TWI618768B - Pressure-sensitive adhesive composition and optical element surface protection film - Google Patents
Pressure-sensitive adhesive composition and optical element surface protection film Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- 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
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- 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
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- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
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- 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
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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Abstract
本發明為一種黏著劑組成物,含有:(甲基)丙烯酸共聚物,包含下列通式(1)表示之第1構成單元及來自具有羥基之單體之第2構成單元;於聚醚末端具有羥基之聚醚改性矽酮;及鹼金屬鹽。下列通式(1)中,R1表示氫原子或甲基,L表示由選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成之2價連結基。 The present invention is an adhesive composition containing: a (meth) acrylic acid copolymer, comprising a first constitutional unit represented by the following general formula (1) and a second constitutional unit derived from a monomer having a hydroxyl group; Polyether-modified silicones with hydroxyl groups; and alkali metal salts. In the following general formula (1), R 1 represents a hydrogen atom or a methyl group, and L represents a divalent linking group composed of at least one selected from the group consisting of an alkylene group, an alkylene group, a carbonyl group, and an oxygen atom. .
Description
本發明係關於黏著劑組成物及光學構件表面保護膜。 The present invention relates to an adhesive composition and a surface protective film for an optical member.
液晶顯示裝置由於薄型輕量且使用消耗電力少,近年利用於各種資訊相關設備。例如,將液晶顯示裝置利用於作為文字處理器、筆記型電腦的畫面顯示裝置。如此之液晶顯示板,係同時使用為主要部分之內藏液晶的玻璃晶槽(液晶胞)以及偏光板、相位差板等之光學構件。 Liquid crystal display devices have been used in various information-related equipment in recent years because they are thin and light and consume less power. For example, a liquid crystal display device is used as a screen display device of a word processor or a notebook computer. Such a liquid crystal display panel is an optical member such as a glass cell (liquid crystal cell) in which liquid crystal is contained as a main part and a polarizing plate and a retardation plate.
該等之光學構件,通常,進一步以表面保護膜黏接被覆光學構件而形成長形光學構件疊層體,以避免在經由衝壓加工、檢查、輸送、組裝液晶顯示面板等之各步驟期間其表面被污染或損傷。該表面保護膜在已不需要表面保護之階段時,從光學構件予以剝離去除。 These optical members are usually covered with a surface protective film to cover the optical member to form a long optical member laminate, so as to avoid the surface of the optical member during the steps of stamping, inspection, transportation, and assembly of the liquid crystal display panel. Contaminated or damaged. This surface protection film is peeled and removed from the optical member when the surface protection film is no longer needed.
如此之表面保護膜,要求於光學構件需要表面保護之期間,在該構件的表面上以不發生偏移或者從表面脫落的程度黏著於其表面。與其同時,要求表面保護膜應為高度透明,以不造成妨礙液晶的性能檢查等各種的檢查,及要求於黏著劑層內及該黏著劑層與光學構件之界面無膨起、穿隧(tunneling)、剝落等之缺陷。表面保護膜從光學構件剝離時,要求表面保護膜能夠容易地剝離,而不發生因為伴隨剝離而液晶顯示板歪斜而導致損傷 光學構件及液晶胞,及光學構件從液晶胞光學構件剝離等之不利的情況。更者,表面保護膜在剝離時,要求於光學構件上不產生來自表面保護膜之殘渣,亦即,要求對被接著物之污染性(以下亦簡單稱為「污染性」)低。 Such a surface protection film is required to adhere to the surface of the member so as not to shift or fall off from the surface during the period when the optical member needs surface protection. At the same time, the surface protection film is required to be highly transparent so as not to cause various inspections such as performance inspections that hinder liquid crystal, and it is required that there is no swelling or tunneling in the adhesive layer and the interface between the adhesive layer and the optical member ), Defects such as peeling. When the surface protective film is peeled from the optical member, it is required that the surface protective film can be easily peeled off without causing damage to the liquid crystal display panel due to the peeling. Disadvantages such as the optical member and the liquid crystal cell, and the peeling of the optical member from the optical member of the liquid crystal cell. In addition, when the surface protective film is peeled off, it is required that no residues from the surface protective film be generated on the optical member, that is, it is required that the contamination property to the adherend (hereinafter simply referred to as "contamination property") is low.
近年,以作業效率提升為目的,表面保護膜的剝離速度,有高速化之傾向,作為黏著劑的特性,也已要求表面保護膜在高速剝離中的作業性。 In recent years, for the purpose of improving work efficiency, the peeling speed of the surface protective film tends to increase. As a characteristic of the adhesive, the workability of the surface protective film in high-speed peeling has also been required.
另一方面,若表面保護膜從光學構件剝離時發生靜電,則光學膜表面吸附污垢或灰塵而對產品發生不利的情況。又,剝離表面保護膜時,若發生很大的靜電則有顯示構件電路損壞之顧慮。因此在表面保護膜剝離時,要求要有良好的抗靜電性。 On the other hand, if static electricity is generated when the surface protective film is peeled from the optical member, dirt or dust is adsorbed on the surface of the optical film, which is disadvantageous to the product. In addition, when the surface protection film is peeled off, if a large static electricity occurs, the display member circuit may be damaged. Therefore, when the surface protective film is peeled off, good antistatic properties are required.
相關於前述,在日本特開2009-275128號公報,揭示含有丙烯酸共聚物、金屬鹽、及具有聚伸烷氧基之有機聚矽氧烷的黏著劑。該黏著劑,對於被接著物的污染少,剝離帶電導致之靜電的發生少。 In relation to the foregoing, Japanese Patent Application Laid-Open No. 2009-275128 discloses an adhesive containing an acrylic copolymer, a metal salt, and an organopolysiloxane having a polyalkyleneoxy group. This adhesive has less contamination of the adherend, and has less occurrence of static electricity due to peeling and charging.
又,在日本特開2002-277634號公報,揭示一種具有黏著劑層之黏著型光學膜,該黏著劑層含有:含具有羧基之特定結構的單體單元而成之丙烯酸系聚合物藉由多官能性化合物交聯而成者。此黏著型光學膜,再加工性與應力緩和性優秀。 Also, Japanese Patent Application Laid-Open No. 2002-277634 discloses an adhesive optical film having an adhesive layer containing an acrylic polymer including a monomer unit having a specific structure having a carboxyl group. Cross-linked functional compounds. This adhesive optical film is excellent in reworkability and stress relaxation.
更者,在日本特開2011-063712號公報,揭示一種表面保護膜,具有在丙烯酸系黏著劑中另外添加聚醚改性有機聚矽氧烷等含有矽之化合物而成之黏著劑層。該表面保護膜可抑制靜電的發生。 Furthermore, Japanese Patent Application Laid-Open No. 2011-063712 discloses a surface protection film having an adhesive layer formed by adding a silicon-containing compound such as polyether-modified organic polysiloxane to an acrylic adhesive. This surface protection film can suppress the occurrence of static electricity.
然而,記載於日本特開2009-275128號公報、日本特開2002-277634號公報、及日本特開2011-063712號公報之黏著劑,有時難以更高水準兼具抗靜電性與低污染性。 However, the adhesives described in Japanese Patent Application Laid-Open No. 2009-275128, Japanese Patent Application Laid-Open No. 2002-277634, and Japanese Patent Application Laid-Open No. 2011-063712 are sometimes difficult to achieve higher levels of both antistatic properties and low pollution. .
本發明之課題係提供能夠高水準地兼具抗靜電性及對被接著物之污染性低的黏著劑組成物及使用此而成之光學構件表面保護膜。 An object of the present invention is to provide a high-level adhesive composition having both antistatic properties and low contamination to adherends, and an optical member surface protective film using the same.
本發明包含以下之態樣。 The present invention includes the following aspects.
<1>一種黏著劑組成物,含有:第1(甲基)丙烯酸共聚物,包含下列通式(1)表示之第1構成單元及來自具有羥基之單體之第2構成單元,與於聚醚末端具有羥基之聚醚改性矽酮,與鹼金屬鹽。 <1> An adhesive composition comprising: a first (meth) acrylic acid copolymer, comprising a first constitutional unit represented by the following general formula (1) and a second constitutional unit derived from a monomer having a hydroxyl group, and Polyether-modified silicone with a hydroxyl group at the end of the ether, and an alkali metal salt.
通式(1)中,R1表示氫原子或甲基。L表示由選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成之2價連結基。 In the general formula (1), R 1 represents a hydrogen atom or a methyl group. L represents a divalent linking group composed of at least one selected from the group consisting of an alkylene group, an arylene group, a carbonyl group, and an oxygen atom.
<2>如前述<1>記載之黏著劑組成物,其中,前述通式(1)中之L,係選自於由下列通式(2a)表示之2價連結基及下列通式(2b)表示之2價連結基構成之群組中之至少1種。 <2> The adhesive composition according to the aforementioned <1>, wherein L in the general formula (1) is selected from a divalent linking group represented by the following general formula (2a) and the following general formula (2b) At least one of the groups consisting of the divalent linking bases indicated by).
通式(2a)及(2b)中,R21~R24各自獨立地表示碳數1~12之伸烷基或碳數6~10之伸芳基。n表示0~10之數值,m表示1~10之數值。 In the general formulae (2a) and (2b), R 21 to R 24 each independently represent an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms. n represents a value from 0 to 10, and m represents a value from 1 to 10.
<3>如前述<1>或<2>記載之黏著劑組成物,其中,前述第1(甲基)丙烯酸共聚物中之前述第1構成單元的含有率為0.5質量%~5質量%。 <3> The adhesive composition according to the above <1> or <2>, wherein the content rate of the first constituent unit in the first (meth) acrylic copolymer is 0.5% by mass to 5% by mass.
<4>如前述<1>~<3>中之任一者記載之黏著劑組成物,其中,前述聚醚改性矽酮的含量,相對於前述(甲基)丙烯酸共聚物100質量份,為0.05質量份~0.50質量份。 <4> The adhesive composition according to any one of <1> to <3>, wherein the content of the polyether-modified silicone is 100 parts by mass relative to the (meth) acrylic copolymer, It is 0.05 to 0.50 parts by mass.
<5>如前述<1>~<4>中之任一者記載之黏著劑組成物,更含有第2(甲基)丙烯酸共聚物,其包含具有聚伸烷氧基之構成單元且較前述第1(甲基)丙烯酸共聚物的分子量低。 <5> The adhesive composition according to any one of the above <1> to <4>, further comprising a second (meth) acrylic acid copolymer, which contains a constitutional unit having a polyalkyleneoxy group and is larger than the foregoing The molecular weight of the 1st (meth) acrylic acid copolymer is low.
<6>一種光學構件表面保護膜,具備:聚酯基材;與黏著劑層,設置於前述聚酯基材上,來自於如前述<1>~<5>中之任一項記載之黏著劑組成物。 <6> A protective film for the surface of an optical member, comprising: a polyester substrate; and an adhesive layer provided on the polyester substrate and derived from the adhesion as described in any one of the above <1> to <5>剂 组合 物。 Composition.
根據本發明,能夠提供可高水準地兼具抗靜電性及對被接著物污染性低的黏著劑組成物及使用此而成之光學構件表面保護膜。 According to the present invention, it is possible to provide an adhesive composition having both a high level of antistatic properties and low contamination to an adherend, and an optical member surface protective film using the same.
在本說明書中,使用「~」所表示之數值範圍,係表示分別包含記載於「~」之前後的數值作為最小值及最大值的範圍。又在本說明書中,當言及針對組成物中各成分的量之情形時,在組成物中符合各成分之物質多數存在之情形時,除非有特別指示,則其係意謂存在於組成物中的該多數物質的合計量。 In this specification, the use of a numerical range indicated by "~" means a range that includes numerical values before and after "~" as the minimum and maximum values, respectively. Also in this specification, when referring to the case of the amount of each component in the composition, when a majority of the substances in the composition are present in the composition, unless specifically instructed, it means that it is present in the composition. The total amount of the majority of substances.
更者,(甲基)丙烯酸酯,意指丙烯酸酯及丙烯酸甲酯中之至少一者;類 似(甲基)丙烯酸酯之(甲基)丙烯酸共聚物等之語句也係同樣之含意。 Furthermore, (meth) acrylate means at least one of acrylate and methyl acrylate; (Meth) acrylic acid-like (meth) acrylic acid copolymer-like terms have the same meaning.
<黏著劑組成物> <Adhesive composition>
本發明之黏著劑組成物含有:第1(甲基)丙烯酸共聚物,包含以下列通式(1)表示之第1構成單元及來自具有羥基之單體之第2構成單元;與於聚醚末端具有羥基之聚醚改性矽酮;與鹼金屬鹽。前述黏著劑組成物視須要也可進一步含有其他的成分。 The adhesive composition of the present invention contains: a first (meth) acrylic acid copolymer including a first constituent unit represented by the following general formula (1) and a second constituent unit derived from a monomer having a hydroxyl group; and a polyether Polyether-modified silicones with hydroxyl groups at the ends; and alkali metal salts. The said adhesive composition may further contain another component as needed.
通式(1)中,R1表示氫原子或甲基。L表示由選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成之2價連結基。 In the general formula (1), R 1 represents a hydrogen atom or a methyl group. L represents a divalent linking group composed of at least one selected from the group consisting of an alkylene group, an arylene group, a carbonyl group, and an oxygen atom.
黏著劑組成物含有:包含具有羧基之特定結構的第1構成單元及來自具有羥基之單體之第2構成單元的第1(甲基)丙烯酸共聚物,與於聚醚末端具有羥基之聚醚改性矽酮,與鹼金屬鹽;而藉此於抗靜電性及對於被接著物之低污染性兩者優秀,更具有優良黏著性,有優秀之可靠性。該黏著劑組成物能夠理想地應用於光學構件表面保護膜。 The adhesive composition includes a first (meth) acrylic copolymer including a first structural unit having a specific structure having a carboxyl group and a second structural unit derived from a monomer having a hydroxyl group, and a polyether having a hydroxyl group at a polyether terminal. Modified silicone, and alkali metal salt; by this, it is excellent in both antistatic properties and low pollution to the adherend, it also has excellent adhesion and excellent reliability. This adhesive composition can be ideally applied to the surface protective film of an optical member.
此例如能夠推測如下。據認為黏著劑組成物因含有聚醚改性矽酮,及藉由聚醚改性矽酮與鹼金屬鹽之交互作用,而在黏著劑組成物的表面附近鹼金屬鹽可局部化,黏著劑組成物展現優良抗靜電性。更者,據認為藉由第1(甲基)丙烯酸共聚物與聚醚改性矽酮交互作用,黏著劑組成物的表面電阻值有效的降低,黏著劑組成物展現更優良抗靜電性。此據認為可歸因於 第1(甲基)丙烯酸共聚物具有特定結構的第1構成單元及第2構成單元兩者。尤其,據認為若不是包含特定結構的第1構成單元作為羧基之構成單元之,而是包含來自(甲基)丙烯酸等之含羧基之構成單元的(甲基)丙烯酸共聚物,則無法充分得到如此之功效。更者,據認為藉由聚醚改性矽酮於聚醚末端具有羥基,將黏著劑從被接著物剝離時,可有效抑制黏著劑組成物的構成成分殘留於被接著物上,黏著劑組成物能夠展現對於被接著物之優良低污染性。 This can be estimated as follows, for example. It is considered that the adhesive composition contains polyether-modified silicone and the interaction between the polyether-modified silicone and the alkali metal salt, so that the alkali metal salt can be localized near the surface of the adhesive composition. The composition exhibits excellent antistatic properties. Furthermore, it is thought that the surface resistance value of the adhesive composition is effectively reduced by the interaction between the first (meth) acrylic acid copolymer and the polyether-modified silicone, and the adhesive composition exhibits more excellent antistatic properties. This is believed to be attributable to The 1st (meth) acrylic copolymer has both the 1st structural unit and the 2nd structural unit of a specific structure. In particular, it is considered that a (meth) acrylic copolymer containing a carboxyl-containing structural unit derived from (meth) acrylic acid, etc., is not sufficient unless it is a structural unit containing a first structural unit of a specific structure as a carboxyl group. So effective. Furthermore, it is thought that the polyether-modified silicone has a hydroxyl group at the end of the polyether, and when the adhesive is peeled from the adherend, the constituents of the adhesive composition can be effectively suppressed from remaining on the adherend. The object can exhibit excellent low pollution to the adherend.
[(甲基)丙烯酸共聚物] [(Meth) acrylic copolymer]
黏著劑組成物,至少含有1種第1(甲基)丙烯酸共聚物(以下亦稱為「樹脂A」),該第1(甲基)丙烯酸共聚物包含前述通式(1)表示之第1構成單元及來自具有羥基之單體之第2構成單元。黏著劑組成物視須要也可更包含與第1(甲基)丙烯酸共聚物相異之(甲基)丙烯酸共聚物。 The adhesive composition contains at least one first (meth) acrylic copolymer (hereinafter also referred to as "resin A"), and the first (meth) acrylic copolymer includes the first The structural unit and the second structural unit derived from a monomer having a hydroxyl group. The adhesive composition may further include a (meth) acrylic copolymer different from the 1st (meth) acrylic copolymer, if necessary.
在此,(甲基)丙烯酸共聚物係指構成共聚物之全部單體成分(有將構成共聚物之單體簡單記載為共聚合成分的情形)的50質量%以上,理想為90質量%以上為(甲基)丙烯酸單體之共聚物。 Here, the (meth) acrylic copolymer refers to 50% by mass or more of all monomer components constituting the copolymer (in the case where the monomers constituting the copolymer are simply described as copolymerization components), and preferably 90% by mass or more. It is a copolymer of (meth) acrylic monomers.
