TWI720949B - Layered body - Google Patents
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- TWI720949B TWI720949B TW104130878A TW104130878A TWI720949B TW I720949 B TWI720949 B TW I720949B TW 104130878 A TW104130878 A TW 104130878A TW 104130878 A TW104130878 A TW 104130878A TW I720949 B TWI720949 B TW I720949B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Abstract
本發明係有關於一種用以提供貼合於表面形狀呈各式各樣的被黏物時的黏著特性優良，而且在高溫、高壓力的嚴峻條件下保存時，也不易對被黏物產生汙染的積層體之組成物、及由前述組成物所構成之積層體。 The present invention relates to a method for providing excellent adhesion properties when sticking to adherends with various surface shapes, and it is not easy to pollute the adherend when stored under severe conditions of high temperature and high pressure. The composition of the laminated body, and the laminated body composed of the aforementioned composition.
一種組成物，其係滿足下述條件1：條件1 在頻率1Hz、應變0.01%下所測得之動態黏彈性之損失正切的溫度分散，在-50℃以上50℃以下的範圍具有至少2個極大值。 A composition that satisfies the following condition 1: Condition 1 The temperature dispersion of the loss tangent of dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01% has at least 2 in the range of -50 ℃ above 50 ℃ maximum.
Description
本發明係有關於一種用以提供貼合於表面形狀呈各式各樣的被黏物時的黏著特性優良，而且在高溫、高壓力的嚴峻條件下保存時，也不易對被黏物產生汙染的積層體之組成物、及由前述組成物所構成之積層體。 The present invention relates to a method for providing excellent adhesion properties when sticking to adherends with various surface shapes, and it is not easy to pollute the adherend when stored under severe conditions of high temperature and high pressure. The composition of the laminated body, and the laminated body composed of the aforementioned composition.
包含合成樹脂、金屬、玻璃等各種素材的製品，為防止加工步驟、輸送步驟、保存中所生成的傷痕或髒汙，多有黏貼供保護表面的材料而取用處理。其代表例為表面保護薄膜，一般係使用在包含熱塑性樹脂或紙的支持基材上形成有黏著層者，藉由將黏著層面貼附於被黏物並以支持基材加以被覆來保護表面。 For products containing various materials such as synthetic resin, metal, glass, etc., in order to prevent scratches or dirt generated during processing steps, transportation steps, and storage, most of the materials are pasted to protect the surface and processed. A representative example is a surface protection film, which is generally used with an adhesive layer formed on a support substrate containing thermoplastic resin or paper. The surface is protected by attaching the adhesive layer to the adherend and covering it with the support substrate.
特別是近年來，液晶顯示器或觸控面板裝置普及化，而此等係由包含合成樹脂的多數個光學片或光學薄膜等構件所構成。所述光學用構件，由於需極力減少光學扭曲等缺點，而為了防止可能成為缺點來源的傷痕或髒汙，則大多使用表面保護薄膜。 Especially in recent years, liquid crystal displays and touch panel devices have become popular, and these are composed of multiple optical sheets or optical films containing synthetic resin. In the optical member, since it is necessary to minimize defects such as optical distortion, in order to prevent scratches or dirt that may be the source of the defect, a surface protective film is often used.
作為表面保護薄膜的特性，可舉出在受到溫度、濕度等的環境變化或微小應力之程度下不易由被黏物剝離；由被黏物剝離時不會在被黏物殘留黏著劑及黏著劑成分等。 As the characteristics of the surface protection film, it is difficult to peel off from the adherend under environmental changes such as temperature and humidity or slight stress; when peeling from the adherend, no adhesive and adhesive remain on the adherend Ingredients etc.
上述光學用構件當中，如擴散板或稜鏡片等表面具有凹凸的構件，在貼合表面保護薄膜後，黏著層對凹凸部的追隨性不充分，未能獲得所期望的黏著力，而有發生剝離的情形。針對此點，已知有將黏著層軟化的方法或使用增黏劑來提高黏著力的方法等(例如專利文獻1~5)。 Among the above-mentioned optical components, such as diffusers or slabs with uneven surfaces, after the surface protection film is laminated, the adhesive layer does not follow the uneven portions sufficiently, and the desired adhesive force may not be obtained, which may occur. The case of peeling. In response to this point, a method of softening the adhesive layer or a method of increasing the adhesive force using a thickener is known (for example, Patent Documents 1 to 5).
