燥機[型號：PHH-200、ESPEC(股)製]內靜置250小時的加速試驗。加速試驗結束後，將試驗樣品從熱風循環型乾燥機取出，於環境溫度23℃、50%RH之環境下靜置24小時。然後，使用剝離試驗機[型號：橫向型TE-720、Tester sangyo(股)製]作為測定裝置，以環境溫度23℃、50%RH之環境下、剝離速度30m/分鐘之條件，從PET薄膜將剝離力評價用保護薄膜片(構成：黏著劑層/基材)於長邊(150mm)方向進行180°剝離。對剝離後之PET薄膜之表面吹氣後，目視觀察其表面的狀態。另外，依下列評價基準評價拉鍊現象的抑制。 評價結果若為「AA」、「A」、或「B」，則判斷為係即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象的黏著劑層。(2) After accelerated test (2-1) Suppression of zipper phenomenon A test sample was obtained by the same procedure as the above-mentioned "(1-1) Peeling force at low speed". This test sample was subjected to an accelerated test of standing for 250 hours in a hot air circulation type dryer [model: PHH-200, manufactured by ESPEC Co., Ltd.] set at 80°C. After the accelerated test, the test sample was taken out from the hot air circulation type dryer, and was allowed to stand for 24 hours in an environment with an ambient temperature of 23°C and 50% RH. Then, using a peeling tester [model: transverse type TE-720, manufactured by Tester Sangyo Co., Ltd.] as a measuring device, under the conditions of an ambient temperature of 23° C., 50% RH, and a peeling speed of 30 m/min, from the PET film The protective film sheet for peeling force evaluation (configuration: adhesive layer/substrate) was peeled at 180° in the long-side (150 mm) direction. After blowing air on the surface of the peeled PET film, the state of the surface was visually observed. In addition, suppression of the zipper phenomenon was evaluated according to the following evaluation criteria. When the evaluation result is "AA", "A", or "B", it is judged that it is an adhesive layer that does not easily generate a zipper phenomenon even when it is adhered to an adherend for a long time and then peeled off from the adherend at a high speed.

-評價基準- AA：完全未確認到條痕狀缺陷。 A：略微確認到條痕狀缺陷。 B：稍有確認到條痕狀缺陷，但係容許之範圍。 C：顯著確認到條痕狀缺陷。-Evaluation criteria- AA: No streak defect was recognized at all. A: A streak-like defect was slightly recognized. B: A streak-like defect is slightly observed, but it is within the allowable range. C: A streak-like defect was remarkably recognized.

[表7]

Figure 02_image017
[Table 7]
Figure 02_image017

[表8]

Figure 02_image019
[Table 8]
Figure 02_image019

[表9]