(第1(甲基)丙烯酸共聚物) (1st (meth) acrylic copolymer)
第1(甲基)丙烯酸共聚物至少包含1種前述通式(1)表示之第1構成單元。在前述通式(1)表示之第1構成單元中,L表示由選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成之2價連結基。L中之伸烷基也可為直鏈狀、分枝鏈狀及環狀中之任一者。L中之伸烷基為直鏈狀或分枝鏈狀的情形時,伸烷基之碳數較佳為1~12,更佳為2~10,又更佳為2~6。 The 1st (meth) acrylic copolymer contains at least 1 sort (s) of 1st structural unit represented by the said General formula (1). In the first constitutional unit represented by the general formula (1), L represents a divalent linking group composed of at least one selected from the group consisting of an alkylene group, an arylene group, a carbonyl group, and an oxygen atom. The alkylene group in L may be any of linear, branched, and cyclic. When the alkylene group in L is linear or branched, the carbon number of the alkylene group is preferably 1 to 12, more preferably 2 to 10, and even more preferably 2 to 6.
又L中之伸烷基為環狀的情形時,伸烷基之碳數,較佳為3~12,更佳為4~8,又更佳為5~6。例如環狀之伸烷基為環伸己基的情形時,鍵結位置為1位及4位、1位及2位、及1位及3位中任一者皆可,理想為1位及2位。 When the alkylene group in L is cyclic, the carbon number of the alkylene group is preferably 3 to 12, more preferably 4 to 8, and still more preferably 5 to 6. For example, when the cyclic alkylene group is cyclohexyl group, the bonding position may be any of the 1st and 4th positions, the 1st and 2nd positions, and the 1st and 3rd positions, and the 1st and 2nd positions are desirable. Bit.
L中之伸芳基,較佳為碳數6~10,更佳為伸苯基。伸芳基中之鍵結位 置無特別限制。例如伸芳基為伸苯基的情形時,鍵結位置為1位及4位、1位及2位、及1位及3位中任一者皆可,理想為1位及2位。 The arylene group in L is preferably 6 to 10 carbon atoms, and more preferably phenylene. Bonding position in arylene There are no special restrictions. For example, when the arylene group is a phenyl group, the bonding position may be any of the 1st and 4th positions, the 1st and 2nd positions, and the 1st and 3rd positions, and the 1st and 2nd positions are desirable.
L中之伸烷基及伸芳基,也可具有取代基。作為取代基可舉例如:碳數1~12之烷基、鹵素原子、羥基、胺基、硝基、苯基等。 The alkylene and aryl groups in L may have a substituent. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a nitro group, and a phenyl group.
通式(1)中之L表示之2價連結基,從抗靜電性及對被接著物之低污染性之觀點而言,理想為下列通式(2a)或通式(2b)表示之2價連結基。 The divalent linking group represented by L in the general formula (1) is preferably 2 represented by the following general formula (2a) or (2b) from the viewpoints of antistatic properties and low pollution to adherends. Price link base.
通式(2a)及(2b)中,R21~R24各自獨立地表示碳數1~12的伸烷基或碳數6~10的伸芳基。n表示0~10的數值,m表示1~10的數值。 In the general formulae (2a) and (2b), R 21 to R 24 each independently represent an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms. n represents a value from 0 to 10, and m represents a value from 1 to 10.
R21~R24中之伸烷基,可為直鏈狀、分枝鏈狀及環狀中之任一者,較佳為直鏈狀或分枝鏈狀,更佳為直鏈狀。 The alkylene group in R 21 to R 24 may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear.
R21~R24中之伸芳基中之鍵結位置無特別限制。例如伸芳基為伸苯基或環伸己基的情形時,鍵結位置為1位及4位、1位及2位、及1位及3位中之任一者皆可,理想為1位及2位。 The bonding position in the arylene group in R 21 to R 24 is not particularly limited. For example, when the arylene group is a phenylene group or a cyclohexyl group, the bonding position may be any of the 1st and 4th positions, the 1st and 2nd positions, and the 1st and the 3rd positions, and the 1st position is desirable. And 2 people.
R21及R22中之伸烷基,較佳為碳數2~10,更佳為碳數2~6。R21及R22中之伸烷基,可相同也可相異。 The alkylene group in R 21 and R 22 is preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. The alkylene groups in R 21 and R 22 may be the same or different.
R21及R22中之伸芳基,較佳為伸苯基或伸萘基,更佳為伸苯基。 The arylene group in R 21 and R 22 is preferably a phenylene group or a naphthyl group, and more preferably a phenylene group.
通式(2a)中之R21及R22,從抗靜電性及對被接著物之低污染性之觀點而言,較佳為碳數1~12的伸烷基,更佳為碳數2~6之伸烷基,又更佳為碳數2~6且為直鏈狀或分枝鏈狀之伸烷基。 R 21 and R 22 in the general formula (2a) are preferably an alkylene group having 1 to 12 carbon atoms, and more preferably 2 carbon atoms in terms of antistatic properties and low pollution to an adherend. An alkylene group of ~ 6, and more preferably a linear or branched alkylene group having 2 to 6 carbon atoms.
n表示0~10的數值。在第1(甲基)丙烯酸共聚物包含之以通式(1)表示之第1構成單元僅1種的情形時,n為整數;第1構成單元包含2種以上的情形時,n為平均值,亦即有理數。n較佳為0~4,更佳為0~2。 n represents a value from 0 to 10. When the first (meth) acrylic acid copolymer contains only one kind of the first structural unit represented by the general formula (1), n is an integer; when the first constituent unit contains two or more kinds, n is an average Value, which is a rational number. n is preferably 0 to 4, more preferably 0 to 2.
R23較佳為碳數1~12之伸烷基,更佳為碳數2~6之伸烷基,又更佳為碳數2~4之伸烷基。 R 23 is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms.
R24較佳為碳數2~6之直鏈狀或分枝鏈狀之伸烷基、碳數4~8之環狀伸烷基、或碳數6~10之伸芳基,更佳為碳數2~4之直鏈狀或分枝鏈狀之伸烷基、碳數5~6之環狀伸烷基、或伸苯基,又更佳為碳數2~4之直鏈狀或分枝鏈狀之伸烷基、環伸己基、或伸苯基。 R 24 is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, a cyclic alkylene group having 4 to 8 carbon atoms, or an aromatic group having 6 to 10 carbon atoms, and more preferably Linear or branched alkylene group with 2 to 4 carbon atoms, cyclic alkylene group with 5 to 6 carbon atoms or phenylene group, and more preferably a linear or branched chain with 2 to 4 carbon atoms Branched chain alkylene, cyclohexyl, or phenylene.
m表示1~10之數值。第1(甲基)丙烯酸共聚物包含之以通式(1)表示之第1構成單元僅1種的情形時,m為整數;第1構成單元包含2種以上的情形時,m為平均值,亦即有理數。m較佳為1~4,更佳為1~2。 m represents a value from 1 to 10. When the first (meth) acrylic acid copolymer contains only one kind of the first structural unit represented by the general formula (1), m is an integer; when the first constituent unit contains two or more kinds, m is an average value. , Which is a rational number. m is preferably 1 to 4, and more preferably 1 to 2.
第1(甲基)丙烯酸共聚物中之第1構成單元的含有率,從抗靜電性及對被接著物之低污染性之觀點而言,較佳為第1(甲基)丙烯酸共聚物的總質量中的0.5質量%以上5質量%以下,更佳為0.5質量%以上2質量%以下,又更佳為0.5質量%以上1質量%以下。 The content ratio of the first constituent unit in the first (meth) acrylic copolymer is preferably from the viewpoint of antistatic properties and low contamination of the adherend, and 0.5 mass% or more and 5 mass% or less of the total mass, more preferably 0.5 mass% or more and 2 mass% or less, still more preferably 0.5 mass% or more and 1 mass% or less.
若第1(甲基)丙烯酸共聚物中之第1構成單元的含有率相對於第1(甲基)丙烯酸共聚物的總質量為0.5質量%以上,則有黏著劑組成物的表面電阻降低,可獲得更優良抗靜電性之傾向。又,若第1(甲基)丙烯酸共聚物中之第1構成單元的含有率相對於第1(甲基)丙烯酸共聚物的總質量為5質量%以下,則有可抑制黏著劑組成物之隨著時間變化中的黏度上昇,能夠獲得充分的適用期(pot life)之傾向。 When the content rate of the first constituent unit in the first (meth) acrylic copolymer is 0.5% by mass or more with respect to the total mass of the first (meth) acrylic copolymer, the surface resistance of the adhesive-containing composition is reduced. A tendency to obtain more excellent antistatic properties. Moreover, if the content rate of the 1st structural unit in a 1st (meth) acrylic acid copolymer is 5 mass% or less with respect to the total mass of a 1st (meth) acrylic acid copolymer, there exists a possibility of suppressing an adhesive composition. As the viscosity increases over time, a sufficient pot life tends to be obtained.
第1(甲基)丙烯酸共聚物中之第1構成單元,可例如,藉由將以下列通式(1a)表示之單體,與構成第1(甲基)丙烯酸共聚物之其他的單體一同進行共聚合而導入第1(甲基)丙烯酸共聚物。 The first constituent unit in the first (meth) acrylic copolymer may be, for example, a monomer represented by the following general formula (1a) and other monomers constituting the first (meth) acrylic copolymer The copolymerization was carried out together to introduce the first (meth) acrylic acid copolymer.
在通式(1a)中,R1及L與通式(1)中之R1及L分別為同義。 In the general formula (1a), R 1 and L are synonymous with R 1 and L in the general formula (1), respectively.
以通式(1a)表示之單體,也可為以常法製造者,也可為從市售之單體適當選擇者。作為在通式(1a)表示之單體中L為以通式(2a)表示之單體,可舉例如:(甲基)丙烯酸二聚物(理想為通式(2a)中之n的平均值約0.4者)、ω-羧基-聚己內酯單(甲基)丙烯酸酯(理想為通式(2a)中之n的平均值約1.0者)等。該等之單體例如可使用「M-5600」、「M-5300」(以上為東亞合成股份有限公司製之商品名)等市售者。 The monomer represented by the general formula (1a) may be a conventionally produced one, or may be appropriately selected from commercially available monomers. Among the monomers represented by the general formula (1a), L is a monomer represented by the general formula (2a). For example, a (meth) acrylic acid dimer (ideally the average of n in the general formula (2a)) Those having a value of about 0.4), ω-carboxy-polycaprolactone mono (meth) acrylate (preferably, the average value of n in the general formula (2a) is about 1.0), and the like. These monomers can be marketed, for example, "M-5600", "M-5300" (the above are the trade names of Toa Kosei Co., Ltd.).
又,作為在通式(1a)表示之單體中之L為以通式(2b)表示之單體,可舉例如:2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基富馬酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸等。該等之單體例如可使用「LIGHT ESTER HO-MS」、「LIGHT ACRYLATE HOA-MS(N)」、LIGHT ACRYLATE HOA-HH(N)」、「LIGHT ACRYLATE HOA-MPL(N)」(以上為共榮社化學股份有限公司製之商品名)等市售者。 Moreover, as L in the monomer represented by General formula (1a) is a monomer represented by General formula (2b), a 2- (meth) acryloxyethyl succinic acid, 2- ( (Meth) acryloxyethyl fumaric acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, and the like. For these monomers, for example, "LIGHT ESTER HO-MS", "LIGHT ACRYLATE HOA-MS (N)", LIGHT ACRYLATE HOA-HH (N) ", and" LIGHT ACRYLATE HOA-MPL (N) "(the above are Kyoeisha Chemical Co., Ltd.) and other marketers.
第1(甲基)丙烯酸共聚物至少包含1種來自具有羥基之單體之第2構成單元。形成第2構成單元之具有羥基之單體,若為具有至少1個的羥基及可與第1構成單元形成共聚物之聚合性基的單體即可,無特殊限制,可從通常使用之單體中適當選擇使用。 The 1st (meth) acrylic copolymer contains at least 1 kind of 2nd structural unit derived from the monomer which has a hydroxyl group. The monomer having a hydroxyl group forming the second constituent unit may be a monomer having at least one hydroxyl group and a polymerizable group capable of forming a copolymer with the first constituent unit, and is not particularly limited. Use appropriately in the body.
於第1(甲基)丙烯酸共聚物導入來自具有羥基之單體之第2構成單元之方法無特別限制。例如,將包含至少1種之具有羥基之單體、與至少1種之前述通式(1a)表示之單體、及視須要的其他之單體(理想為至少1種之(甲基)丙烯酸烷基酯)之單體組成物實施共聚合,藉此可獲得在分子內包含以通式(1)表示之第1構成單元及來自具有羥基之單體之第2構成單元之第1(甲基)丙烯酸共聚物。 The method for introducing the second constitutional unit derived from the monomer having a hydroxyl group into the first (meth) acrylic copolymer is not particularly limited. For example, at least one monomer having a hydroxyl group, at least one monomer represented by the aforementioned general formula (1a), and other monomers (ideally at least one type of (meth) acrylic acid) The monomer composition of the alkyl ester) is copolymerized to obtain the first (A) containing the first constitutional unit represented by the general formula (1) and the second constitutional unit derived from the monomer having a hydroxyl group in the molecule. Based) acrylic copolymer.
作為具有羥基之單體,可舉例如:具有羥基及乙烯性不飽和鍵結基之單體。作為具有羥基之單體具體而言,可舉例如:(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3-甲基-3-羥基丁酯、(甲基)丙烯酸1,1-二甲基-3-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、單(甲基)丙烯酸甘油酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚(乙二醇-丙二醇)單(甲基)丙烯酸酯等(甲基)丙烯酸酯類;N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等(甲基)丙烯醯胺類;烯丙醇、甲烯丙基醇等不飽和醇;等。 Examples of the monomer having a hydroxyl group include monomers having a hydroxyl group and an ethylenically unsaturated bonding group. Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (methyl) ) 4-hydroxybutyl acrylate, 3-methyl-3-hydroxybutyl (meth) acrylate, 1,1-dimethyl-3-butyl (meth) acrylate, 1,3 (meth) acrylate -Dimethyl-3-hydroxybutyl, 2,2,4-trimethyl-3-hydroxypentyl (meth) acrylate, 2-ethyl-3-hydroxyhexyl (meth) acrylate, mono ( (Meth) acrylic acid, such as glyceryl methacrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. Esters; (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamides; unsaturated allyl alcohols, allyl alcohols, etc. Alcohol; etc.
其中尤以,從與其他之單體之互溶性及共聚合性良好的點,及與交聯劑之交聯反應良好的點而言,具有羥基之單體,較佳為具有1個羥基與碳數2~6之烷基之(甲基)丙烯酸酯,更佳為(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸4-羥基丁酯。 Among them, from the point of good mutual solubility and copolymerizability with other monomers and the point of good cross-linking reaction with the cross-linking agent, the monomer having a hydroxyl group preferably has one hydroxyl group and The (meth) acrylate of an alkyl group having 2 to 6 carbon atoms is more preferably 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate.
作為第1(甲基)丙烯酸共聚物中之來自具有羥基之單體之第2構成單元的含有率,較佳為在第1(甲基)丙烯酸共聚物的總質量中為0.1質量%以上10.0質量%以下,更佳為2.0質量%以上8.0質量%以下,又更佳為2.0質量%以上5.0質量%以下。藉由將來自具有羥基之單體之構成單元的含有率設為前述下限值以上,則有更為有效地抑制對被接著物發生污染的傾向。又藉由將來自具有羥基之單體之構成單元的含有率設為前述上限值以下,則有順應性(透濕性)更為良好之傾向。 The content rate of the second constituent unit derived from the monomer having a hydroxyl group in the first (meth) acrylic copolymer is preferably 0.1% by mass or more and 10.0 in the total mass of the first (meth) acrylic copolymer. Mass% or less, more preferably 2.0 mass% or more and 8.0 mass% or less, and still more preferably 2.0 mass% or more and 5.0 mass% or less. When the content rate of the constituent unit derived from the monomer having a hydroxyl group is equal to or more than the aforementioned lower limit value, there is a tendency that contamination of the adherend is more effectively suppressed. Moreover, when the content rate of the structural unit derived from the monomer which has a hydroxyl group is below the said upper limit, compliance (moisture permeability) tends to be more favorable.
第1(甲基)丙烯酸共聚物中之第1構成單元與第2構成單元之含有比率無特別限制。從抗靜電性及對被接著物之低污染性之觀點而言,第1(甲基)丙烯酸共聚物中之第1構成單元相對於第2構成單元之含有比率(第1構成單元/第2構成單元),以質量基準計較佳為1/10~2/1,更佳為1/5~4/3。 The content ratio of the first constituent unit and the second constituent unit in the first (meth) acrylic copolymer is not particularly limited. From the viewpoint of antistatic properties and low pollution to adherends, the content ratio of the first constituent unit to the second constituent unit in the first (meth) acrylic copolymer (first constituent unit / second Constituent unit), preferably 1/10 to 2/1, more preferably 1/5 to 4/3 on a mass basis.