專利文獻1 日本特開2008-214437號公報 Patent Document 1 JP 2008-214437 A
專利文獻2 日本特開2005-298630號公報 Patent Document 2 JP 2005-298630 A
專利文獻3 日本特開2012-77244號公報 Patent Document 3 JP 2012-77244 A
專利文獻4 日本特開平05-194923號公報 Patent Document 4 Japanese Patent Laid-Open No. 05-194923
專利文獻5 日本特開2012-111793號公報 Patent Document 5 JP 2012-111793 A
然而，就上述方法而言，有隨著時間經過黏著力增大，剝離性惡化的情形。又，在施予高溫或壓力的狀態下保存時，亦同樣有剝離性惡化的情形。更者，於剝離之際，有黏著層成分附著於被黏物表面，而成為髒汙來源的情形。 However, in the above-mentioned method, the adhesive force may increase over time, and the releasability may deteriorate. In addition, when stored in a state where high temperature or pressure is applied, the releasability may similarly deteriorate. Moreover, during peeling, the adhesive layer component may adhere to the surface of the adherend and become a source of contamination.
本發明係鑑於上述課題，提供一種用以提供對表面具有凹凸的各式各樣被黏物均具有適度的黏著特性，而且在高溫、高壓力的嚴峻條件下保存時，也不易對被黏物產生汙染的積層體之組成物、及使用前述組成物所構成之積層體。 In view of the above-mentioned problems, the present invention provides a method for providing various adherends with irregularities on the surface that have moderate adhesion characteristics, and are not easy to adhere to the adherend when stored under severe conditions of high temperature and high pressure. The composition of the layered body that is contaminated, and the layered body formed by using the aforementioned composition.
本案發明人等為解決上述課題而致力重複研究的結果，完成以下發明。亦即，本發明係如下所述。 The inventors of the present application have made the following inventions as a result of repeated studies to solve the above-mentioned problems. That is, the present invention is as follows.
1)一種組成物，其特徵為滿足下述條件1：條件1 在頻率1Hz、應變0.01%下所測得之動態黏彈性之損失正切的溫度分散，在-50℃以上50℃以下的範圍具有至少2個極大值。 1) A composition characterized by satisfying the following condition 1: Condition 1 The temperature dispersion of the loss tangent of dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01%, which has a temperature dispersion in the range of -50°C to 50°C At least 2 maximum values.
2)如1)之組成物，其中前述組成物係滿足下述條件2：條件2 前述損失正切的溫度分散於高溫側的極大值為0.1以上1.0以下。 2) The composition according to 1), wherein the aforementioned composition satisfies the following condition 2: Condition 2 The maximum value of the temperature dispersion of the aforementioned loss tangent on the high temperature side is 0.1 or more and 1.0 or less.
3)如1)或2)之組成物，其中前述組成物係滿足下述條件3：條件3 前述損失正切的溫度分散於高溫側的極大值為0.3以上1.0以下。 3) The composition according to 1) or 2), wherein the aforementioned composition system satisfies the following condition 3: Condition 3 The maximum value of the dispersion of the aforementioned loss tangent temperature on the high temperature side is 0.3 or more and 1.0 or less.
根據本發明，鑑於上述課題，可提供一種用以提供對表面具有凹凸的各式各樣被黏物均具有適度的黏著特性，而且在高溫、高壓力的嚴峻條件下保存時，也不易對被黏物產生汙染的積層體之組成物、及由前述組成物所構成之積層體。 According to the present invention, in view of the above-mentioned problems, it is possible to provide a method for providing various adherends with irregularities on the surface that have moderate adhesion characteristics, and are not easy to be stored under severe conditions of high temperature and high pressure. The composition of the laminated body where the sticky matter is contaminated, and the laminated body composed of the aforementioned composition.
以下，就本發明之組成物及積層體的構成要件詳細加以說明。 Hereinafter, the constituent elements of the composition and laminate of the present invention will be described in detail.
本發明之組成物係滿足下述條件1：條件1：在頻率1Hz、應變0.01%下所測得之動態黏彈性之損失正切的溫度分散，在-50℃以上50℃以下的範圍具有至少2個極大值。 The composition of the present invention satisfies the following condition 1: Condition 1: The temperature dispersion of the loss tangent of dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01% has at least 2 in the range of -50°C to 50°C A maximum value.