Figure 02_image021
[Table 9]
Figure 02_image021

如表7及8所示，由實施例1～29之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡良好，且即使長期間貼附於被黏體後從被黏體以高速剝離時，亦不易發生拉鍊現象，實施例1～29之黏著劑組成物含有：(甲基)丙烯酸系聚合物(A)[亦即，特定(甲基)丙烯酸系聚合物(A)]，具有羥基及羧基中之至少一者，且重量平均分子量超過20萬且在200萬以下之範圍；(甲基)丙烯酸系聚合物(B)[亦即，特定(甲基)丙烯酸系聚合物(B)]，具有羥基及羧基中之至少一者，玻璃轉移溫度為0℃以上且45℃以下之範圍，且重量平均分子量為6000以上且15萬以下之範圍；(甲基)丙烯酸系聚合物(C)[亦即，特定(甲基)丙烯酸系聚合物(C)]，玻璃轉移溫度為-30℃以下，且重量平均分子量為6000以上且15萬以下之範圍；及異氰酸酯系交聯劑(D)；特定(甲基)丙烯酸系聚合物(B)之含量，相對於特定(甲基)丙烯酸系聚合物(A)100質量份，為7質量份以上且70質量份以下之範圍，特定(甲基)丙烯酸系聚合物(C)之含量，相對於特定(甲基)丙烯酸系聚合物(A)100質量份，為0.5質量份以上且5質量份以下之範圍。As shown in Tables 7 and 8, for the adhesive layers formed from the adhesive compositions of Examples 1 to 29, it was confirmed that the low-speed peeling force and the high-speed peeling force were well balanced, and even after being adhered to the adherend for a long period of time, the When the adherend is peeled off at a high speed, the zipper phenomenon is not easy to occur, and the adhesive compositions of Examples 1 to 29 contain: (meth)acrylic polymer (A) [that is, specific (meth)acrylic polymer (A)], having at least one of a hydroxyl group and a carboxyl group, and having a weight average molecular weight in the range of more than 200,000 and 2,000,000 or less; (meth)acrylic polymer (B) [that is, a specific (methyl) Acrylic polymer (B)], having at least one of a hydroxyl group and a carboxyl group, a glass transition temperature in the range of 0°C or higher and 45°C or lower, and a weight average molecular weight in the range of 6,000 or higher and 150,000 or lower; (methyl ) acrylic polymer (C) [that is, specific (meth)acrylic polymer (C)], the glass transition temperature is -30°C or lower, and the weight average molecular weight is in the range of 6,000 or more and 150,000 or less; and Isocyanate-based crosslinking agent (D); content of the specific (meth)acrylic polymer (B) is 7 parts by mass or more and 70 mass parts with respect to 100 parts by mass of the specific (meth)acrylic polymer (A) The content of the specific (meth)acrylic polymer (C) is within the range of 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the specific (meth)acrylic polymer (A). .

另一方面，如表9所示，由(甲基)丙烯酸系聚合物(A)不具有羥基及羧基中之任一者之比較例1之黏著劑組成物形成的黏著劑層，無法從被黏體剝離而無法進行評價試驗。 由(甲基)丙烯酸系聚合物(B)不具有羥基及羧基中之任一者之比較例2之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由不含特定(甲基)丙烯酸系聚合物(B)之比較例3之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由特定(甲基)丙烯酸系聚合物(B)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份未達7質量份的比較例4之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由特定(甲基)丙烯酸系聚合物(B)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份超過70質量份之比較例5之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度未達0℃之比較例6之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度超過45℃之比較例7之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由(甲基)丙烯酸系聚合物(B)之重量平均分子量未達6000之比較例8之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由(甲基)丙烯酸系聚合物(B)之重量平均分子量超過15萬之比較例9之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。On the other hand, as shown in Table 9, the adhesive layer formed from the adhesive composition of Comparative Example 1 in which the (meth)acrylic polymer (A) did not have either a hydroxyl group or a carboxyl group could not The adhesive peeled off and the evaluation test could not be performed. In the adhesive layer formed from the adhesive composition of Comparative Example 2 in which the (meth)acrylic polymer (B) does not have either a hydroxyl group or a carboxyl group, it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was not good . In the adhesive layer formed from the adhesive composition of Comparative Example 3 not containing the specific (meth)acrylic polymer (B), it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was poor. The adhesive formed from the adhesive composition of Comparative Example 4 in which the content of the specific (meth)acrylic polymer (B) is less than 7 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer (A) layer, and it was confirmed that the balance between the low-speed peel force and the high-speed peel force was not good. The adhesive layer formed from the adhesive composition of Comparative Example 5 in which the content of the specific (meth)acrylic polymer (B) exceeds 70 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer (A) , it was confirmed that after being attached to the adherend for a long period of time, the zipper phenomenon is likely to occur when peeled off from the adherend at a high speed. In the adhesive layer formed from the adhesive composition of Comparative Example 6 in which the glass transition temperature of the (meth)acrylic polymer (B) did not reach 0° C., it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was poor. The adhesive layer formed of the adhesive composition of Comparative Example 7 in which the glass transition temperature of the (meth)acrylic polymer (B) exceeded 45° C. was confirmed to be adhered to the adherend for a long period of time, and then the adhesive layer disappeared from the adherend. When peeling at a high speed, a zipper phenomenon is likely to occur. In the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of Comparative Example 8 in which the weight average molecular weight of the (meth)acrylic polymer (B) was less than 6,000, it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was poor. The adhesive layer formed from the adhesive composition of Comparative Example 9 having the weight-average molecular weight of the (meth)acrylic polymer (B) exceeding 150,000 was confirmed to be adhered to the adherend for a long period of time, and then the adhesive layer gradually disappeared from the adherend. When peeling at a high speed, a zipper phenomenon is likely to occur.