第1(甲基)丙烯酸共聚物中之第1構成單元及第2構成單元的總含有率無特別限制。從抗靜電性及對被接著物之低污染性之觀點而言,第1(甲基)丙烯酸共聚物中之第1構成單元及第2構成單元的總含有率,較佳為第1(甲基)丙烯酸共聚物的總質量中之1質量%以上15質量%以下,更佳為2質量%以上10質量%以下,又更佳為3質量%以上8質量%以下。 The total content of the first constituent unit and the second constituent unit in the first (meth) acrylic copolymer is not particularly limited. From the viewpoint of antistatic properties and low pollution to the adherend, the total content of the first constituent unit and the second constituent unit in the first (meth) acrylic copolymer is preferably the first (a 1% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and still more preferably 3% by mass or more and 8% by mass or less of the total mass of the acrylic copolymer.
第1(甲基)丙烯酸共聚物,除了第1構成單元及第2構成單元以外,理想為更包含至少1種之來自(甲基)丙烯酸烷基酯的第三構成單元。 The first (meth) acrylic copolymer preferably contains, in addition to the first structural unit and the second structural unit, at least one type of third structural unit derived from an alkyl (meth) acrylate.
(甲基)丙烯酸烷基酯中之烷基也可為直鏈狀,也可為分枝鏈狀。又,(甲基)丙烯酸烷基酯中之烷基的碳數,從黏著性之觀點而言,較佳為1~18,更佳為2~10。 The alkyl group in the alkyl (meth) acrylate may be linear or branched. The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably from 1 to 18, more preferably from 2 to 10, from the viewpoint of adhesion.
作為(甲基)丙烯酸烷基酯具體而言可舉例如:(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)丙烯酸正十二酯、(甲基)丙烯酸十八酯等之碳數1~18的直鏈狀或分枝鏈狀之具有烷基之(甲基)丙烯酸烷基酯及該等的衍生物。 Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, (formyl) (N-decyl acrylate), n-dodecyl (meth) acrylate, octadecyl (meth) acrylate, etc., linear or branched (meth) groups having an alkyl group having 1 to 18 carbon atoms Alkyl acrylate and derivatives thereof.
第1(甲基)丙烯酸共聚物,也可僅包含1種、也可包含2種以上之來自(甲基)丙烯酸烷基酯之第三構成單元,理想為包含2種以上。第1(甲基)丙烯酸共聚物包含2種第三構成單元的情形時,較佳為一者為具有碳數1~5之直鏈狀或分枝鏈狀之烷基的來自(甲基)丙烯酸烷基酯之構成單元,另一者為具有碳數6~18之直鏈狀或分枝鏈狀之烷基的來自(甲基)丙烯酸烷基酯之構成單元,更佳為一者為具有碳數2~5之直鏈狀之烷基的來自(甲基)丙烯酸 烷基酯之構成單元,另一者為具有碳數6~10之分枝鏈狀之烷基的來自(甲基)丙烯酸烷基酯之構成單元。 The first (meth) acrylic copolymer may contain only one kind, or may include two or more kinds of third constituent units derived from the alkyl (meth) acrylate, and preferably contains two or more kinds. When the 1st (meth) acrylic acid copolymer contains 2 types of 3rd structural units, it is preferable that one is a (meth) -derived (meth) group which has a linear or branched alkyl group having 1 to 5 carbon atoms. The other structural unit of the alkyl acrylate is a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group having 6 to 18 carbon atoms, and more preferably one is (Meth) acrylic acid having a linear alkyl group having 2 to 5 carbon atoms The other structural unit of an alkyl ester is a structural unit derived from an alkyl (meth) acrylate having a branched chain alkyl group having 6 to 10 carbon atoms.
第1(甲基)丙烯酸共聚物包含第三構成單元的情形時,第三構成單元的含有率,較佳為第1(甲基)丙烯酸共聚物的總質量中之60質量%以上99.9質量%以下,更佳為72質量%以上99.5質量%以下,又更佳為85質量%以上99質量%以下。若第三構成單元的含有率為前述下限值以上,則順應性(透濕性)有成為更良好之傾向。又,第三構成單元的含有率若為前述上限值以下,則有高速剝離時的黏著力不會變為過大,高速剝離時之作業性更為優秀之傾向。 When the 1st (meth) acrylic copolymer contains a 3rd structural unit, it is preferable that the content rate of a 3rd structural unit is 60 mass%-99.9 mass% of the total mass of a 1 (meth) acrylic copolymer Hereinafter, it is more preferably 72% by mass or more and 99.5% by mass or less, and still more preferably 85% by mass or more and 99% by mass or less. When the content rate of the third constituent unit is equal to or more than the aforementioned lower limit value, the compliance (moisture permeability) tends to be more favorable. In addition, if the content rate of the third constituent unit is equal to or less than the aforementioned upper limit value, the adhesive force during high-speed peeling does not become excessively large, and the workability during high-speed peeling tends to be more excellent.
第1(甲基)丙烯酸共聚物,視須要也可更包含除了第1構成單元、第2構成單元及第三構成單元以外之其他構成單元。作為形成其他構成單元之單體,可舉例如:(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯等具有環狀基之(甲基)丙烯酸酯;飽和脂肪酸乙烯酯,例如甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、「叔碳酸乙烯酯(vinyl versatate)」(商品名、新癸酸乙烯酯)等脂肪族乙烯基單體;苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯基單體;丙烯腈、甲基丙烯腈等氰基乙烯基單體;馬來酸二甲酯、馬來酸二正丁酯、馬來酸二-2-乙基己酯、馬來酸二正辛酯、富馬酸二甲酯、富馬酸二正丁酯、富馬酸二-2-乙基己酯、富馬酸二正辛酯等馬來酸或富馬酸之二酯單體;等。 The 1st (meth) acrylic copolymer may further contain the structural unit other than a 1st structural unit, a 2nd structural unit, and a 3rd structural unit as needed. Examples of monomers forming other constituent units include (meth) acrylates having a cyclic group such as cyclohexyl (meth) acrylate and benzyl (meth) acrylate; vinyl esters of saturated fatty acids such as ethylene formate Esters, vinyl acetate, vinyl propionate, "vinyl versatate" (trade name, vinyl neodecanoate) and other aliphatic vinyl monomers; styrene, α-methylstyrene, ethylene Aromatic vinyl monomers such as methyl toluene; cyano vinyl monomers such as acrylonitrile, methacrylonitrile; dimethyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate Esters, di-n-octyl maleate, dimethyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, di-n-octyl fumarate, etc. Diester of maleic acid; etc.
更者,作為形成其他構成單元之單體,可舉例如:分子內除了具有1個自由基聚合性基以外尚具有至少1個的官能基之單體,係與形成第1構成單元之單體及形成第2構成單元之單體相異之單體(以下亦稱為「官能性單體」)。作為官能性單體可舉例如:具有羧基、醯胺基、經取代或未經取代之醯胺基、經取代或未經取代之胺基、烷氧基、環氧基、巰基、含矽基等官能基之單體。又,作為形成其他構成單元之單體,也可使用分子內具有2個以上自由基聚合性基之單體。 Furthermore, as a monomer forming another constituent unit, for example, a monomer having at least one functional group in addition to a radical polymerizable group in the molecule, and a monomer forming the first constituent unit And monomers that are different from the monomers that form the second constituent unit (hereinafter also referred to as "functional monomers"). Examples of the functional monomer include a carboxyl group, an amido group, a substituted or unsubstituted amido group, a substituted or unsubstituted amino group, an alkoxy group, an epoxy group, a mercapto group, and a silicon-containing group. Isofunctional monomers. Moreover, as a monomer which forms another structural unit, the monomer which has two or more radically polymerizable groups in a molecule | numerator can also be used.
作為該等官能性單體之具體例,可舉例如:(甲基)丙烯酸、亞甲基丁二 酸、馬來酸酐等含有羧基或其酐基之單體;(甲基)丙烯醯胺、二丙酮丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-正丁氧基甲基(甲基)丙烯醯胺、N-異丁氧基甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺等含有經取代或未經取代之醯胺基之單體;(甲基)丙烯酸胺基乙酯、N,N-(甲基)丙烯酸二甲基胺基乙酯、N,N-(甲基)丙烯酸二乙基胺基乙酯等含有經取代或未經取代之胺基之單體;(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-正丁氧基乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、(甲基)丙烯酸2-乙氧基乙氧基乙酯、(甲基)丙烯酸2-正丁氧基乙氧基乙酯、甲氧基聚乙二醇單(甲基)丙烯酸酯、甲氧基聚乙二醇單甲基丙烯酸酯等含有烷氧基之單體;(甲基)丙烯酸環氧丙酯、環氧丙基烯丙醚、環氧丙基甲基烯丙醚等含有環氧基之單體;烯丙基硫醇等含有巰基之單體;乙烯基三氯矽烷、乙烯基三溴矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三正丙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯基三正丁氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、乙烯基參(2-羥基甲氧基乙氧基)矽烷、乙烯基三乙醯氧基矽烷、乙烯基二乙氧基矽醇、乙烯基乙氧基矽二醇、乙烯基甲基二乙氧基矽烷、乙烯基二甲基乙氧基矽烷、乙烯基甲基二乙醯氧基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷、3-(甲基)丙烯醯氧丙基三甲氧基矽烷、3-(甲基)丙烯醯氧丙基三乙氧基矽烷、3-(甲基)丙烯醯氧丙基參(2-甲氧基乙氧基)矽烷、3-(甲基)丙烯醯氧丙基甲基二乙氧基矽烷、3-(甲基)丙烯醯氧丙基二甲基乙氧基矽烷、3-(甲基)丙烯醯氧丙基二甲基甲氧基矽烷、2-(甲基)丙烯醯胺乙基三乙氧基矽烷等具有含矽基之單體;等之單體群。 Specific examples of such functional monomers include (meth) acrylic acid and methylene butane Monomers containing carboxyl groups or anhydride groups, such as acids, maleic anhydride; (meth) acrylamide, diacetoneacrylamide, N-methylol (meth) acrylamide, N-n-butoxymethyl (Meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamine Amines and other monomers containing substituted or unsubstituted amido groups; aminoethyl (meth) acrylate, dimethylamino ethyl N, N- (meth) acrylate, N, N- (methyl Group) monomers containing substituted or unsubstituted amine groups such as diethylaminoethyl acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2-n-butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, (methyl ) 2-n-butoxyethoxyethyl acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol monomethacrylate and other monomers containing alkoxy groups; (Meth) acrylates containing epoxy groups, such as glycidyl acrylate, glycidyl allyl ether, glycidyl methallyl ether ; Mercapto-containing monomers such as allyl mercaptan; vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, ethylene Triisopropoxysilane, vinyltri-n-butoxysilane, vinyl ginseng (2-methoxyethoxy) silane, vinyl ginseng (2-hydroxymethoxyethoxy) silane, vinyl Triethoxysilane, vinyldiethoxysilanol, vinylethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldisiloxane Ethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3- (meth) acryloxypropyl ginseng (2-methoxyethoxy) silane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3 -(Meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 2- (meth) acrylamine ethyl triethyl Silicon-containing group Monomers; etc. monomer group.
第1(甲基)丙烯酸共聚物包含其他構成單元的情形時,其他構成單元的含有率,較佳為第1(甲基)丙烯酸共聚物的總質量中之30質量%以下,更佳為20質量%以下,又更佳為10質量%以下。若其他構成單元的含有率為前述上限值以下,則有低速剝離與高速剝離之黏著力的平衡性能夠更為良好之傾向。 When the 1st (meth) acrylic copolymer contains other structural units, the content rate of the other structural units is preferably 30% by mass or less, more preferably 20% of the total mass of the 1 (meth) acrylic copolymer. Mass% or less, and more preferably 10 mass% or less. When the content rate of the other constituent units is equal to or lower than the aforementioned upper limit value, there is a tendency that the balance between the adhesion of low-speed peeling and high-speed peeling can be more favorable.
更者,作為第1(甲基)丙烯酸共聚物之其他構成單元,若為係來自包含 官能性單體且係具有羧基之單體之構成單元的情形時,此來自具有羧基之單體之構成單元的含有率,較佳為第1(甲基)丙烯酸共聚物之總質量中之0.5質量%以下,更佳為0.2質量%以下,又更佳為不包含。若來自具有羧基之單體之構成單元的含有率為前述上限值以下,則有抗靜電性能能夠更為良好之傾向。 Furthermore, as the other constituent unit of the 1st (meth) acrylic copolymer, if it is derived from When the functional monomer is a constituent unit of a monomer having a carboxyl group, the content rate of the constituent unit derived from the monomer having a carboxyl group is preferably 0.5 in the total mass of the first (meth) acrylic copolymer Mass% or less, more preferably 0.2 mass% or less, and even more preferably not included. If the content rate of the constituent unit derived from the monomer having a carboxyl group is equal to or lower than the aforementioned upper limit value, the antistatic performance tends to be more favorable.
第1(甲基)丙烯酸共聚物的重量平均分子量無特別限制。第1(甲基)丙烯酸共聚物的重量平均分子量(Mw),較佳為20萬以上100萬以下,更佳為30萬以上80萬以下。若第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為前述下限值以上,則有可更為有效地抑制對被接著物污染的發生。又,第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)若為前述上限值以下,則有順應性(透濕性)成為更良好之傾向。 The weight average molecular weight of the 1st (meth) acrylic acid copolymer is not specifically limited. The weight average molecular weight (Mw) of the 1st (meth) acrylic acid copolymer is preferably 200,000 to 1 million, and more preferably 300,000 to 800,000. When the weight average molecular weight (Mw) of the 1st (meth) acrylic acid copolymer is more than the said lower limit, the occurrence of contamination of an adherend can be suppressed more effectively. When the weight average molecular weight (Mw) of the first (meth) acrylic copolymer is equal to or less than the aforementioned upper limit value, the compliance (moisture permeability) tends to be better.
又第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)與數量平均分子量(Mn)之比亦即分散度(Mw/Mn),較佳為20以下,更佳為15以下,又更佳為3~10之範圍。若分散度(Mw/Mn)的值為該上限值以下,則有可更為抑制對被接著物污染的發生之傾向。 The ratio of the weight average molecular weight (Mw) of the first (meth) acrylic acid copolymer to the number average molecular weight (Mn), that is, the degree of dispersion (Mw / Mn), is preferably 20 or less, more preferably 15 or less, and more It is preferably in the range of 3 to 10. When the value of the degree of dispersion (Mw / Mn) is equal to or less than the upper limit value, there is a tendency that the occurrence of contamination of the adherend can be further suppressed.
再者,第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)及數量平均分子量(Mn),係依據下列方法測定之值。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the first (meth) acrylic acid copolymer are values measured in accordance with the following methods.
平均分子量(Mw及Mn)的測定方法: Measurement method of average molecular weight (Mw and Mn):
按照下列(1)~(3)實施測定。 The measurement was performed in accordance with the following (1) to (3).
(1)將(甲基)丙烯酸共聚物的溶液塗佈於剝離紙,在100℃乾燥2分鐘,而獲得膜狀之(甲基)丙烯酸共聚物。 (1) A solution of a (meth) acrylic copolymer is applied to a release paper and dried at 100 ° C. for 2 minutes to obtain a film-like (meth) acrylic copolymer.
(2)使用在前述(1)獲得之膜狀(甲基)丙烯酸共聚物與四氫呋喃,而獲得固體成分濃度為0.2質量%之試樣溶液。 (2) Using the film-like (meth) acrylic copolymer and tetrahydrofuran obtained in the above (1), a sample solution having a solid content concentration of 0.2% by mass was obtained.
(3)以下列條件,使用凝膠滲透層析(GPC),作為標準聚苯乙烯換算值,測定(甲基)丙烯酸共聚物的重量平均分子量(Mw)及數量平均分子量(Mn)。 (3) Under the following conditions, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic copolymer were measured using gel permeation chromatography (GPC) as standard polystyrene conversion values.
(條件) (condition)
GPC:HLC-8220 GPC[東曹(股)公司製] GPC: HLC-8220 GPC [Tosoh Corporation]
管柱:TSK-GEL GMHXL使用4根 Column: TSK-GEL GMHXL uses 4
移動相溶媒:四氫呋喃 Mobile phase solvent: tetrahydrofuran
流速:0.6ml/分鐘 Flow rate: 0.6ml / min
管柱溫度:40℃ Column temperature: 40 ℃
黏著劑組成物中之第1(甲基)丙烯酸共聚物的含有率,可因應目的等適當進行選擇。第1(甲基)丙烯酸共聚物的含有率,較佳為黏著劑組成物的固體成分總質量中之80質量%以上99質量%以下,更佳為85質量%以上99質量%以下,又更佳為90質量%以上98質量%以下。 The content rate of the 1st (meth) acrylic acid copolymer in an adhesive composition can be suitably selected according to the objective etc. The content rate of the 1st (meth) acrylic acid copolymer is preferably 80% by mass or more and 99% by mass or less, and more preferably 85% by mass or more and 99% by mass or less of the total solid content of the adhesive composition. It is preferably 90% by mass or more and 98% by mass or less.
再者,固體成分總質量意指從黏著劑組成物,去除了溶劑等之揮發性成分後之殘渣的總質量。 In addition, the total solid content means the total mass of the residue after removing volatile components such as solvents from the adhesive composition.