藉由在前述範圍具有2個極大值，將本發明之組成物使用於供保護被黏物用的積層體之黏著層時，對於稜鏡片等表面具有凹凸的被黏物亦可獲得良好的貼合性，隨時間經過也不易發生剝離，而且由被黏物剝離時可得良好的剝離性。 By having two maximum values in the aforementioned range, when the composition of the present invention is used in the adhesive layer of a laminate for protecting adherends, it is possible to obtain a good paste for adherends with irregularities on the surface such as scallops. Adhesiveness, it is not easy to peel off with the passage of time, and good peelability can be obtained when peeling from the adherend.
於此，極大值係指呈連續變化的動態黏彈性之損失正切的溫度分散，於此溫度前後由增加轉為減少的點的值，可由動態黏彈性之損失正切的溫度分散曲線的形狀、或其微分係數來判斷。亦即，微分係數為零的點，且於此前後微分係數由負轉正的點為極大值。 Here, the maximum value refers to the temperature dispersion of the loss tangent of dynamic viscoelasticity that continuously changes, and the value at the point before and after the temperature increases from increase to decrease, which can be determined by the shape of the temperature dispersion curve of the loss tangent of dynamic viscoelasticity, or Its differential coefficient to judge. That is, the point where the differential coefficient is zero, and the point where the differential coefficient changes from negative to positive before and after is the maximum value.
於此，所稱「動態黏彈性測定」，係指藉由對試料隨時間賦予變動(振動)的應變或應力，並測定隨之而生的應力或應變，來探究試料的力學性質的測定，其測定模式有拉伸/壓縮、剪切、3點彎曲等多種，此處係以依剪切所得的測定值為對象。 Here, the "dynamic viscoelasticity measurement" refers to the measurement of the mechanical properties of the sample by applying a variable (vibration) strain or stress to the sample over time and measuring the resulting stress or strain. The measurement modes include tension/compression, shearing, 3-point bending, etc. The measurement values obtained by shearing are targeted here.
又，損失正切係指藉動態黏彈性測定所得之損失彈性模數除以儲存彈性模數所得的值。於此，損失彈性模數係指施加應力之際，提供的能量轉換為熱而逸 散的黏性成分；儲存彈性模數則指保持內部累積之應力的彈性成分。 In addition, the loss tangent refers to the value obtained by dividing the loss elastic modulus obtained by dynamic viscoelasticity measurement by the storage elastic modulus. Here, the loss of elastic modulus means that when stress is applied, the energy provided is converted into heat and escaped. The loose viscous component; the storage elastic modulus refers to the elastic component that maintains the accumulated internal stress.
再者，溫度分散係指在頻率一定、應變量一定的條件下，即本發明之頻率1Hz、應變0.01%的條件下，一面改變溫度一面求取動態黏彈性之溫度依存性的手法。黏彈性行為的測定方法細節係如後述。 Furthermore, temperature dispersion refers to a method of obtaining the temperature dependence of dynamic viscoelasticity while changing the temperature under the conditions of a constant frequency and a constant amount of strain, that is, under the conditions of the present invention at a frequency of 1 Hz and a strain of 0.01%. The details of the method for measuring the viscoelastic behavior are described later.
更且，前述之至少2個極大值中，較佳的是低溫側的極大值存在於-50℃以上10℃以下的範圍、高溫側的極大值存在於-10℃以上50℃以下的範圍。低溫側的極大值較佳存在於更佳為-50℃以上0℃以下、再更佳為-50℃以上-10℃以下的範圍，高溫側的極大值更佳存在於0℃以上40℃以下的範圍。於此，在-50℃以上50℃以下的範圍若有3個以上的前述極大值時，係以最大的極大值及第2大的極大值當中，處於低溫側者為低溫側的極大值、處於高溫側者為高溫側的極大值。藉由將低溫側的極大值調整於前述範圍，將積層體由被黏物剝離時可得良好的剝離性，因而較佳。又，藉由將高溫側的極大值調整於前述範圍，可得對被黏物之良好的貼合性，因而較佳。 Furthermore, among the aforementioned at least two maximum values, it is preferable that the maximum value on the low temperature side is in the range of -50°C or more and 10°C or less, and the maximum value on the high temperature side is in the range of -10°C or more and 50°C or less. The maximum value on the low temperature side preferably exists in the range of more preferably -50°C or higher and 0°C and more preferably -50°C or higher and -10°C or lower, and the maximum value on the high temperature side is more preferably present in the range of 0°C or higher and 40°C or lower Range. Here, if there are 3 or more of the aforementioned maximum values in the range from -50°C to 50°C, the maximum value and the second maximum value are the maximum value of the low temperature side, and the one on the low temperature side is the maximum value on the low temperature side. Those on the high temperature side are the maximum values on the high temperature side. By adjusting the maximum value on the low temperature side to the aforementioned range, good releasability can be obtained when the laminate is peeled from the adherend, which is preferable. In addition, by adjusting the maximum value on the high temperature side within the aforementioned range, good adhesion to the adherend can be obtained, which is preferable.