由不含特定(甲基)丙烯酸系聚合物(C)之比較例10之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由特定(甲基)丙烯酸系聚合物(C)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份未達0.5質量份之比較例11之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由特定(甲基)丙烯酸系聚合物(C)之含量相對於特定(甲基)丙烯酸系聚合物(A)100質量份超過5質量份之比較例12之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由(甲基)丙烯酸系聚合物(C)之玻璃轉移溫度超過-30℃之比較例13之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由(甲基)丙烯酸系聚合物(C)之重量平均分子量未達6000之比較例14之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。 由(甲基)丙烯酸系聚合物(C)之重量平均分子量超過15萬之比較例15之黏著劑組成物形成的黏著劑層，確認到長期間貼附於被黏體後，從被黏體以高速剝離的話，容易發生拉鍊現象。 由含有環氧系交聯劑來替換含有異氰酸酯系交聯劑之比較例16之黏著劑組成物形成的黏著劑層，確認到低速剝離力與高速剝離力之平衡不佳。When the adhesive layer formed from the adhesive composition of Comparative Example 10 containing no specific (meth)acrylic polymer (C) was confirmed to be attached to the adherend for a long period of time and then peeled off from the adherend at a high speed , prone to zipper phenomenon. The adhesive formed from the adhesive composition of Comparative Example 11 in which the content of the specific (meth)acrylic polymer (C) is less than 0.5 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer (A) It is confirmed that the zipper phenomenon is likely to occur when the layer is peeled off from the adherend at a high speed after being adhered to the adherend for a long period of time. The adhesive layer formed from the adhesive composition of Comparative Example 12 in which the content of the specific (meth)acrylic polymer (C) exceeds 5 parts by mass with respect to 100 parts by mass of the specific (meth)acrylic polymer (A) , it was confirmed that the balance between the low-speed peel force and the high-speed peel force was not good. The adhesive layer formed from the adhesive composition of Comparative Example 13 in which the glass transition temperature of the (meth)acrylic polymer (C) exceeded -30° C. was confirmed to be adhered to the adherend for a long period of time, and the adhesive layer changed from the adherend to the adherend. If the body is peeled off at a high speed, a zipper phenomenon is likely to occur. In the adhesive layer formed from the adhesive composition of Comparative Example 14 in which the weight average molecular weight of the (meth)acrylic polymer (C) was less than 6000, it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was poor. The adhesive layer formed from the adhesive composition of Comparative Example 15 having the weight average molecular weight of the (meth)acrylic polymer (C) exceeding 150,000 was confirmed to be adhered to the adherend for a long period of time, and then the adhesive layer gradually disappeared from the adherend. When peeling at a high speed, a zipper phenomenon is likely to occur. In the adhesive layer formed from the adhesive composition of Comparative Example 16 containing an epoxy-based crosslinking agent in place of the isocyanate-based crosslinking agent, it was confirmed that the balance between the low-speed peeling force and the high-speed peeling force was poor.

Claims (10)