(第2(甲基)丙烯酸共聚物) (Second (meth) acrylic copolymer)
黏著劑組成物,理想為更含有至少1種之第2(甲基)丙烯酸共聚物(以下亦稱為「樹脂B」),該第2(甲基)丙烯酸共聚物包含具有聚伸烷氧基之構成單元,且較第1(甲基)丙烯酸共聚物的分子量低。黏著劑組成物除了含有第1(甲基)丙烯酸共聚物以外,藉由更含有第2(甲基)丙烯酸共聚物,黏著劑組成物可成為抗靜電性更為優良。 The adhesive composition preferably further contains at least one kind of a second (meth) acrylic copolymer (hereinafter also referred to as "resin B"), and the second (meth) acrylic copolymer contains a polyalkyleneoxy group. It is a structural unit and has a lower molecular weight than the first (meth) acrylic copolymer. The adhesive composition contains a second (meth) acrylic copolymer in addition to the first (meth) acrylic copolymer, so that the adhesive composition can have more excellent antistatic properties.
據認為第2(甲基)丙烯酸共聚物因包含具有聚伸烷氧基之構成單元,且分子量較第1(甲基)丙烯酸共聚物小,故在黏著劑組成物中較容易移動。藉此,據認為黏著劑組成物的表面電阻值更為有效地降低,抗靜電性能夠成為更為優良。 It is considered that the second (meth) acrylic copolymer contains constituent units having a polyalkyleneoxy group and has a molecular weight smaller than that of the first (meth) acrylic copolymer, so that it is easier to move in the adhesive composition. Accordingly, it is considered that the surface resistance value of the adhesive composition can be more effectively reduced, and the antistatic property can be more excellent.
第2(甲基)丙烯酸共聚物,至少包含1種具有聚伸烷氧基之構成單元。作為第2(甲基)丙烯酸共聚物中之聚伸烷氧基,較佳為包含碳數2~4的伸烷氧基作為構成單元者,更佳為包含碳數2~3的伸烷氧基作為構成單元。 The 2nd (meth) acrylic copolymer contains at least 1 type of structural unit which has a polyalkyleneoxy group. As the polyalkyleneoxy group in the second (meth) acrylic acid copolymer, it is preferable to include an alkyleneoxy group having 2 to 4 carbon atoms as a constituent unit, and it is more preferable to include an alkyleneoxy group having 2 to 3 carbon atoms. Basis as a constituent unit.
聚伸烷氧基中之伸烷氧基的含有數,可因應目的等適當進行選擇。伸 烷氧基的含有數,從抗靜電性之觀點而言,較佳為20以上,更佳為20~100,又更佳為20~50。當伸烷氧基的含有數為20以上,藉由與後述之鹼金屬鹽之組合,黏著劑組成物可發揮更為明顯的抗靜電功效。再者,伸烷氧基的含有數,在第2(甲基)丙烯酸共聚物包含2種以上之伸烷氧基之構成單元的情形時,成為含有數之平均值即有理數。 The content of the alkyleneoxy group in the polyalkyleneoxy group can be appropriately selected according to the purpose and the like. Stretch From the viewpoint of antistatic properties, the number of alkoxy groups is preferably 20 or more, more preferably 20 to 100, and still more preferably 20 to 50. When the content of the alkoxy group is 20 or more, the adhesive composition can exhibit a more significant antistatic effect by being combined with an alkali metal salt described later. It should be noted that when the content of the alkoxy group is a reasonable number when the second (meth) acrylic acid copolymer contains two or more kinds of constituent units of the alkoxy group, the average is the number of the content.
第2(甲基)丙烯酸共聚物中之聚伸烷氧基的末端部,也可為羥基,也可為烷氧基,從抗靜電性之觀點而言,理想為烷氧基。聚伸烷氧基的末端部為烷氧基的情形時,烷氧基的碳數較佳為1~10,更佳為1~5。 The terminal portion of the polyalkyleneoxy group in the second (meth) acrylic acid copolymer may be a hydroxyl group or an alkoxy group, and is preferably an alkoxy group from the viewpoint of antistatic properties. When the terminal portion of the polyalkoxy group is an alkoxy group, the carbon number of the alkoxy group is preferably 1 to 10, and more preferably 1 to 5.
具有聚伸烷氧基之構成單元,也可為來自具有聚伸烷氧基及聚合性基之單體者,也可為於對不具有聚伸烷氧基之構成單元以高分子反應導入了聚伸烷氧基者。從具有聚伸烷氧基之構成單元的生產性之觀點而言,具有聚伸烷氧基之構成單元,宜為來自具有聚伸烷氧基及聚合性基之單體者較佳。 The structural unit having a polyalkyleneoxy group may be derived from a monomer having a polyalkyleneoxy group and a polymerizable group, or may be introduced by a polymer reaction to the structural unit having no polyalkyleneoxy group. Polyalkoxylates. From the viewpoint of productivity of the constituent unit having a polyalkyleneoxy group, the constituent unit having a polyalkyleneoxy group is preferably derived from a monomer having a polyalkyleneoxy group and a polymerizable group.
作為具有聚伸烷氧基及聚合性基之單體,可舉例如:聚乙二醇(甲基)丙烯酸酯、甲氧基聚伸乙基氧基(甲基)丙烯酸酯、乙氧基聚伸乙基氧基(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚伸丙基氧基(甲基)丙烯酸酯、乙氧基聚伸丙基氧基(甲基)丙烯酸酯等。其中尤以選自於由甲氧基聚伸乙基氧基(甲基)丙烯酸酯及甲氧基聚伸丙基氧基(甲基)丙烯酸酯構成之群組中之至少1種較佳,更佳為選自於由伸乙基氧基之含有數為20以上之甲氧基聚伸乙基氧基(甲基)丙烯酸酯及伸丙基氧基之含有數為20以上之甲氧基聚伸丙基氧基(甲基)丙烯酸酯構成之群組中之至少1種。 Examples of the monomer having a polyalkyleneoxy group and a polymerizable group include polyethylene glycol (meth) acrylate, methoxypolyethyloxy (meth) acrylate, and ethoxypoly Ethyloxy (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypoly (propyl) oxy (meth) acrylate, ethoxypoly (propyl) oxy (meth) Acrylate, etc. Among them, at least one selected from the group consisting of methoxy poly (ethyl) oxy (meth) acrylate and methoxy poly (propyl) oxy (meth) acrylate is particularly preferred, More preferably, it is selected from the group consisting of methoxy polyethenyloxy (meth) acrylates containing 20 or more ethoxy groups and methoxy polyethenes containing 20 or more in propyloxy groups. At least one member of the group consisting of propyloxy (meth) acrylate.
第2(甲基)丙烯酸共聚物,也可僅包含1種、也可包含組合2種以上之具有聚伸烷氧基之構成單元。 The second (meth) acrylic copolymer may include only one kind or a combination of two or more kinds of constituent units having a polyalkyleneoxy group.
第2(甲基)丙烯酸共聚物中之具有聚伸烷氧基之構成單元的含有率,從抗靜電性之觀點而言,較佳為第2(甲基)丙烯酸共聚物的總質量中之1質量 %以上50質量%以下,更佳為1質量%以上30質量%以下,又更佳為5質量%以上20質量%以下。 The content rate of the structural unit having a polyalkyleneoxy group in the second (meth) acrylic acid copolymer is preferably one of the total mass of the second (meth) acrylic acid copolymer from the viewpoint of antistatic properties. 1 quality % To 50% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 20% by mass.
第2(甲基)丙烯酸共聚物,除了具有聚伸烷氧基之構成單元以外,理想為更包含至少1種來自(甲基)丙烯酸烷基酯之構成單元。 The second (meth) acrylic copolymer preferably contains a structural unit derived from an alkyl (meth) acrylate in addition to the structural unit having a polyalkyleneoxy group.
(甲基)丙烯酸烷基酯中之烷基也可為直鏈狀,也可為分枝鏈狀。又,(甲基)丙烯酸烷基酯中之烷基的碳數,從抗靜電性之觀點而言,較佳為1~18,更佳為2~10。 The alkyl group in the alkyl (meth) acrylate may be linear or branched. The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 to 18, and more preferably 2 to 10 from the viewpoint of antistatic properties.
作為(甲基)丙烯酸烷基酯,具體而言可舉例如:(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)丙烯酸正十二酯、(甲基)丙烯酸十八酯等具有碳數1~18的直鏈狀或分枝鏈狀烷基之(甲基)丙烯酸烷基酯及該等之衍生物。 Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, ( (Meth) acrylic acid having linear or branched alkyl groups having 1 to 18 carbon atoms, such as n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, and octadecyl (meth) acrylate Alkyl esters and derivatives thereof.
第2(甲基)丙烯酸共聚物,也可僅包含1種、也可包含2種以上之來自(甲基)丙烯酸烷基酯之構成單元。 The 2nd (meth) acrylic copolymer may contain only 1 type, and may also contain the structural unit derived from the alkyl (meth) acrylate.
第2(甲基)丙烯酸共聚物包含來自(甲基)丙烯酸烷基酯之構成單元的情形時,來自(甲基)丙烯酸烷基酯之構成單元的含有率,在第2(甲基)丙烯酸共聚物的總質量中,較佳為40質量%以上95質量%以下,更佳為70質量%以上90質量%以下,又更佳為80質量%以上90質量%以下。若來自(甲基)丙烯酸烷基酯之構成單元的含有率為前述下限值以上,則有更為有效地抑制對被接著物污染的發生之傾向。又,來自(甲基)丙烯酸烷基酯之構成單元的含有率若為前述上限值以下,則有黏著劑組成物的表面電阻降低,黏著劑組成物獲得更為優良抗靜電性之傾向。 When the 2nd (meth) acrylic acid copolymer contains the structural unit derived from an alkyl (meth) acrylate, the content rate of the structural unit derived from an alkyl (meth) acrylic acid is the same as that of the 2nd (meth) acrylic acid The total mass of the copolymer is preferably from 40% by mass to 95% by mass, more preferably from 70% by mass to 90% by mass, and even more preferably from 80% by mass to 90% by mass. If the content rate of the structural unit derived from the alkyl (meth) acrylate is equal to or more than the aforementioned lower limit value, there is a tendency that the occurrence of contamination of the adherend is more effectively suppressed. Moreover, if the content rate of the structural unit derived from an alkyl (meth) acrylate is below the said upper limit, the surface resistance of an adhesive composition will fall and the adhesive composition will become more excellent in antistatic property.
第2(甲基)丙烯酸共聚物,視須要也可包含具有聚伸烷氧基之構成單元及來自(甲基)丙烯酸烷基酯之構成單元以外的其他構成單元。作為其他構成單元,可舉例如與第1(甲基)丙烯酸共聚物中之其他構成單元同樣者,理想 之態樣亦為相同。 The 2nd (meth) acrylic copolymer may contain the structural unit which has a polyalkyleneoxy group and the structural unit other than the structural unit derived from an alkyl (meth) acrylate as needed. As other structural units, for example, the same as other structural units in the 1st (meth) acrylic copolymer is preferable, The same is true.
第2(甲基)丙烯酸共聚物的分子量,若較第1(甲基)丙烯酸共聚物小則無特別限制。第2(甲基)丙烯酸共聚物的重量平均分子量(Mw),較佳為3,000以上100,000以下,更佳為5,000以上60,000以下,又更佳為5,000以上20,000以下。若第2(甲基)丙烯酸共聚物的重量平均分子量(Mw)為前述下限值以上,則有更為有效地抑制對被接著物污染的發生之傾向。又,若第2(甲基)丙烯酸共聚物的重量平均分子量(Mw)為前述上限值以下,則有更為提升抗靜電性之傾向。 The molecular weight of the second (meth) acrylic copolymer is not particularly limited as long as it is smaller than the first (meth) acrylic copolymer. The weight average molecular weight (Mw) of the second (meth) acrylic copolymer is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 60,000 or less, and still more preferably 5,000 or more and 20,000 or less. When the weight average molecular weight (Mw) of the 2nd (meth) acrylic copolymer is more than the said lower limit, there exists a tendency for the occurrence of contamination to an adherend to be suppressed more effectively. When the weight average molecular weight (Mw) of the second (meth) acrylic copolymer is equal to or less than the aforementioned upper limit value, the antistatic property tends to be further improved.
又,第2(甲基)丙烯酸共聚物的重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn),較佳為10以下,更佳為7以下,又更佳為1~5之範圍。若Mw/Mn的值為該上限值以下,則有更為有效地抑制對被接著物污染的發生之傾向。再者,第2(甲基)丙烯酸共聚物的重量平均分子量(Mw)及數量平均分子量(Mn),以與第1(甲基)丙烯酸共聚物的情形時同樣之方法實施測定。 The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the second (meth) acrylic copolymer is preferably 10 or less, more preferably 7 or less, and even more preferably 1 Range of ~ 5. When the value of Mw / Mn is equal to or less than the upper limit value, there is a tendency that the occurrence of contamination of the adherend is more effectively suppressed. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the second (meth) acrylic acid copolymer were measured in the same manner as in the case of the first (meth) acrylic acid copolymer.
第2(甲基)丙烯酸共聚物相對於第1(甲基)丙烯酸共聚物之重量平均分子量的比(第2/第1),若未達1則無特別限制。從抗靜電性之觀點而言,第2(甲基)丙烯酸共聚物相對於第1(甲基)丙烯酸共聚物之重量平均分子量的比,較佳為0.1以下,更佳為0.006~0.07。 The ratio of the weight average molecular weight of the second (meth) acrylic acid copolymer to the first (meth) acrylic acid copolymer (second / first) is not particularly limited if it is less than 1. From the viewpoint of antistatic properties, the ratio of the weight average molecular weight of the second (meth) acrylic copolymer to the first (meth) acrylic copolymer is preferably 0.1 or less, and more preferably 0.006 to 0.07.
黏著劑組成物中之第2(甲基)丙烯酸共聚物的含有率,可因應目的等適當進行選擇。第2(甲基)丙烯酸共聚物的含量,相對於第1(甲基)丙烯酸共聚物100質量份,較佳為0.05質量份以上2.0質量份以下,更佳為0.1質量份以上1.5質量份以下,又更佳為0.2質量份以上1.0質量份以下。若第2(甲基)丙烯酸共聚物的含量相對於第1(甲基)丙烯酸共聚物100質量份,為0.05質量份以上,則有可獲得更為優良抗靜電功效之傾向。又第2(甲基)丙烯酸共聚物的含量相對於第1(甲基)丙烯酸共聚物100質量份,若為2.0質量份以下,則有更為有效地抑制對被接著物的污染之傾向。 The content of the second (meth) acrylic copolymer in the adhesive composition can be appropriately selected depending on the purpose and the like. The content of the second (meth) acrylic copolymer is preferably 0.05 to 2.0 parts by mass, and more preferably 0.1 to 1.5 parts by mass based on 100 parts by mass of the first (meth) acrylic copolymer. And more preferably 0.2 mass part to 1.0 mass part. When the content of the second (meth) acrylic copolymer is 0.05 parts by mass or more relative to 100 parts by mass of the first (meth) acrylic copolymer, there is a tendency that a more excellent antistatic effect can be obtained. In addition, if the content of the second (meth) acrylic copolymer is 2.0 parts by mass or less relative to 100 parts by mass of the first (meth) acrylic copolymer, there is a tendency that contamination of the adherend is more effectively suppressed.
第1(甲基)丙烯酸共聚物及第2(甲基)丙烯酸共聚物(以下,亦將該等總稱為「共聚物」),可以藉由將能夠形成該等共聚物所包含之構成單元的單體的混合物進行聚合而加以製造。前述共聚物的聚合方法,無特別限制,可從溶液聚合法、乳化聚合法、懸浮聚合法等之公知方法適當選擇。該等之中尤以,針對使用藉由聚合而獲得的共聚物而製造本發明之黏著劑組成物時處理步驟較簡單且能夠於短時間實施之考量,理想為利用溶液聚合法進行聚合。 The first (meth) acrylic acid copolymer and the second (meth) acrylic acid copolymer (hereinafter, these are also collectively referred to as "copolymers") can be formed by a method capable of forming constituent units included in these copolymers. A mixture of monomers is polymerized to produce it. The polymerization method of the copolymer is not particularly limited, and may be appropriately selected from known methods such as a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. Among these, in particular, for the consideration that the processing steps in the production of the adhesive composition of the present invention using a copolymer obtained by polymerization are relatively simple and can be implemented in a short time, it is desirable to perform polymerization using a solution polymerization method.
溶液聚合法,一般可藉由使用下述等公知方法實施:於聚合槽內放入既定之有機溶劑、單體、聚合起始劑、及視須要使用之鏈轉移劑,在氮氣氣流中、有機溶劑的回流溫度下,於攪拌的狀態進行數小時的加熱反應。 The solution polymerization method can generally be carried out by using a known method such as: putting a predetermined organic solvent, monomer, polymerization initiator, and chain transfer agent as needed in a polymerization tank, in a nitrogen gas stream, organically At the reflux temperature of the solvent, a heating reaction was performed for several hours with stirring.
再者,第1(甲基)丙烯酸共聚物及第2(甲基)丙烯酸共聚物的重量平均分子量及分散度,可藉由反應溫度、時間、溶劑量、觸媒的種類及量而輕易地進行調節。 The weight average molecular weight and dispersion of the first (meth) acrylic acid copolymer and the second (meth) acrylic acid copolymer can be easily determined by the reaction temperature, time, solvent amount, and type and amount of the catalyst. Make adjustments.