此外，前述高溫側的損失正切的極大值較佳為0.1以上1.0以下，更佳為0.3以上1.0以下，特佳為0.5以上0.8以下。高溫側的極大值小於0.1時，貼合於被黏物時的貼合性不足。高溫側的極大值大於1.0時，則貼合性過大，有由被黏物剝除時不易剝離的情形、或對被黏物產生汙染(殘膠)的情形。 In addition, the maximum value of the loss tangent on the high temperature side is preferably 0.1 or more and 1.0 or less, more preferably 0.3 or more and 1.0 or less, and particularly preferably 0.5 or more and 0.8 or less. When the maximum value on the high-temperature side is less than 0.1, the adhesion at the time of adhesion to the adherend is insufficient. When the maximum value on the high temperature side is greater than 1.0, the adhesion is too high, and it may not be easy to peel when peeled off from the adherend, or the adherend may be contaminated (residual glue).
本發明之組成物只要滿足屬構成要件的條件1則不特別限定，可使用丙烯酸系、聚矽氧系等的交聯系、天然橡膠系、合成橡膠系等的非交聯系或者類交聯系(熱塑系)之任一種材料，而基於可回收性觀點，較佳以熱塑性樹脂為主成分。於此，所稱「以熱塑性樹脂為主成分」，係指組成物中之熱塑性樹脂的比例為50質量%以上之意，更佳為70質量%以上。 The composition of the present invention is not particularly limited as long as it satisfies the condition 1 of the constituent requirements. It can use acrylic, silicone, etc. cross-linked, natural rubber, synthetic rubber, etc. non-cross-linked or similar cross-linked (thermal Any material of plastic series), and from the viewpoint of recyclability, it is preferable to use a thermoplastic resin as the main component. Here, the term "contains a thermoplastic resin as the main component" means that the proportion of the thermoplastic resin in the composition is 50% by mass or more, more preferably 70% by mass or more.
本發明之組成物只要滿足屬構成要件的條件1，則可為單一種樹脂、或由包含複數種樹脂的混合物構成，較佳為使用：顯示以與條件1同樣方式測得之損失正切的溫度分散的極大值之溫度不同的、包含至少二種以上之樹脂的混合物的方法。作為於低溫側具有前述損失正切的極大值的樹脂，較佳為在-50℃以上10℃以下，較佳為-50℃以上0℃以下，更佳為-50℃以上-10℃以下的範圍具有極大值的樹脂；作為於高溫側具有前述損失正切的極大值的樹脂，較佳使用在-10℃以上50℃以下，較佳為0℃以上40℃以下的範圍具有極大值的樹脂。 The composition of the present invention may be a single resin or a mixture containing plural resins as long as it satisfies the condition 1 which is a constituent requirement. It is preferably used: the temperature showing the loss tangent measured in the same manner as the condition 1 A method of mixing at least two resins with different maximum dispersion temperatures. As the resin having the maximum value of the aforementioned loss tangent on the low temperature side, it is preferably in the range of -50°C or higher and 10°C or lower, preferably -50°C or higher and 0°C or lower, and more preferably -50°C or higher and -10°C or lower. A resin having a maximum value; as a resin having the aforementioned maximum value of the loss tangent on the high temperature side, a resin having a maximum value in the range of -10°C or higher and 50°C or lower, preferably 0°C or higher and 40°C or lower, is preferably used.