一種光學構件保護薄膜用黏著劑組成物，含有： (甲基)丙烯酸系聚合物(A)，具有羥基及羧基中之至少一者，且重量平均分子量超過20萬且在200萬以下之範圍； (甲基)丙烯酸系聚合物(B)，具有羥基及羧基中之至少一者，玻璃轉移溫度為0℃以上且45℃以下之範圍，且重量平均分子量為6000以上且15萬以下之範圍； (甲基)丙烯酸系聚合物(C)，玻璃轉移溫度為-30℃以下，且重量平均分子量為6000以上且15萬以下之範圍；及 異氰酸酯系交聯劑(D)； 該(甲基)丙烯酸系聚合物(B)之含量，相對於該(甲基)丙烯酸系聚合物(A)100質量份為7質量份以上且70質量份以下之範圍， 該(甲基)丙烯酸系聚合物(C)之含量，相對於該(甲基)丙烯酸系聚合物(A)100質量份為0.5質量份以上且5質量份以下之範圍。An adhesive composition for an optical component protective film, comprising: (Meth)acrylic polymer (A), having at least one of a hydroxyl group and a carboxyl group, and having a weight-average molecular weight in the range of more than 200,000 and less than 2,000,000; (Meth)acrylic polymer (B) having at least one of a hydroxyl group and a carboxyl group, a glass transition temperature in the range of 0°C or higher and 45°C or lower, and a weight average molecular weight in the range of 6,000 or more and 150,000 or less; (Meth)acrylic polymer (C), the glass transition temperature is -30°C or lower, and the weight average molecular weight is in the range of 6,000 or more and 150,000 or less; and Isocyanate based crosslinking agent (D); The content of the (meth)acrylic polymer (B) is in the range of 7 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic polymer (A), Content of this (meth)acrylic-type polymer (C) is the range of 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of this (meth)acrylic-type polymer (A). 如請求項1之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(A)具有羥基，且羥值為0.3mgKOH/g以上且40mgKOH/g以下之範圍。The adhesive composition for an optical member protective film according to claim 1, wherein the (meth)acrylic polymer (A) has a hydroxyl group, and the hydroxyl value is in the range of 0.3 mgKOH/g or more and 40 mgKOH/g or less. 如請求項1或2之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(A)具有羧基，且酸價為0.7mgKOH/g以上且24mgKOH/g以下之範圍。The adhesive composition for an optical member protective film according to claim 1 or 2, wherein the (meth)acrylic polymer (A) has a carboxyl group and has an acid value in the range of not less than 0.7 mgKOH/g and not more than 24 mgKOH/g . 如請求項1或2之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(B)具有羥基，且羥值為0.3mgKOH/g以上且40mgKOH/g以下之範圍。The adhesive composition for an optical member protective film according to claim 1 or 2, wherein the (meth)acrylic polymer (B) has a hydroxyl group, and the hydroxyl value is in the range of 0.3 mgKOH/g or more and 40 mgKOH/g or less . 如請求項1或2之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(B)具有羧基，且酸價為0.7mgKOH/g以上且24mgKOH/g以下之範圍。The adhesive composition for an optical member protective film according to claim 1 or 2, wherein the (meth)acrylic polymer (B) has a carboxyl group and has an acid value in the range of not less than 0.7 mgKOH/g and not more than 24 mgKOH/g . 如請求項1或2之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(C)之羥值為40mgKOH/g以下。The adhesive composition for an optical member protective film according to claim 1 or 2, wherein the (meth)acrylic polymer (C) has a hydroxyl value of 40 mgKOH/g or less. 如請求項1或2之光學構件保護薄膜用黏著劑組成物，其中，該(甲基)丙烯酸系聚合物(C)之重量平均分子量比該(甲基)丙烯酸系聚合物(B)之重量平均分子量小。The adhesive composition for an optical member protective film according to claim 1 or 2, wherein the weight average molecular weight of the (meth)acrylic polymer (C) is higher than the weight of the (meth)acrylic polymer (B) The average molecular weight is small. 如請求項1或2之光學構件保護薄膜用黏著劑組成物，含有抗靜電劑。The adhesive composition for an optical member protective film as claimed in claim 1 or 2 contains an antistatic agent. 如請求項1或2之光學構件保護薄膜用黏著劑組成物，含有聚醚改性聚矽氧化合物。The adhesive composition for an optical member protective film as claimed in claim 1 or 2 contains a polyether-modified polysiloxane compound. 一種光學構件保護薄膜，具備： 基材；及 黏著劑層，係設置於該基材上，且由如請求項1至9中任一項之光學構件保護薄膜用黏著劑組成物形成。An optical component protective film, comprising: substrate; and The adhesive layer is provided on the base material, and is formed of the adhesive composition for an optical member protective film according to any one of claims 1 to 9.
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