作為使用在第1(甲基)丙烯酸共聚物及第2(甲基)丙烯酸共聚物的聚合之聚合用的有機溶劑,可舉例如:苯、甲苯、乙苯、正丙苯、三級丁苯、鄰二甲苯、間二甲苯、對二甲苯、四氫萘、十氫萘、芳香族石油腦等芳香族烴類;正己烷、正庚烷、正辛烷、異辛烷、正癸烷、二戊烯、石油精、石油腦、松節油等脂肪系或脂環族系成分烴類;乙酸乙酯、醋酸正丁酯、醋酸正戊酯、醋酸2-羥基乙酯、醋酸2-丁氧基乙酯、醋酸3-甲氧基丁酯、苯甲酸甲酯等酯類;丙酮、甲基乙基酮、甲基異丁基酮、異佛酮、環己酮、甲基環己酮等酮類;乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚等二醇醚類;甲醇、乙醇、正丙醇、異丙基醇、正丁醇、異丁醇、二級丁醇、三級丁醇等醇類;等。該等有機溶劑分別可單獨使用1種,或混合2種以上使用。 Examples of the organic solvent for polymerization used in the polymerization of the first (meth) acrylic acid copolymer and the second (meth) acrylic acid copolymer include benzene, toluene, ethylbenzene, n-propylbenzene, and tertiary butylbenzene. , O-xylene, m-xylene, p-xylene, tetrahydronaphthalene, decahydronaphthalene, aromatic petroleum brain and other aromatic hydrocarbons; n-hexane, n-heptane, n-octane, isooctane, n-decane, Dipentene, petroleum spirit, petroleum naphtha, turpentine and other aliphatic or cycloaliphatic hydrocarbons; ethyl acetate, n-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-butoxy acetate Ester such as ethyl ester, 3-methoxybutyl acetate, methyl benzoate; acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone and other ketones Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and other glycol ethers; Alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, secondary butanol, tertiary butanol; etc. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
作為前述之聚合起始劑,能使用在通常的溶液聚合法中可使用之有機過氧化物、偶氮化合物等。作為有機過氧化物,可舉例如:三級丁基過氧化 氫、異丙苯過氧化氫、二異丙苯基過氧化物、苯甲醯基過氧化物、月桂醯基過氧化物、己醯基過氧化物、過氧二碳酸二異丙酯、過氧二碳酸二-2-乙基己酯、過氧化三甲基乙酸三級丁酯、2,2-雙(4,4-二-三級丁基過氧環己基)丙烷、2,2-雙(4,4-二-三級戊基過氧環己基)丙烷、2,2-雙(4,4-二-三級辛基過氧環己基)丙烷、2,2-雙(4,4-二-α-異丙苯基過氧環己基)丙烷、2,2-雙(4,4-二-三級丁基過氧環己基)丁烷、2,2-雙(4,4-二-三級辛基過氧環己基)丁烷等。作為偶氮化合物,可舉例如:2,2’-偶氮雙異丁腈、2,2’-偶氮雙-2,4-二甲基戊腈、2,2’-偶氮雙-4-甲氧基-2,4-二甲基戊腈等。 As the aforementioned polymerization initiator, organic peroxides, azo compounds, and the like that can be used in a general solution polymerization method can be used. Examples of organic peroxides include tertiary butyl peroxide Hydrogen, cumene hydroperoxide, dicumyl peroxide, benzamyl peroxide, lauryl peroxide, hexamethylene peroxide, diisopropyl peroxydicarbonate, peroxide Di-2-ethylhexyl oxydicarbonate, tert-butyl peroxytrimethylacetate, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 2,2- Bis (4,4-di-tertiary pentylperoxycyclohexyl) propane, 2,2-bis (4,4-di-tertiary octylperoxycyclohexyl) propane, 2,2-bis (4, 4-di-α-cumyl peroxycyclohexyl) propane, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) butane, 2,2-bis (4,4 -Di-tertiary octylperoxycyclohexyl) butane and the like. As the azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4 -Methoxy-2,4-dimethylvaleronitrile and the like.
又,在製造第1(甲基)丙烯酸共聚物及第2(甲基)丙烯酸共聚物時,普通不使用鏈轉移劑,但在不損及本發明之目的及功效的範圍內,視須要可使用。作為鏈轉移劑,可舉例如:氰醋酸;氰醋酸之碳數1~8的烷酯類;溴醋酸;溴醋酸之碳數1~8的烷醋類;蒽、菲、茀、9-苯基茀等芳香族化合物類;對硝苯胺、硝苯、二硝苯、對硝苯甲酸、對硝苯酚、對硝甲苯等芳香族硝基化合物類;苯醌、2,3,5,6-四甲基對苯醌等苯醌衍生物類;三丁基硼烷等硼烷衍生物;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、3-氯-1-丙烯等鹵化烴類;氯醛、呋喃甲醛等醛類:碳數1~18的烷基硫醇類;硫苯酚、甲苯硫醇等芳香族硫醇類;巰基醋酸、巰基醋酸之碳數1~10的烷酯類;碳數1~12的羥基烷基硫醇類;蒎烯(pinene)、品油烯(terpinolene)等萜類;等。 In the production of the first (meth) acrylic acid copolymer and the second (meth) acrylic acid copolymer, a chain transfer agent is generally not used. However, as long as the purpose and efficacy of the present invention are not impaired, it may be necessary. use. Examples of the chain transfer agent include: cyanoacetic acid; alkyl esters of 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters of 1 to 8 carbon atoms of bromoacetic acid; Aromatic compounds such as hydrazone; p-nitroaniline, n-benzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene and other aromatic nitro compounds; benzoquinone, 2,3,5,6- Benzoquinone derivatives such as tetramethyl p-benzoquinone; Borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene , Trichloroethylene, bromotrichloromethane, tribromomethane, 3-chloro-1-propene and other halogenated hydrocarbons; aldehydes such as chloroaldehyde and furanaldehyde: alkyl mercaptans having 1 to 18 carbon atoms; thiophenol, toluene Aromatic mercaptans such as mercaptans; mercaptoacetic acid, mercaptoacetic acid alkyl esters having 1 to 10 carbons; hydroxyalkyl mercaptans having 1 to 12 carbons; pinene, terpinolene And other terpenes; etc.
作為聚合溫度,一般為約30℃~180℃的範圍。 The polymerization temperature is generally in the range of about 30 ° C to 180 ° C.
在製造第1(甲基)丙烯酸共聚物及第2(甲基)丙烯酸共聚物時,也可設置將在聚合反應獲得的聚合物進行精製之精製步驟。藉由精製步驟,在溶液聚合法等獲得之聚合物中包含未反應的單體的情形時,可去除該單體。作為精製步驟可從通常使用之精製方法適當進行選擇。例如,可利用以甲醇等之再沈澱法進行精製。 When manufacturing a 1st (meth) acrylic acid copolymer and a 2nd (meth) acrylic acid copolymer, the purification process which refine | purifies the polymer obtained by a polymerization reaction may be provided. When the polymer obtained by the solution polymerization method or the like contains an unreacted monomer by the purification step, the monomer can be removed. The refining step can be appropriately selected from refining methods generally used. For example, purification can be performed by a reprecipitation method using methanol or the like.
[聚醚改性矽酮] [Polyether modified silicone]
黏著劑組成物,至少含有1種於聚醚末端具有羥基之聚醚改性矽酮(以下亦稱為「特定聚矽氧烷化合物」)。聚醚改性矽酮藉由在聚醚末端具有羥基,黏著劑組成物展現優良抗靜電性,可有效地抑制對被接著物之污染。 The adhesive composition contains at least one type of polyether-modified silicone having a hydroxyl group at the end of the polyether (hereinafter also referred to as "specific polysiloxane compound"). Polyether-modified silicone has excellent antistatic properties by having a hydroxyl group at the end of the polyether, which can effectively inhibit contamination of the adherend.
特定聚矽氧烷化合物,藉由於分子內末端具有羥基亦即聚伸烷氧基,可有效地發揮抗靜電性能。原因推測為例如,因為特定聚矽氧烷化合物集中存在從黏著劑組成物而來之黏著劑層的表面附近,導致與鹼金屬鹽交互作用之聚伸烷氧基成為存在於黏著劑層的表面附近,其結果,降低了黏著劑層的表面中之表面電阻值。 The specific polysiloxane compound can effectively exhibit antistatic properties by having a hydroxyl group, that is, a polyalkyleneoxy group, at the end of the molecule. The reason is speculated that, for example, a specific polysiloxane compound is concentrated in the vicinity of the surface of the adhesive layer from the adhesive composition, and the polyalkyleneoxy group which interacts with the alkali metal salt is present on the surface of the adhesive layer. As a result, the surface resistance value in the surface of the adhesive layer is reduced.
一般而言,於黏著劑組成物,若含有作為聚矽氧烷化合物之於聚醚末端具有羥基之聚醚改性矽酮,則有無法充分獲得黏著劑組成物的表面電阻值降低功效之傾向。然而,在本發明中,藉由含有包含有通式(1)表示之第1構成單元的第1(甲基)丙烯酸共聚物,可使黏著劑組成物的表面電阻值充分地降低。另一方面,包含來自具有(甲基)丙烯酸等之含羧基之構成單元的(甲基)丙烯酸共聚物,難以將黏著劑組成物的表面電阻值充分地降低。更者,據認為第1(甲基)丙烯酸共聚物藉由包含來自具有羥基之單體之第2構成單元,能夠更有效的降低黏著劑組成物的表面電阻值。 In general, if the adhesive composition contains a polyether-modified silicone having a hydroxyl group at a polyether terminal as a polysiloxane compound, there is a tendency that the surface resistance of the adhesive composition cannot be sufficiently reduced. . However, in the present invention, the surface resistance value of the adhesive composition can be sufficiently reduced by containing the first (meth) acrylic copolymer containing the first constituent unit represented by the general formula (1). On the other hand, it is difficult to sufficiently reduce the surface resistance value of the adhesive composition by including a (meth) acrylic copolymer derived from a carboxyl group-containing structural unit having (meth) acrylic acid or the like. Furthermore, it is thought that the 1st (meth) acrylic copolymer contains the 2nd structural unit derived from the monomer which has a hydroxyl group, and can reduce the surface resistance value of an adhesive composition more effectively.
特定聚矽氧烷化合物,從抗靜電性與對被接著物之低污染性之觀點而言,宜為包含來自二烷基矽氧烷之結構單元與來自烷基(羥基聚伸烷氧基烷基)矽氧烷之結構單元之聚矽氧烷化合物較佳。 The specific polysiloxane compound preferably contains a structural unit derived from a dialkyl siloxane and an alkyl group derived from an alkyl (hydroxy polyalkylene oxide alkane) from the viewpoints of antistatic properties and low pollution to an adherend. Polysiloxane compounds in the structural unit of siloxane) are preferred.
二烷基矽氧烷中之烷基,較佳為碳數1~4,更佳為1。 The alkyl group in the dialkylsiloxane is preferably 1 to 4 carbon atoms, and more preferably 1.
又,烷基(羥基聚伸烷氧基烷基)矽氧烷中之伸烷氧基,較佳為碳數2~4,更佳為2~3。烷基(羥基聚伸烷氧基烷基)矽氧烷中之伸烷氧基的含有數,較佳為1~100,更佳為10~100。烷基(羥基聚伸烷氧基烷基)矽氧烷中之烷基,較佳為碳數1~4。 The alkylene (hydroxy polyalkyleneoxyalkyl) siloxane has preferably 2 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms. The number of alkoxy groups in the alkyl (hydroxy polyalkyleneoxyalkyl) siloxane is preferably 1 to 100, and more preferably 10 to 100. The alkyl group in the alkyl group (hydroxy polyalkyleneoxyalkyl) siloxane is preferably 1 to 4 carbon atoms.
特定聚矽氧烷化合物,包含來自二烷基矽氧烷之結構單元與來自烷基(羥基聚伸烷氧基烷基)矽氧烷之結構單元的情形時,來自二烷基矽氧烷之結 構單元的含有數較佳為100以下,更佳為1~80。又,來自烷基(羥基聚伸烷氧基烷基)矽氧烷之結構單元的含有數較佳為2~100,更佳為2~80。 When a specific polysiloxane compound includes a structural unit derived from a dialkylsiloxane and a structural unit derived from an alkyl (hydroxy polyalkyleneoxyalkyl) siloxane, the Knot The number of constituent units is preferably 100 or less, and more preferably 1 to 80. The content of the structural unit derived from an alkyl (hydroxy polyalkyleneoxyalkyl) siloxane is preferably from 2 to 100, more preferably from 2 to 80.
特定聚矽氧烷化合物,從黏著性、抗靜電性及對被接著物之低污染性之觀點而言,理想為下列通式(3)表示之聚矽氧烷化合物。 The specific polysiloxane compound is preferably a polysiloxane compound represented by the following general formula (3) from the viewpoints of adhesiveness, antistatic properties, and low contamination to an adherend.
通式(3)中,p為二甲基矽氧烷結構單元之重複數,表示0~100的數值。q為具有聚伸乙基氧基之甲基伸丙基矽氧烷結構單元的重複數,表示2~100的數值。又a為伸乙基氧基結構單元的重複數,分別表示1~100的數值。在此,在通式(3)表示之化合物係多數之化合物的集合體的情形時,p、q及a係就化合物之集合體而言之平均值,係有理數。 In the general formula (3), p is a repeating number of a dimethylsiloxane structural unit, and represents a value from 0 to 100. q is a repeating number of a methyl propylene siloxane structure unit having a polyethylenyloxy group, and represents a value of 2 to 100. A is the repeating number of the ethylenoxy structural unit, and each represents a value of 1 to 100. Here, in the case where the compound represented by the general formula (3) is an aggregate of a large number of compounds, p, q, and a are average values of the aggregate of the compounds, and are rational numbers.
聚伸乙基氧基結構單元的重複數a為1~100的數值,理想為10~100的數值。若a為1以上則有可獲得足夠之導電性、提升抗靜電功效之傾向。又若a為100以下,則有與構成黏著劑組成物之其他的成分的互溶性提升,且黏著劑層的透明性更為提升之傾向。 The repeating number a of the polyethylenoxy structural unit is a value of 1 to 100, and preferably a value of 10 to 100. If a is 1 or more, there is a tendency that sufficient conductivity can be obtained and antistatic effect can be improved. When a is 100 or less, the mutual solubility with other components constituting the adhesive composition is improved, and the transparency of the adhesive layer tends to be further improved.
又,二甲基矽氧烷結構單元的重複數p為0~100的數值,理想為1~80的數值。p為0以上的情形時有提升抗靜電功效之傾向。又若p為100以下,則有與構成黏著劑組成物之其他的成分的互溶性提升,且黏著劑層的透明性提升之傾向。 The repetition number p of the dimethylsilane structural unit is a value of 0 to 100, and preferably a value of 1 to 80. When p is 0 or more, the antistatic effect tends to be improved. When p is 100 or less, the compatibility with other components constituting the adhesive composition is improved, and the transparency of the adhesive layer tends to be improved.
更者,伸丙基矽氧烷結構單元的重複數q為2~100的數值,理想為2~80的數值。若q為2以上,則有能獲得足夠之導電性,抗靜電功效提升之傾 向。又若q為100以下,則有與構成黏著劑組成物之其他的成分的互溶性提升,且黏著劑層的透明性提升之傾向。 Furthermore, the repeating number q of the propylene siloxane structure unit is a value from 2 to 100, and preferably a value from 2 to 80. If q is 2 or more, there is a tendency to obtain sufficient conductivity and improve antistatic effect. to. When q is 100 or less, the mutual solubility with other components constituting the adhesive composition is improved, and the transparency of the adhesive layer tends to be improved.
特定聚矽氧烷化合物的重量平均分子量無特別限制,例如,特定聚矽氧烷化合物的重量平均分子量,可設為5,000以上20,000以下,理想為6,000以上15,000以下。 The weight average molecular weight of the specific polysiloxane compound is not particularly limited. For example, the weight average molecular weight of the specific polysiloxane compound may be 5,000 or more and 20,000 or less, and preferably 6,000 or more and 15,000 or less.
又,特定聚矽氧烷化合物的HLB值無特別限制,但從與樹脂之互溶性、表面不均勻分布性、及黏著性之觀點而言,較佳為5以上未達16,更佳為7以上15以下。 In addition, the HLB value of a specific polysiloxane compound is not particularly limited, but from the viewpoint of mutual solubility with the resin, uneven surface distribution, and adhesiveness, it is preferably 5 or more and less than 16, and more preferably 7 Above 15 and below.
前述HLB值,係表示特定聚矽氧烷化合物(界面活性劑)的親水性與疏水性的平衡性之尺度。在本發明中,係按照以下列式1算出之格力芬法(Griffin method)的定義,但特定聚矽氧烷化合物為市售品的情形時,優先採用其商品型錄資料。 The HLB value is a scale indicating the balance between the hydrophilicity and hydrophobicity of a specific polysiloxane compound (surfactant). In the present invention, according to the definition of the Griffin method calculated by the following formula 1, when a specific polysiloxane compound is a commercially available product, its catalogue data is preferably used.
式1 {(親水性基部分的式量的總和)/(界面活性劑的分子量)}×20 Formula 1 {(Sum of formula amount of hydrophilic group part) / (Molecular weight of surfactant)} × 20
前述特定聚矽氧烷化合物在分子內具有二甲基矽氧烷結構單元,與具有聚伸乙基氧基之甲基伸丙基矽氧烷結構單元。該等之結構單元,也可構成嵌段性共聚物,也可構成無規性共聚物。 The aforementioned specific polysiloxane compound has a dimethylsiloxane structure unit in the molecule and a methylphenylpropylsiloxane structure unit having a polyethoxy group. These structural units may constitute a block copolymer or a random copolymer.