作為於低溫側具有損失正切之極大值的樹脂，可使用該領域所熟知者，可舉出例如苯乙烯系彈性體，具體而言可舉出苯乙烯‧丁二烯共聚物(SBR)、苯乙烯‧異戊二烯‧苯乙烯共聚物(SIS)、苯乙烯‧丁二烯‧苯乙烯共聚物(SBS)等的苯乙烯‧共軛二烯系共聚物及彼等的氫化物，例如氫化苯乙烯‧丁二烯共聚物(HSBR)或苯乙烯‧乙烯‧丁烯‧苯乙烯共聚物(SEBS)、苯乙烯‧異丁烯系共聚物，例如苯乙烯‧異丁烯‧苯乙烯三嵌段 共聚物(SIBS)或苯乙烯‧異丁烯二嵌段共聚物(SIB)、或此等的混合物等。此等苯乙烯系彈性體可僅使用1種，亦可併用2種以上。 As the resin having the maximum value of the loss tangent on the low temperature side, those well-known in the field can be used, for example, styrene-based elastomers, specifically styrene-butadiene copolymer (SBR), benzene Ethylene‧isoprene‧styrene copolymer (SIS), styrene‧butadiene‧styrene copolymer (SBS) and other styrene‧conjugated diene copolymers and their hydrogenated products, such as hydrogenated Styrene‧butadiene copolymer (HSBR) or styrene‧ethylene‧butene‧styrene copolymer (SEBS), styrene‧isobutylene copolymer, such as styrene‧isobutylene‧styrene triblock Copolymer (SIBS) or styrene‧isobutylene diblock copolymer (SIB), or a mixture of these, etc. Only one type of these styrene-based elastomers may be used, or two or more types may be used in combination.
苯乙烯系彈性體的重量平均分子量較佳為50,000~400,000的範圍，更佳為50,000~200,000的範圍。重量平均分子量小於50,000時，黏著層的凝聚力降低，由被黏物剝離時發生殘膠；大於400,000時黏度變高而導致生產性降低。 The weight average molecular weight of the styrene elastomer is preferably in the range of 50,000 to 400,000, more preferably in the range of 50,000 to 200,000. When the weight average molecular weight is less than 50,000, the cohesive force of the adhesive layer is reduced, and residual glue occurs when peeling from the adherend; when the weight average molecular weight is greater than 400,000, the viscosity becomes higher and the productivity is reduced.
苯乙烯系彈性體中的苯乙烯含量較佳為5~30質量%的範圍，更佳為8~20質量%的範圍。苯乙烯含量小於5質量%時，黏著層的凝聚力降低，由被黏物剝離時發生殘膠；大於30質量%時對被黏物的貼合性降低，尤其是對具有凹凸的被黏物的黏著性不足。 The styrene content in the styrene-based elastomer is preferably in the range of 5 to 30% by mass, and more preferably in the range of 8 to 20% by mass. When the styrene content is less than 5% by mass, the cohesive force of the adhesive layer is reduced, and residual glue occurs when peeling from the adherend; when the styrene content is greater than 30% by mass, the adhesion to the adherend is reduced, especially for the uneven adherend. Insufficient adhesion.
作為於高溫側具有損失正切之極大值的樹脂，不特別限定，較佳的是以與屬本發明之組成物之構成要件的條件1同樣方式測得之損失正切的溫度分散的極大值存在於-10℃以上50℃以下，較佳為0℃以上40℃以下的範圍，且其值為0.3以上。極大值更佳為0.5以上，特佳為0.8以上。極大值小於0.3時，本發明之組成物未滿足條件1。亦即，本發明之組成物，於上述損失正切的溫度分散下，在-50℃以上50℃以下的範圍僅顯示1個極大值。 The resin having the maximum value of the loss tangent on the high temperature side is not particularly limited. It is preferable that the maximum value of the temperature dispersion of the loss tangent measured in the same manner as Condition 1 of the constituent elements of the composition of the present invention exists in -10°C or higher and 50°C or lower, preferably 0°C or higher and 40°C or lower, and its value is 0.3 or higher. The maximum value is more preferably 0.5 or more, particularly preferably 0.8 or more. When the maximum value is less than 0.3, the composition of the present invention does not satisfy Condition 1. That is, the composition of the present invention shows only one maximum value in the range of -50°C or more and 50°C or less under the temperature dispersion of the aforementioned loss tangent.