作為前述通式(3)表示之特定聚矽氧烷化合物之具體例,可舉例如:「SF-8428」、「FZ-2162」、「SH-3773M」[以上為東麗-道康寧矽酮(股)公司製]等。 Specific examples of the specific polysiloxane compound represented by the aforementioned general formula (3) include, for example, "SF-8428", "FZ-2162", and "SH-3773M" [The above is Toray-Dow Corning Silicone ( Share) company system] and so on.
特定聚矽氧烷化合物,也可為如從前述市售品選擇者,又,也可將具有不飽和鍵及聚伸乙基氧基之有機化合物藉由氫化矽烷化反應接枝於具有氫化矽之二甲基聚矽氧烷主鏈而獲得。 The specific polysiloxane compound may be selected from the aforementioned commercially available products, or an organic compound having an unsaturated bond and a polyethyloxy group may be grafted to a compound having a hydrogenated silane by a hydrosilylation reaction. Dimethyl polysiloxane is obtained from the main chain.
黏著劑組成物中之特定聚矽氧烷化合物的含量,相對於第1(甲基)丙烯酸共聚物100質量份,較佳為0.05質量份以上0.5質量份以下,更佳為0.05 質量份以上0.4質量份以下,又更佳為0.05質量份以上0.3質量份以下。 The content of the specific polysiloxane compound in the adhesive composition is preferably 0.05 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.05 parts by mass relative to 100 parts by mass of the first (meth) acrylic copolymer. At least 0.4 parts by mass and more preferably at least 0.05 parts by mass and not more than 0.3 parts by mass.
藉由將特定聚矽氧烷化合物含量設為前述下限值以上,可更為有效地獲得剝離表面保護膜時的抗靜電功效。又,藉由將特定聚矽氧烷化合物含量設為前述上限值以下,可抑制對被接著物的污染(污點)的發生,又,可抑制與丙烯酸共聚物之互溶性降低而發生之白濁。 By setting the content of the specific polysiloxane compound to be equal to or more than the aforementioned lower limit value, the antistatic effect when the surface protective film is peeled off can be obtained more effectively. In addition, by setting the content of the specific polysiloxane compound to be equal to or less than the aforementioned upper limit value, it is possible to suppress the occurrence of contamination (stain) on the adherend, and to suppress white turbidity caused by the decrease in the mutual solubility with the acrylic copolymer .
黏著劑組成物,除了以前述通式(3)表示之聚矽氧烷化合物以外,也可在不損及本發明之效果的範圍內,含有具有與通式(3)相異之結構且包含聚伸乙基氧基之二甲基聚矽氧烷化合物。 In addition to the polysiloxane compound represented by the aforementioned general formula (3), the adhesive composition may contain a structure different from that of the general formula (3) and include the same as long as the effect of the present invention is not impaired. Polyethyloxy dimethyl polysiloxane compound.
作為具有與通式(3)相異之結構且包含聚伸乙基氧基之二甲基聚矽氧烷化合物,可舉例如:聚伸乙基氧基末端為烷氧基、醯氧基等之化合物,於主鏈或末端包含聚伸乙基氧基而非於側鏈包含聚伸乙基氧基之化合物等。 As a dimethylpolysiloxane compound having a structure different from that of the general formula (3) and containing a polyethylenyloxy group, for example, the polyethylenyloxy terminal is an alkoxy group, a fluorenyloxy group, or the like Compounds that include polyethoxy groups in the main chain or terminal instead of polyethoxy groups in the side chain.
具體而言可舉例如:「BY-16-201」、「FZ-77」、「FZ-2104」、「FZ-2110」、「FZ-2203」、「FZ-2207」、「FZ-2208」、「L-7001」、「L-7002」、「SF-8427」、「SH-3749」、「SH-8400」[以上為東麗-道康寧矽酮(股)公司製]等。 Specific examples include: "BY-16-201", "FZ-77", "FZ-2104", "FZ-2110", "FZ-2203", "FZ-2207", "FZ-2208" , "L-7001", "L-7002", "SF-8427", "SH-3749", "SH-8400" [The above are manufactured by Toray Dow Corning Silicone Co., Ltd.], etc.
前述黏著劑組成物含有具有與前述通式(3)相異之結構且為包含聚伸乙基氧基之二甲基聚矽氧烷化合物的情形時,其含有率較佳為在聚矽氧烷化合物的總質量中為0.05質量%以下,更佳為0.03質量%以下。 In the case where the adhesive composition contains a dimethylpolysiloxane compound having a structure different from the general formula (3) and containing a polyethylenoxy group, the content rate is preferably in a polysiloxane group. The total mass of the alkane compound is 0.05% by mass or less, and more preferably 0.03% by mass or less.
[鹼金屬鹽] [Alkali metal salt]
黏著劑組成物,至少含有1種鹼金屬鹽。前述鹼金鹽,若是以鋰離子(Li+)、鈉離子(Na+)、鉀離子(K+)、銣(Rb+)等作為陽離子之金屬鹽即可,無特別限制。 The adhesive composition contains at least one alkali metal salt. The alkali gold salt is not particularly limited as long as it is a metal salt using lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium (Rb + ) as a cation.
具體而言,前述鹼金屬鹽,宜使用由Li+、Na+、K+等陽離子與Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-等陰離子構成之金屬鹽。 Specifically, the alkali metal salt is preferable to use a Li +, Na +, K + cations and Cl -, Br -, I - , BF 4 -, PF 6 -, SCN -, ClO 4 -, CF 3 SO 3 -, (CF 3 SO 2 ) 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) 3 C - anions of the metal salts.
其中尤以鹼金屬鹽,從抗靜電之觀點而言,宜為使用LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C等之鋰鹽。 Among them, alkali metal salts are particularly preferred. From the viewpoint of antistatic, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 , 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.
尤其鹼金屬鹽,從抗靜電功效、金屬腐蝕性之觀點而言,較佳為LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C等之含氟甲基磺醯基之鋰鹽,更佳為選自於由LiCF3SO3、Li(CF3SO2)2N及Li(C2F5SO2)2N構成之群組中之至少1種。 In particular, the alkali metal salt is preferably LiCF 3 SO 3 , 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 containing fluorine methylsulfonyl are more preferably selected from the group consisting of LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N and Li (C 2 F 5 SO 2 ) At least one member of the group consisting of 2 N.
該等之鹼金屬鹽也可僅使用1種,又也可混合2種以上使用。 These alkali metal salts may be used alone or in combination of two or more.
黏著劑組成物中之鹼金屬鹽的含量,相對於第1(甲基)丙烯酸共聚物100質量份,較佳為0.005質量份以上0.6質量份以下,更佳為0.005質量份以上0.3質量份以下,又更佳為0.01質量份以上0.2質量份以下。 The content of the alkali metal salt in the adhesive composition is preferably 0.005 parts by mass or more and 0.6 parts by mass or less, more preferably 0.005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the first (meth) acrylic copolymer. And more preferably 0.01 mass part or more and 0.2 mass part or less.
藉由使鹼金屬鹽的含量相對於第1(甲基)丙烯酸共聚物100質量份為0.005質量份以上可獲得足夠的靜電特性。另一方面,藉由使鹼金屬鹽的含量相對於第1(甲基)丙烯酸共聚物100質量份為0.6質量份以下可獲得相對於含量之足夠的抗靜電功效。 When the content of the alkali metal salt is 0.005 part by mass or more with respect to 100 parts by mass of the first (meth) acrylic copolymer, sufficient electrostatic characteristics can be obtained. On the other hand, when the content of the alkali metal salt is 0.6 parts by mass or less with respect to 100 parts by mass of the first (meth) acrylic copolymer, a sufficient antistatic effect relative to the content can be obtained.
作為黏著劑組成物中之特定聚矽氧烷化合物相對於前述鹼金屬鹽之質量比(特定聚矽氧烷化合物/鹼金屬鹽),從抗靜電功效與黏著性之觀點而言,較佳為0.1以上5以下,更佳為0.5以上4以下。 The mass ratio of the specific polysiloxane compound to the alkali metal salt (specific polysiloxane compound / alkali metal salt) in the adhesive composition is preferably from the viewpoint of antistatic effect and adhesion. 0.1 or more and 5 or less, and more preferably 0.5 or more and 4 or less.
黏著劑組成物中之特定聚矽氧烷化合物及鹼金屬鹽的總含量,相對於第1(甲基)丙烯酸共聚物100質量份,較佳為0.10質量份以上1.00質量份以下,更佳為0.10質量份以上0.50質量份以下。 The total content of the specific polysiloxane compound and the alkali metal salt in the adhesive composition is preferably 0.10 part by mass or more and 1.00 part by mass, more preferably 100 parts by mass of the first (meth) acrylic copolymer. 0.10 parts by mass or more and 0.50 parts by mass or less.
[聚異氰酸酯化合物] [Polyisocyanate compound]
黏著劑組成物,理想為除了前述必要成分以外,更包含至少1種聚異氰酸酯化合物。聚異氰酸酯化物,與第1(甲基)丙烯酸共聚物及特定聚矽氧烷化合物,分別藉由交聯反應,平衡性良好地提升黏著性,與對被接著物之低污染性。 The pressure-sensitive adhesive composition preferably contains at least one polyisocyanate compound in addition to the aforementioned essential components. The polyisocyanate, the first (meth) acrylic copolymer and the specific polysiloxane compound, respectively, have a well-balanced promotion of adhesion by cross-linking reaction and low pollution to the adherend.
作為前述聚異氰酸酯化合物,可舉例如:亞二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、三苯基甲烷三異氰酸酯、甲伸苯基二異氰酸酯等芳香族聚異氰酸酯化合物;例如,六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、該芳香族聚異氰酸酯化合物之氫化物等脂肪族或脂環族聚異氰酸酯化合物;彼等聚異氰酸酯化合物之二聚體或三聚體;該等聚異氰酸酯化合物,與三羥甲基丙烷等之與多元醇化合物之加成物等。該等聚異氰酸酯化合物中,較佳為選自於由六亞甲基二異氰酸酯及六亞甲基二異氰酸酯的二聚體、三聚體及加成物構成之群組中之至少1種,特佳為六亞甲基二異氰酸酯的三聚體。 Examples of the polyisocyanate compound include aromatic polyisocyanate compounds such as xylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and methylenephenyl diisocyanate; for example, hexamethylene diisocyanate Aliphatic or alicyclic polyisocyanate compounds such as isocyanate, isophorone diisocyanate, and the hydride of the aromatic polyisocyanate compound; dimers or trimers of their polyisocyanate compounds; these polyisocyanate compounds, and Additions of trimethylolpropane and the like to polyol compounds. Among these polyisocyanate compounds, at least one selected from the group consisting of dimers, trimers, and adducts of hexamethylene diisocyanate and hexamethylene diisocyanate is preferred, and Trimers of hexamethylene diisocyanate are preferred.
該等聚異氰酸酯化合物,可單獨或混合2種以上使用。 These polyisocyanate compounds can be used individually or in mixture of 2 or more types.
前述聚異氰酸酯化合物,可適當地使用例如:「CORONATE HX」、「CORONATE HL-S」、「CORONATE 2234」、「AQUANATE 200」、「AQUANATE 210」[以上為日本聚胺甲酸酯股份有限公司製],「Desmodur N3300」、「Desmodur N3400」[以上為住友拜耳聚氨酯股份有限公司製],「DURANATE E-405-80T」、「DURANATE 24A-100」、「DURANATE TSE-100」[以上為旭化成工業股份有限公司製],「TAKENATE D-110N」、「TAKENATE D-120N」、「TAKENATE M-631N」、「MT-OLESTER NP1200」[以上為三井武田藥品股份有限公司製]等之利用商品名進行市售者。 As the aforementioned polyisocyanate compound, for example, "CORONATE HX", "CORONATE HL-S", "CORONATE 2234", "AQUANATE 200", "AQUANATE 210" can be suitably used. [The above are manufactured by Japan Polyurethane Co., Ltd. ], "Desmodur N3300", "Desmodur N3400" [The above are manufactured by Sumitomo Bayer Polyurethane Co., Ltd.], "DURANATE E-405-80T", "DURANATE 24A-100", "DURANATE TSE-100" [The above are Asahi Kasei Industries Co., Ltd.], "TAKENATE D-110N", "TAKENATE D-120N", "TAKENATE M-631N", "MT-OLESTER NP1200" [The above is made by Mitsui Takeda Pharmaceutical Co., Ltd.] Marketer.
該等聚異氰酸酯化合物的含量,相對於前述第1(甲基)丙烯酸共聚物100質量份,較佳為0.1質量份以上10質量份以下,更佳為0.5質量份以上5質量份以下。 The content of these polyisocyanate compounds is preferably from 0.1 to 10 parts by mass, and more preferably from 0.5 to 5 parts by mass based on 100 parts by mass of the first (meth) acrylic copolymer.
又,視須要,也可於黏著劑組成物進一步添加二月桂酸二丁基錫等之硬化觸媒。 If necessary, a hardening catalyst such as dibutyltin dilaurate may be further added to the adhesive composition.
黏著劑組成物,除了以上述及之第1(甲基)丙烯酸共聚物、特定聚矽氧烷化合物及鹼金屬鹽以外,視須要可適當地含有耐候性穩定劑、增黏劑、塑化劑、軟化劑、剝離助劑、染料、顏料、無機填充劑、界面活性劑等。 The adhesive composition, in addition to the above-mentioned 1st (meth) acrylic acid copolymer, specific polysiloxane compound, and alkali metal salt, may suitably contain a weather resistance stabilizer, a tackifier, and a plasticizer, if necessary. , Softeners, peeling aids, dyes, pigments, inorganic fillers, surfactants, etc.
<光學構件表面保護膜> <Optical member surface protective film>
本發明之光學構件表面保護膜,具備聚酯基材;與設置於前述聚酯基材上之從前述黏著劑組成物而來之黏著劑層。 The optical member surface protective film of the present invention includes a polyester substrate; and an adhesive layer formed from the adhesive composition provided on the polyester substrate.
前述黏著劑層,因係為從前述黏著劑組成物而來之者,故可構成於黏著性、抑制剝離帶電導致之靜電發生、及對被接著物之低污染性皆優良之黏著劑層。 Since the adhesive layer is derived from the adhesive composition, the adhesive layer can be constituted as an adhesive layer which is excellent in adhesion, suppresses generation of static electricity caused by peeling and charging, and has low pollution to adherends.
使用於本發明之光學構件表面保護膜之基材,若為可在該基材上形成黏著劑層即可,無特別限制。 The base material used for the surface protection film of the optical member of the present invention is not particularly limited as long as it can form an adhesive layer on the base material.
前述基材,從通過透視進行光學構件的檢查及管理之觀點而言,可舉例由聚酯系樹脂、醋酸酯系樹脂、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、丙烯酸系樹脂等構成之膜。其中尤以從表面保護性能之觀點而言,前述基材較佳為聚酯系樹脂,若考慮實用性則特佳為聚對苯二甲酸乙二酯樹脂。 Examples of the base material include a polyester resin, an acetate resin, a polyether fluorene resin, a polycarbonate resin, a polyamine resin, and Film made of polyimide resin, polyolefin resin, acrylic resin, etc. Among them, from the viewpoint of surface protection performance, the aforementioned substrate is preferably a polyester resin, and in view of practicality, it is particularly preferably a polyethylene terephthalate resin.
前述基材的厚度,可例示如:一般可定為500μm以下,較佳為5μm~300μm,更佳為10μm~200μm左右的厚度。 The thickness of the substrate can be exemplified as follows: generally, it can be set to 500 μm or less, preferably 5 μm to 300 μm, and more preferably about 10 μm to 200 μm.
在前述基材的單面或兩面,以剝離時的抗靜電為目的,也可設置抗靜電層。又,在前述基材設置有黏著劑層之一側的表面,為提升與黏著劑層之密合性也可施加電暈放電處理等。 An antistatic layer may be provided on one or both sides of the substrate for the purpose of antistatic during peeling. In addition, a corona discharge treatment or the like may be applied to the surface of one side of the base material on which the adhesive layer is provided in order to improve the adhesion with the adhesive layer.
於前述基材上,設置有從前述黏著劑組成物而來之黏著劑層。 An adhesive layer is provided on the base material from the adhesive composition.
作為黏著劑層的形成方法,例如可採用以下方法:將包含聚異氰酸酯化合物之黏著劑組成物,以直接或視須要以適當的溶媒稀釋,再將其直接塗佈至表面保護基膜(基材)後,進行乾燥去除溶媒。 As a method of forming the adhesive layer, for example, the following method can be adopted: the adhesive composition containing a polyisocyanate compound is diluted directly or optionally with an appropriate solvent, and then coated directly on the surface protective base film (substrate) ), The solvent is removed by drying.
又,也可採用以下之方法:首先,在由利用矽酮樹脂等經施加脫模處理之紙或聚酯膜等適當之膜所構成之剝離片上,例如,塗佈包含聚異氰酸酯化合物之黏著劑組成物,並加熱乾燥使形成黏著劑層,然後將該剝離片之黏著劑層側壓接至表面保護基膜(基材),而將該黏著劑層轉印至該保護膜。 In addition, the following method can also be adopted: first, apply a pressure-sensitive adhesive containing a polyisocyanate compound to a release sheet composed of an appropriate film such as a silicone resin or the like that has been subjected to a mold release treatment or a polyester film; The composition is heated and dried to form an adhesive layer, and then the adhesive layer side of the release sheet is pressure-bonded to a surface protective base film (base material), and the adhesive layer is transferred to the protective film.
在本發明中之前述黏著劑層,理想為藉由前述黏著劑組成物包含之聚異氰酸酯化合物,使第1(甲基)丙烯酸共聚物及特定聚矽氧烷化合物交聯而成之黏著劑層較佳。藉此更為提升黏著劑層的黏著性與對被接著物之低污染性。 The aforementioned adhesive layer in the present invention is preferably an adhesive layer obtained by crosslinking the first (meth) acrylic acid copolymer and the specific polysiloxane compound with the polyisocyanate compound contained in the aforementioned adhesive composition. Better. Thereby, the adhesiveness of the adhesive layer and the low pollution to the adherend are further improved.
以聚異氰酸酯化合物將第1(甲基)丙烯酸共聚物及特定聚矽氧烷化合物交聯之條件無特別限制。 The conditions for cross-linking the first (meth) acrylic acid copolymer and the specific polysiloxane compound with a polyisocyanate compound are not particularly limited.
前述黏著劑層,例如,對於使用於20吋以上之液晶顯示畫面之大型的光學構件具有足夠的黏著力(低速剝離的黏著力足夠大)且高速剝離時可輕易進行剝離(高速剝離時的黏著力不會變大)且順應性良好(裁切的情形時裁切端不會捲起)係為理想。 The above-mentioned adhesive layer has, for example, sufficient adhesion to a large-sized optical member used for a liquid crystal display screen of 20 inches or more (adhesion at low speed peeling is sufficiently large) and can be easily peeled off at high speed (adhesion at high speed peeling) The force will not increase) and the compliance is good (the cutting end will not roll up in the case of cutting).
亦即,前述黏著劑組成物之對於光學構件在23℃的180度剝離的黏著力,較佳為剝離速度0.3m/分(低速剝離)之黏著力(剝離力)為0.05N/25mm以上,更佳為0.06N/25mm以上。 That is, the adhesive force of the aforementioned adhesive composition to the 180-degree peeling of the optical member at 23 ° C. is preferably such that the peeling force (peeling force) at a peeling speed of 0.3 m / min (low-speed peeling) is 0.05 N / 25 mm or more. More preferably, it is 0.06N / 25mm or more.
將前述黏著劑組成物之對於光學構件之低速剝離時的黏著力定為0.05N/25mm以上,藉此可抑制捲曲或偏移的發生。 The adhesive force of the aforementioned adhesive composition at the time of low-speed peeling of the optical member is set to 0.05 N / 25 mm or more, thereby suppressing the occurrence of curl or offset.
又,若前述黏著劑組成物之對於光學構件之黏著力變高,則在大面積中之高速剝離時之作業性降低,因此,較佳為在剝離速度30m/分(高速剝離)之黏著力(剝離力)為未達1.5N/25mm,更佳為未達1.2N/25mm。 In addition, if the adhesive force of the adhesive composition to the optical member is increased, workability during high-speed peeling in a large area is reduced. Therefore, the adhesive force at a peeling speed of 30 m / min (high-speed peeling) is preferred. The (peeling force) is less than 1.5 N / 25 mm, and more preferably 1.2 N / 25 mm.
再者,若表面保護膜剝離時的靜電很大,則會有造成光學構件損傷的情形,因此,本發明之黏著劑組成物對於防眩性偏光板之以30m/分剝離時的剝離靜電壓的絕對值較佳為0.9kV以下,更佳為0.4kV以下,又更佳為0.35kV以下。 Furthermore, if the static electricity at the time of peeling of the surface protection film is large, the optical member may be damaged. Therefore, the peeling static voltage of the adhesive composition of the present invention when peeling off the anti-glare polarizing plate at 30 m / min. The absolute value of is preferably 0.9 kV or less, more preferably 0.4 kV or less, and still more preferably 0.35 kV or less.
又從防止表面保護膜剝離時之膜側的靜電之觀點,理想為前述黏著劑層的表面電阻值為未達1.0E+12(Ω/□)(1.0×1012Ω/□)。 From the viewpoint of preventing static electricity on the film side when the surface protective film is peeled off, the surface resistance value of the adhesive layer is preferably less than 1.0E + 12 (Ω / □) (1.0 × 10 12 Ω / □).
基材上形成之黏著劑層的厚度,可因應對表面保護膜所期待的黏著力,及光學構件表面粗糙度等適當進行設定。基材上形成之黏著劑層的厚度,可例示:一般為1μm~100μm,更佳為5μm~50μm,又更佳為15μm~30μm左右之厚度。 The thickness of the adhesive layer formed on the substrate can be appropriately set in accordance with the adhesion force expected from the surface protective film, and the surface roughness of the optical member. The thickness of the adhesive layer formed on the substrate can be exemplified: generally 1 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 15 μm to 30 μm.
藉由上述所獲得之光學構件表面保護膜,係疊層於光學構件之表面,保護其光學構件的表面不被污染或者損傷,且該光學構件在加工或液晶顯示板等時,該保護膜以保持疊層於光學構件的狀態,供應至衝壓加工、檢查、輸送、組裝液晶顯示面板等之各步驟,並視須要施以高壓釜處理、高溫熟成處理等之加熱加壓處理,且在已不需要表面保護的階段時從光學構件剝離去除。 The surface protective film for an optical member obtained as described above is laminated on the surface of the optical member to protect the surface of the optical member from being contaminated or damaged. When the optical member is processed or a liquid crystal display panel, the protective film is The state of being laminated on the optical member is supplied to each step of stamping, inspection, transportation, and assembly of the liquid crystal display panel, and heat and pressure treatments such as autoclave treatment and high-temperature ripening treatment are applied as necessary, and When a surface protection is required, it peels and removes from an optical member.
以下,藉由實施例更為具體說明本發明,但本發明並不限定於此等之實施例者。再者,除非另有說明以外,「份」及「%」係質量基準。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to those examples. In addition, unless otherwise stated, "part" and "%" are quality standards.
(製造例1) (Manufacturing example 1)
-第1(甲基)丙烯酸共聚物之製造1- -Manufacture of 1st (meth) acrylic copolymer
在具備溫度計、攪拌機、氮氣導入管及回流冷卻器之反應器內,放入乙酸乙酯20份,甲苯10份;又於別的容器,放入作為單體之丙烯酸丁酯(BA)50份、丙烯酸2-乙基己酯(2EHA)46份、作為具有羥基之單體之4-羥基丙烯酸丁酯(4HBA)3份、作為通式(1a)表示之單體之ARONIX M-5300(M5300、東亞合成股份有限公司製)1份,加以混合製成單體混合物。將此單體混合物中之25%加入反應容器中,其次將該反應容器的空氣以氮氣取代後,添加偶氮雙異丁腈(以下稱為AIBN)0.02份作為聚合起始劑,於攪拌下在氮氣環境中使該反應容器內的混合物溫度昇溫至70℃使初期反應開始進行。初期反應大致結束後,將殘留之單體混合物75%、及乙酸乙酯20份、甲苯10份及AIBN 0.2份之混合物分別逐次添加,同時使其反應約2小時,接著進一步使其反應2小時。其後,將AIBN0.25份溶解至 甲苯25份而成之溶液費時1小時進行滴加,進一步使反應1.5小時。反應完成後,以甲苯125份稀釋反應混合物,獲得固體成分35%之第1(甲基)丙烯酸共聚物溶液A-1。 In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux cooler, put 20 parts of ethyl acetate and 10 parts of toluene; and in another container, put 50 parts of butyl acrylate (BA) as a monomer. 46 parts of 2-ethylhexyl acrylate (2EHA), 3 parts of 4-hydroxybutyl acrylate (4HBA) as a monomer having a hydroxyl group, and ARONIX M-5300 (M5300) as a monomer represented by the general formula (1a) (Manufactured by Toa Synthesis Co., Ltd.) 1 part, and mixed to make a monomer mixture. 25% of this monomer mixture was added to the reaction vessel, and after replacing the air in the reaction vessel with nitrogen, 0.02 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) was added as a polymerization initiator, with stirring. The temperature of the mixture in the reaction vessel was raised to 70 ° C. in a nitrogen atmosphere to start the initial reaction. After the initial reaction was almost completed, 75% of the remaining monomer mixture and 20 parts of ethyl acetate, 10 parts of toluene, and 0.2 parts of AIBN were added successively, and allowed to react for about 2 hours, and then allowed to react for 2 hours. . Thereafter, 0.25 parts of AIBN was dissolved to A solution of 25 parts of toluene was added dropwise over 1 hour, and the reaction was further allowed to proceed for 1.5 hours. After the reaction was completed, the reaction mixture was diluted with 125 parts of toluene to obtain a 1% (meth) acrylic acid copolymer solution A-1 having a solid content of 35%.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為53萬,分散度(Mw/Mn)為8.2。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 530,000, and the degree of dispersion (Mw / Mn) was 8.2.
(製造例2) (Manufacturing example 2)
-第1(甲基)丙烯酸共聚物之製造2- -Manufacture of 1st (meth) acrylic acid copolymer 2-
在製造例1中,除了將丙烯酸2-乙基己酯(2EHA)的摻合量變更為45份,M5300的摻合量變更為2份以外,與製造例1同樣方式實施,製成第1(甲基)丙烯酸共聚物溶液A-2。 In Manufacturing Example 1, except that the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 45 parts, and the blending amount of M5300 was changed to 2 parts, the same procedure as in Manufacturing Example 1 was performed to make the first (Meth) acrylic copolymer solution A-2.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為52萬,分散度(Mw/Mn)為8.0。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 520,000, and the degree of dispersion (Mw / Mn) was 8.0.
(製造例3) (Manufacture example 3)
-第1(甲基)丙烯酸共聚物之製造3- -Manufacture of 1st (meth) acrylic copolymer 3-
在製造例1中,除了將丙烯酸2-乙基己酯(2EHA)的摻合量變更為43份,M5300的摻合量變更為4份以外,與製造例1同樣方式實施,製成第1(甲基)丙烯酸共聚物溶液A-3。 In Production Example 1, except that the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 43 parts, and the blending amount of M5300 was changed to 4 parts, the same procedure as in Production Example 1 was carried out to make the first (Meth) acrylic acid copolymer solution A-3.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為48萬,分散度(Mw/Mn)為7.7。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 480,000, and the degree of dispersion (Mw / Mn) was 7.7.
(製造例4) (Manufacturing example 4)
-第1(甲基)丙烯酸共聚物之製造4- -Manufacture of 1st (meth) acrylic copolymer 4-
在製造例1中,除了以LIGHT ACRYLATE HO-AMS(HOAMS、共榮社化學股份有限公司製)1份替代M5300作為通式(1a)表示之單體以外,與製造例1同樣方式實施,製成第1(甲基)丙烯酸共聚物溶液A-4。 In Production Example 1, except that one part of LIGHT ACRYLATE HO-AMS (HOAMS, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of M5300 as the monomer represented by the general formula (1a), it was implemented in the same manner as in Production Example 1. It becomes the 1st (meth) acrylic acid copolymer solution A-4.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為50萬,分散度(Mw/Mn)為8.4。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 500,000, and the degree of dispersion (Mw / Mn) was 8.4.
(製造例5) (Manufacturing example 5)
-第1(甲基)丙烯酸共聚物之製造5- -Manufacture of 1st (meth) acrylic copolymer 5-
在製造例1中,除了將丙烯酸丁酯(BA)的摻合量變更為96份,丙烯酸2-乙基己酯(2EHA)的摻合量變更為0份以外,與製造例1同樣方式實施,製成第1(甲基)丙烯酸共聚物溶液A-5。 Production Example 1 was carried out in the same manner as in Production Example 1 except that the blending amount of butyl acrylate (BA) was changed to 96 parts and the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 0 parts. To prepare a first (meth) acrylic acid copolymer solution A-5.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為54萬,分散度(Mw/Mn)為6.9。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 540,000, and the degree of dispersion (Mw / Mn) was 6.9.
(製造例6) (Manufacturing example 6)
-第1(甲基)丙烯酸共聚物之製造6- -Manufacture of 1st (meth) acrylic copolymer
在製造例1中,除了將丙烯酸丁酯(BA)的摻合量變更為0份,丙烯酸2-乙基己酯(2EHA)的摻合量變更為96份以外,與製造例1同樣方式實施,製成第1(甲基)丙烯酸共聚物溶液A-6。 Production Example 1 was carried out in the same manner as in Production Example 1 except that the blending amount of butyl acrylate (BA) was changed to 0 parts and the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 96 parts. To prepare the first (meth) acrylic acid copolymer solution A-6.
獲得之第1(甲基)丙烯酸共聚物的重量平均分子量(Mw)為41萬,分散度(Mw/Mn)為8.3。 The weight average molecular weight (Mw) of the obtained 1st (meth) acrylic acid copolymer was 410,000, and the degree of dispersion (Mw / Mn) was 8.3.
(製造例7) (Manufacturing example 7)
-(甲基)丙烯酸共聚物之製造C1- -Manufacture of (meth) acrylic copolymer C1-
在製造例1中,除了將丙烯酸2-乙基己酯(2EHA)的摻合量變更為47份,M5300變更為未摻合(0份)以外,與製造例1同樣方式實施,製成(甲基)丙烯酸共聚物溶液C-1。 Production Example 1 was carried out in the same manner as in Production Example 1 except that the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 47 parts and M5300 was changed to unblended (0 parts). Methacrylic acid copolymer solution C-1.
獲得之(甲基)丙烯酸共聚物的重量平均分子量(Mw)為53萬,分散度(Mw/Mn)為8.9。 The weight average molecular weight (Mw) of the obtained (meth) acrylic copolymer was 530,000, and the degree of dispersion (Mw / Mn) was 8.9.
(製造例8) (Manufacturing example 8)
-(甲基)丙烯酸共聚物之製造C2- -Manufacture of (meth) acrylic copolymer C2-
在製造例1中,除了將丙烯酸2-乙基己酯(2EHA)的摻合量變更為46.5份,以丙烯酸(AA)0.5份替代M5300使用以外,與製造例1同樣方式實施,製成(甲基)丙烯酸共聚物溶液C-2。 In Production Example 1, except that the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 46.5 parts, and 0.5 part of acrylic acid (AA) was used instead of M5300, it was implemented in the same manner as in Production Example 1 to obtain ( Methacrylic acid copolymer solution C-2.
獲得之(甲基)丙烯酸共聚物的重量平均分子量(Mw)為50萬,分散度 (Mw/Mn)為8.3。 The weight average molecular weight (Mw) of the obtained (meth) acrylic copolymer was 500,000, and the degree of dispersion (Mw / Mn) was 8.3.
(製造例9) (Manufacturing example 9)
-(甲基)丙烯酸共聚物之製造C3- -Manufacture of (meth) acrylic copolymer C3-
在製造例1中,除了將丙烯酸2-乙基己酯(2EHA)的摻合量變更為46.5份,以甲基丙烯酸(MAA)0.5份替代M5300使用以外,與製造例1同樣方式實施,製成(甲基)丙烯酸共聚物溶液C-3。 In Manufacturing Example 1, except that the blending amount of 2-ethylhexyl acrylate (2EHA) was changed to 46.5 parts, and 0.5 parts of methacrylic acid (MAA) was used instead of M5300, the same procedure as in Manufacturing Example 1 was carried out. It becomes (meth) acrylic copolymer solution C-3.
獲得之(甲基)丙烯酸共聚物的重量平均分子量(Mw)為49萬,分散度(Mw/Mn)為8.3。 The weight average molecular weight (Mw) of the obtained (meth) acrylic copolymer was 490,000, and the degree of dispersion (Mw / Mn) was 8.3.
(製造例10) (Manufacturing example 10)
-第2(甲基)丙烯酸共聚物之製造1- -Manufacture of 2nd (meth) acrylic copolymer
於具備攪拌葉片、溫度計、氮氣導入管、冷卻器、滴液漏斗之四口燒瓶放入甲基丙烯酸正丁酯(n-BMA)90份、作為含有聚伸烷氧基之單體之甲氧基聚乙二醇甲基丙烯酸酯(伸乙基氧基的重複數的平均值為23)10份、作為聚合起始劑之AIBN0.8份、乙酸乙酯400份,緩慢地攪拌的同時導入氮氣,且將燒瓶內的液溫保持於70℃實施6小時聚合反應,製備固體成分20%之第2(甲基)丙烯酸共聚物的溶液B-1。 In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, a cooler, and a dropping funnel, 90 parts of n-butyl methacrylate (n-BMA) was placed as a methoxy group containing a polyalkyleneoxy monomer. 10 parts of poly (ethylene glycol methacrylate) (average number of repeats of ethoxy groups is 23), 0.8 parts of AIBN as a polymerization initiator, and 400 parts of ethyl acetate, and introduce while slowly stirring The temperature of the liquid in the flask was maintained at 70 ° C. under nitrogen for 6 hours to perform a polymerization reaction to prepare a solution B-1 of the second (meth) acrylic copolymer having a solid content of 20%.
獲得之第2(甲基)丙烯酸共聚物的重量平均分子量為7,000。 The weight average molecular weight of the 2nd (meth) acrylic acid copolymer obtained was 7,000.