作為於高溫側具有損失正切之極大值的樹脂，可舉出例如低結晶性聚丙烯、非晶性聚丙烯、α-烯烴共聚物等的烯烴系彈性體、或苯乙烯‧乙烯基異戊二 烯‧苯乙烯共聚物、苯乙烯‧丁二烯共聚物及此等的氫化物等的苯乙烯系彈性體。 Examples of resins having a maximum loss tangent on the high temperature side include olefin elastomers such as low crystalline polypropylene, amorphous polypropylene, and α-olefin copolymers, or styrene·vinyl isoprene Styrenic elastomers such as ene·styrene copolymers, styrene·butadiene copolymers, and hydrogenated compounds.
作為前述α-烯烴共聚物，可舉出乙烯‧α-烯烴共聚物、丙烯‧α-烯烴共聚物、4-甲基-1-戊烯‧α-烯烴共聚物等。作為α-烯烴，較佳為碳原子數2~20之直鏈狀或分支狀的α-烯烴，特佳為碳原子數2~10。可舉出例如乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯等，惟可不受此限定地使用。 Examples of the aforementioned α-olefin copolymer include ethylene‧α-olefin copolymer, propylene‧α-olefin copolymer, 4-methyl-1-pentene‧α-olefin copolymer, and the like. The α-olefin is preferably a linear or branched α-olefin having 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc. can be mentioned, but they can be used without limitation.
於高溫側具有損失正切之極大值的樹脂，上述當中較佳使用低結晶性聚丙烯、非晶性聚丙烯、α-烯烴共聚物等的烯烴系彈性體，更佳的是，較佳使用例如如日本特開2013-194132號公報所揭示的4-甲基-1-戊烯‧α-烯烴共聚物。 Resins having a maximum loss tangent on the high temperature side. Among the above-mentioned resins, olefin elastomers such as low crystalline polypropylene, amorphous polypropylene, and α-olefin copolymers are preferably used. More preferably, for example, As disclosed in Japanese Patent Application Laid-Open No. 2013-194132, 4-methyl-1-pentene‧α-olefin copolymer.
一般而言，混合複數種樹脂使用時，係選擇相溶性良好的樹脂們。或者，當相溶性較差時，為提高相溶性而有時使用相溶劑。另一方面，於本發明之組成物中，前述之於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂，較佳組合相溶性低的樹脂們而使用。使用相溶性優良的樹脂們時，本發明之組成物未滿足條件1。亦即，本發明之組成物，於上述損失正切的溫度分散下，在-50℃以上50℃以下的範圍僅顯示1個極大值，而無法達成本發明之目的。 Generally speaking, when mixing multiple types of resins, select resins with good compatibility. Or, when the compatibility is poor, a phase solvent is sometimes used in order to improve the compatibility. On the other hand, in the composition of the present invention, the aforementioned resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side are preferably used in combination with resins with low compatibility. When resins with excellent compatibility are used, the composition of the present invention does not satisfy Condition 1. That is, the composition of the present invention shows only one maximum value in the range of -50°C or more and 50°C or less under the temperature dispersion of the loss tangent mentioned above, which cannot achieve the purpose of the invention.
於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂的含量，若設其合計量為100質量%時，較佳分別調整於10~90質量%的範 圍，更佳為20~80質量%，特佳為30~70質量%。藉由將於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂的含量調整於上述範圍，可理想地調整組成物之損失正切的溫度分散。 The content of the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side, if the total amount is set to 100% by mass, it is better to adjust to the range of 10~90% by mass. The circumference is more preferably 20 to 80% by mass, particularly preferably 30 to 70% by mass. By adjusting the content of the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side within the above range, the temperature dispersion of the loss tangent of the composition can be ideally adjusted.