<實施例1> <Example 1>
於具備攪拌葉片、溫度計、冷卻器、滴液漏斗之四口燒瓶,分別放入:在前述獲得之第1(甲基)丙烯酸共聚物溶液A-1(在表中為樹脂A)以固體成分換算為100份、第2(甲基)丙烯酸共聚物溶液B-1(在表中為樹脂B)以固體成分換算0.4份、作為特定聚矽氧烷化合物之SH-3773M(東麗道康寧股份有限公司製、側鏈聚醚改性矽酮、聚醚末端為羥基)0.1份,LiCF3SO3(森田化學工業股份有限公司製、LiTFS)0.05份,並將燒瓶內的液溫保持於25℃,實施4.0小時之混合攪拌,而獲得(甲基)丙烯酸共聚物混合溶液。 In a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, each of the four (1) (meth) acrylic acid copolymer solution A-1 (resin A in the table) obtained as the solid component was placed in SH-3773M (Toray Dow Corning Co., Ltd. Limited), which is converted into 100 parts of the second (meth) acrylic acid copolymer solution B-1 (Resin B in the table) in terms of solid content, as a specific polysiloxane compound 0.1 part of side chain polyether modified silicone, polyether terminal is hydroxyl), LiCF 3 SO 3 (Morida Chemical Industry Co., Ltd., LiTFS) 0.05 part, and the liquid temperature in the flask was kept at 25 ° C The mixture was stirred for 4.0 hours to obtain a (meth) acrylic copolymer mixed solution.
於其中添加作為聚異氰酸酯化合物之商品名:Desmodur N3300[HMDI三聚體型、固體成分100重量%;住化拜耳聚氨酯股份有限公司)製]2.5份, 充分攪拌,而獲得表面保護膜用黏著劑組成物(以下,亦簡稱為「黏著劑組成物」)。 To this was added 2.5 parts of Desmodur N3300 [HMDI trimer type, solid content 100% by weight; manufactured by Sumitomo Bayer Polyurethane Co., Ltd.] as a polyisocyanate compound, Stir well to obtain an adhesive composition for a surface protective film (hereinafter, also simply referred to as "adhesive composition").
此黏著劑組成物係具有充分之應用期者。 This adhesive composition has a sufficient application period.
使用獲得之黏著劑組成物,按照以下的測試用表面保護膜的製作方法製作測試用表面保護膜,實施各種物性測試。將獲得之結果表示於表1。 Using the obtained adhesive composition, a test surface protection film was produced according to the following production method of a test surface protection film, and various physical property tests were performed. The obtained results are shown in Table 1.
(1)測試用表面保護膜之製作 (1) Production of surface protective film for testing
在已經矽酮系脫模劑進行表面處理之脫模紙上,塗佈黏著劑組成物使乾燥後之塗佈量為20g/m2,並以熱風循環式乾燥機以100℃、60秒鐘實施乾燥而形成黏著劑層後,載置於聚對苯二甲酸乙二酯(PET)膜[商品名;E5001;東洋紡績(股)製]上,使該黏著劑層面接觸,並藉由加壓軋輥加以壓接貼合後,在23℃、50%RH的環境下實施熟成10天(aging),而獲得測試用表面保護膜。 On the release paper that has been surface-treated with a silicone-based release agent, the adhesive composition is applied so that the coating amount after the drying is 20 g / m 2 , and it is carried out in a hot air circulation dryer at 100 ° C. for 60 seconds. After drying to form an adhesive layer, it is placed on a polyethylene terephthalate (PET) film [trade name; E5001; manufactured by Toyo Industries Co., Ltd.], and the adhesive layer is brought into contact and pressurized After the rolls were pressure-bonded and bonded, they were aged for 10 days in an environment of 23 ° C. and 50% RH to obtain a test surface protection film.
(2)黏著力之測定 (2) Determination of adhesion
將前述(1)製作之測試用表面保護膜裁切為25mm×150mm後,從此表面保護膜片剝除脫模紙,使用桌上型疊合機,將其壓接於經防眩性處理之偏光膜[商品名;SQ-1852AP-AG6;住友化學工業(股)製],以作為測試樣本。 After cutting the test surface protection film prepared in (1) above to 25mm × 150mm, peel the release paper from this surface protection film, and use a desktop laminator to crimp it to the anti-glare treatment. A polarizing film [trade name; SQ-1852AP-AG6; manufactured by Sumitomo Chemical Industries, Ltd.] was used as a test sample.
將此測試樣本在23℃、50%RH的環境下放置24小時(調理處理(conditioning))後,分別以剝離速度0.3m/分(低速剝離)的條件,與剝離速度30m/分(高速剝離)的條件測定從偏光膜將表面保護膜連同黏著層,從長邊(150mm)方向剝離的情形時之180°剝離中的黏著力。 This test sample was left for 24 hours (conditioning) in an environment of 23 ° C and 50% RH, and the peeling speed was 0.3 m / min (low-speed peeling), and the peeling speed was 30 m / min (high-speed peeling). ) Conditions. The 180 ° peeling force was measured when the surface protective film and the adhesive layer were peeled from the polarizing film in the direction of the long side (150 mm).
(3)黏著劑層中之水之接觸角(污染性評價) (3) Contact angle of water in the adhesive layer (pollution evaluation)
將前述(1)製作之測試用表面保護膜放置在60℃、90%RH的環境下48小時。又在23℃、50%RH的環境下放置1小時後,從測試用表面保護膜剝離脫模薄膜而使黏著劑層面露出。在黏著劑層面上滴下2μl的純水,在30秒後使用接觸角測定裝置(協和界面化學股份有限公司製:Contact angle meter CA-D)測定水的接觸角,按照下列評價基準評價對被接著物之污染性。 The test surface protection film prepared in the above (1) was left in an environment of 60 ° C. and 90% RH for 48 hours. After being left in an environment of 23 ° C. and 50% RH for another 1 hour, the release film was peeled from the surface protection film for testing to expose the adhesive layer. 2 μl of pure water was dropped on the adhesive layer, and the contact angle of the water was measured using a contact angle measuring device (contact angle meter CA-D, manufactured by Kyowa Interface Chemical Co., Ltd.) after 30 seconds, and the following was evaluated according to the following evaluation criteria. Contamination of things.
~評價基準~ ~ Evaluation criteria ~
AA:接觸角為90°以上。 AA: The contact angle is 90 ° or more.
A:接觸角為80°以上未達90°。 A: The contact angle is 80 ° to 90 °.
B:接觸角為50°以上未達80°。 B: The contact angle is 50 ° or more and less than 80 °.
C:接觸角為未達50°。 C: The contact angle is less than 50 °.
(4)表面電阻值之測定 (4) Measurement of surface resistance
從前述(1)製作之測試用表面保護膜剝除剝離紙,使用表面電阻測定裝置(Advantest(股):R12704 RESISTIVITY CHAMBER)測定露出之黏著劑層表面的表面電阻值,按照下列評價基準評價抗靜電性。 The release paper was peeled off from the test surface protective film prepared in (1) above, and the surface resistance value of the surface of the exposed adhesive layer was measured using a surface resistance measuring device (Advantest (share): R12704 RESISTIVITY CHAMBER), and the resistance was evaluated according to the following evaluation criteria Static electricity.
~評價基準~ ~ Evaluation criteria ~
AA:表面電阻值未達1.0E+11(Ω/□)。 AA: The surface resistance value does not reach 1.0E + 11 (Ω / □).
A:表面電阻值為1.0E+11(Ω/□)以上未達5.0E+11(Ω/□)。 A: The surface resistance value is 1.0E + 11 (Ω / □) or more and less than 5.0E + 11 (Ω / □).
B:表面電阻值為5.0E+11(Ω/□)以上未達1.0E+12(Ω/□)。 B: The surface resistance value is 5.0E + 11 (Ω / □) or more and less than 1.0E + 12 (Ω / □).
C:表面電阻值為1.0E+12(Ω/□)以上。 C: The surface resistance value is 1.0E + 12 (Ω / □) or more.
(5)剝離靜電壓測定 (5) Measurement of peeling static voltage
將前述(1)製作之測試用表面保護膜裁切為25mm×150mm後,將此表面保護膜片,使用桌上型疊合機,壓接於經防眩性處理之偏光膜[商品名;SQ-1852AP-AG6;住友化學工業(股)製]而作為測試樣本。將此樣本放置在23℃、50%RH的條件下24小時(調理處理)後,以180°剝離、剝離速度30m/分鐘(高速剝離條件)進行剝離。將此時發生之偏光板表面的電位(kV),以固定於垂直於偏光板其面之上10mm位置之電位測定機[春日電機(股)製KSD-03031進行測定。測定為在23℃、50%RH的環境下進行。 After cutting the surface protection film for test prepared in (1) above to 25mm × 150mm, this surface protection film was crimped to the anti-glare-treated polarizing film using a desktop laminator [trade name; SQ-1852AP-AG6; Sumitomo Chemical Industry Co., Ltd.] as test samples. This sample was left under conditions of 23 ° C. and 50% RH for 24 hours (conditioning treatment), and then peeled at a peeling speed of 180 ° and a peeling speed of 30 m / minute (high-speed peeling conditions). The potential (kV) on the surface of the polarizing plate generated at this time was measured with a potentiometer [KSD-03031, manufactured by Kasuga Electric Co., Ltd.] fixed to a position 10 mm above the surface of the polarizing plate. The measurement was performed under the environment of 23 ° C and 50% RH.
<實施例2~實施例13> <Example 2 to Example 13>
在實施例1中,除了將使用於製備表面保護膜用黏著劑組成物之各成分分別變更如表1及表2所示以外,以與實施例1同樣方式實施製作表面保護膜用黏著劑組成物,並且以同樣方式實施各種物性測試。將獲得之結果表示於表1及表2。 In Example 1, the components of the surface protective film adhesive composition were changed in the same manner as in Example 1 except that the components used to prepare the surface protective film adhesive composition were changed as shown in Tables 1 and 2, respectively. And perform various physical property tests in the same manner. The obtained results are shown in Tables 1 and 2.
<比較例1~比較例4> <Comparative Example 1 to Comparative Example 4>
在實施例1中,除了將使用於製備表面保護膜用黏著劑組成物之各成分變更如表2所示以外,以與實施例1同樣方式實施製作表面保護膜用黏著劑組成物,並且以同樣方式實施各種物性測試。將獲得之結果表示於表2。 In Example 1, except that the components used to prepare the adhesive composition for surface protection film were changed as shown in Table 2, the production of the adhesive composition for surface protection film was performed in the same manner as in Example 1, and Various physical property tests were performed in the same manner. The obtained results are shown in Table 2.
再者,表1及表2中之簡稱係如下述。 The abbreviations in Tables 1 and 2 are as follows.
BA:丙烯酸丁酯;2EHA:丙烯酸2-乙基己酯;4HBA:4-羥基丙烯酸丁酯;M5300:東亞合成(股)製,ARONIX M-5300,ω-羧基-聚己內酯(n≒2)單丙烯酸酯;HOAMS:共榮社化學(股)製,LIGHT ACRYLATE HOA-MS(N),琥珀酸2-丙烯醯氧基乙酯;AA:丙烯酸;MAA:甲基丙烯酸;n-BMA:甲基丙烯酸正丁酯;MePEGMA:甲氧基聚乙二醇甲基丙烯酸酯(伸乙基氧基的重複數的平均值為23);N3300:Desmodur N3300[六亞甲基二異氰酸酯三聚體,住化拜耳聚氨酯(股)公司製];SH-3773M:東麗道康寧(股)製,側鏈聚醚改性矽酮,通式(3)表示之聚矽氧烷化合物;FZ-2162:東麗道康寧(股)製,側鏈聚醚改性矽酮,通式(3)表示之聚矽氧烷化合物;SH-8400:東麗道康寧(股)製,側鏈聚醚改性矽酮;AS劑:抗靜電劑;LiTFSI:Li(CF3SO2)2N;LiTFS:LiCF3SO3。 BA: Butyl acrylate; 2EHA: 2-Ethylhexyl acrylate; 4HBA: 4-Hydroxybutyl acrylate; M5300: manufactured by Toa Kosei Co., Ltd .; ARONIX M-5300; 2) Monoacrylate; HOAMS: manufactured by Kyoeisha Chemical Co., Ltd., Light ACRYLATE HOA-MS (N), 2-propenyloxyethyl succinate; AA: acrylic acid; MAA: methacrylic acid; n-BMA : N-butyl methacrylate; MePEGMA: methoxy polyethylene glycol methacrylate (average number of repeats of ethoxy group is 23); N3300: Desmodur N3300 [hexamethylene diisocyanate trimer Body, manufactured by Sumitomo Bayer Polyurethanes Co., Ltd.]; SH-3773M: Toray Dow Corning Co., Ltd., a side chain polyether modified silicone, a polysiloxane compound represented by the general formula (3); FZ-2162 : Toray Dow Corning Co., Ltd., side chain polyether modified silicone, polysiloxane compound represented by general formula (3); SH-8400: Toray Dow Corning Co., Ltd., side chain polyether modified silicon Ketones; AS agent: antistatic agent; LiTFSI: Li (CF 3 SO 2 ) 2 N; LiTFS: LiCF 3 SO 3 .
【表1】
【表2】
從表1及表2得知,本發明之黏著劑組成物的黏著性、抑制剝離帶電導致之靜電的發生、及對被接著物之低污染性優秀。 As can be seen from Tables 1 and 2, the adhesive composition of the present invention is excellent in adhesion, suppresses generation of static electricity caused by peeling and electrification, and has low pollution to adherends.
[順應性之評價] [Evaluation of compliance]
將使用在實施例1~實施例13製作之黏著劑組成物而製作之測試用表面保護膜,裁切為200mm×150mm之後,剝除脫模膜,在23℃、50%RH的條件下將黏著劑層從中心部分貼合至經防眩性處理之偏光膜,測定藉由自然重力而擴大潤濕的時間,此時,在全部的樣本中直到端部為止完全潤濕的時間皆未達60秒,展現優良順應性。 The test surface protective film prepared using the adhesive composition prepared in Examples 1 to 13 was cut into a size of 200 mm × 150 mm, and then the release film was peeled off. The conditions were 23 ° C and 50% RH. The adhesive layer was laminated from the central part to the anti-glare-treated polarizing film, and the time to extend the wetting by natural gravity was measured. At this time, in all the samples, the time to complete wetting was not reached until the end. 60 seconds, showing excellent compliance.
【產業上利用性】 [Industrial availability]
根據本發明,可提供高水準地兼具抗靜電性及對被接著物之低污染性的黏著劑組成物及使用此而成之光學構件表面保護膜。 According to the present invention, it is possible to provide an adhesive composition having both a high level of antistatic properties and low contamination to an adherend, and an optical member surface protective film using the same.
日本專利申請案第2012-286049號之揭示內容全部應參考而併入於本說明書。 The disclosure of Japanese Patent Application No. 2012-286049 is incorporated herein by reference in its entirety.
本說明書之所有文獻、專利申請案、及技術規格,係與各自之文獻、專利申請案、及技術規格以參考而納入而具體且分別記載的情形為同程度地納入於本說明書作為參考。 All documents, patent applications, and technical specifications in this specification are incorporated into this specification for reference to the same extent as if the respective documents, patent applications, and technical specifications were incorporated by reference, and were specifically and separately described.
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JP6673621B2 (en) * | 2016-01-19 | 2020-03-25 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition and optical member surface protection film |
JP6633923B2 (en) * | 2016-01-26 | 2020-01-22 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for protective film and protective film |
JP6969147B2 (en) * | 2017-05-02 | 2021-11-24 | 三菱ケミカル株式会社 | Adhesive composition, adhesive, adhesive tape and airtight waterproof adhesive tape |
JP7020606B2 (en) * | 2017-08-10 | 2022-02-16 | 日本カーバイド工業株式会社 | Adhesive composition for protective film and protective film |
KR102464960B1 (en) * | 2017-08-10 | 2022-11-08 | 닛뽕 카바이도 고교 가부시키가이샤 | Adhesive composition for protective film, and protective film |
JP7107804B2 (en) * | 2018-09-27 | 2022-07-27 | 藤森工業株式会社 | Adhesive composition, and adhesive film and surface protective film using the same |
KR102480720B1 (en) * | 2018-12-03 | 2022-12-23 | 디아이씨 가부시끼가이샤 | Pressure-sensitive adhesive composition and laminated film using the same |
WO2020184161A1 (en) * | 2019-03-08 | 2020-09-17 | Dic株式会社 | Pressure-sensitive adhesive composition and lamination film using same |
CN111621249A (en) * | 2020-05-15 | 2020-09-04 | 中国乐凯集团有限公司 | Adhesive composition, protective film, composite film, and device |
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JP5047557B2 (en) * | 2006-07-28 | 2012-10-10 | リンテック株式会社 | Adhesive composition, and adhesive sheet and adhesive optical member using the same |
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JP5361254B2 (en) * | 2008-06-06 | 2013-12-04 | 日本カーバイド工業株式会社 | Conductive adhesive composition and processing process protective film |
CN102131880B (en) * | 2008-09-01 | 2014-08-06 | 日本电石工业株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and optical film |
JP5611527B2 (en) * | 2009-01-08 | 2014-10-22 | 日本カーバイド工業株式会社 | Adhesive and optical film |
JP5623020B2 (en) * | 2009-02-27 | 2014-11-12 | 日東電工株式会社 | Adhesive composition, adhesive layer, and adhesive sheet |
JP5544800B2 (en) * | 2009-09-17 | 2014-07-09 | サイデン化学株式会社 | Surface protection film |
JP2011236267A (en) * | 2010-05-06 | 2011-11-24 | Nippon Carbide Ind Co Inc | Adhesive composition for surface protective film, and surface protective film using this |
JP5648494B2 (en) * | 2011-01-25 | 2015-01-07 | 住友化学株式会社 | Adhesive sheet, optical film with adhesive, and optical laminate |
JP5879160B2 (en) * | 2012-03-06 | 2016-03-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
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