本發明之組成物可適當組合上述之材料而構成，例如，較佳選擇氫化苯乙烯‧丁二烯共聚物(HSBR)及/或苯乙烯‧乙烯‧丁烯‧苯乙烯共聚物(SEBS)及/或苯乙烯‧異丁烯系共聚物，例如苯乙烯‧異丁烯‧苯乙烯三嵌段共聚物(SIBS)及/或苯乙烯‧異丁烯二嵌段共聚物(SIB)作為於低溫側具有損失正切之極大值的樹脂，選擇低結晶性聚丙烯及/或非晶性聚丙烯及/或α-烯烴共聚物作為於高溫側具有損失正切之極大值的樹脂並加以組合。更佳的是，可舉出使用苯乙烯‧異丁烯系共聚物，例如苯乙烯‧異丁烯‧苯乙烯三嵌段共聚物(SIBS)及/或苯乙烯‧異丁烯二嵌段共聚物(SIB)作為於低溫側具有損失正切之極大值的樹脂、使用4-甲基-1戊烯‧α-烯烴共聚物作為於高溫側具有損失正切之極大值的樹脂之組合。 The composition of the present invention can be formed by appropriately combining the above-mentioned materials. For example, hydrogenated styrene·butadiene copolymer (HSBR) and/or styrene·ethylene·butene·styrene copolymer (SEBS) and / Or styrene‧ isobutylene copolymers, such as styrene‧ isobutylene‧ styrene triblock copolymer (SIBS) and/or styrene‧ isobutylene diblock copolymer (SIB) as having the greatest loss tangent on the low temperature side For resins with high values, low-crystalline polypropylene and/or amorphous polypropylene and/or α-olefin copolymers are selected as resins with the maximum value of loss tangent on the high-temperature side and combined. More preferably, the use of styrene‧isobutylene-based copolymers, such as styrene‧isobutylene‧styrene triblock copolymer (SIBS) and/or styrene‧isobutylene diblock copolymer (SIB) as the A combination of resins with the maximum loss tangent on the low temperature side and 4-methyl-1-pentene‧α-olefin copolymer as the resin with the maximum loss tangent on the high temperature side.
又，當本發明之組成物含有上述之苯乙烯‧異丁烯系共聚物及4-甲基-1-戊烯‧α-烯烴共聚物時，亦可進一步含有苯乙烯‧共軛二烯系共聚物或其氫化物，藉此，將本發明之組成物用於供保護被黏物之表面的積層體之黏著層時，可獲得黏著層表面的外觀優良的積層體。 In addition, when the composition of the present invention contains the above-mentioned styrene‧isobutylene copolymer and 4-methyl-1-pentene‧α-olefin copolymer, it may further contain styrene‧conjugated diene copolymer Or its hydride, whereby when the composition of the present invention is used for the adhesive layer of a laminate for protecting the surface of an adherend, a laminate with an excellent appearance on the surface of the adhesive layer can be obtained.
上述苯乙烯‧共軛二烯系共聚物或其氫化物可使用周知者，較佳使用氫化苯乙烯‧丁二烯共聚物(HSBR)或苯乙烯‧乙烯‧丁烯‧苯乙烯共聚物(SEBS)。 The above-mentioned styrene‧conjugated diene copolymer or its hydrogenated product can use well-known ones, preferably hydrogenated styrene‧butadiene copolymer (HSBR) or styrene‧ethylene‧butene‧styrene copolymer (SEBS ).
本發明之組成物可僅由前述之於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂構成，亦可含有此等以外的其它的成分。組成物中之於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂的合計含量，若設組成物全體為100質量%時，較佳為40質量%以上，更佳為50質量%以上。前述組成物的含量小於30質量%時，將積層體貼合於被黏物時無法獲得充分的貼合性。 The composition of the present invention may be composed only of the aforementioned resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side, or may contain other components other than these. The total content of the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side in the composition is preferably 40% by mass or more when the total composition is 100% by mass. More preferably, it is 50% by mass or more. When the content of the aforementioned composition is less than 30% by mass, sufficient adhesion cannot be obtained when the laminate is bonded to the adherend.
本發明之組成物，除於低溫側具有損失正切之極大值的樹脂及於高溫側具有損失正切之極大值的樹脂以外，在不損及本發明之目的的範圍亦可適當添加其它的成分。 In the composition of the present invention, in addition to the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side, other components may be appropriately added within a range that does not impair the purpose of the present invention.
例如，本發明之組成物亦可含有由以下之(d)、(e)及(f)中選出的至少1種，藉此，可調整黏著力、或良好地控制作為積層體使用時之黏著層表面的外觀。 For example, the composition of the present invention may also contain at least one selected from the following (d), (e) and (f), whereby the adhesive force can be adjusted or the adhesion when used as a laminate can be well controlled The appearance of the layer surface.
(d)由石蠟、烯烴蠟及此等的改質蠟中選出的至少1種蠟 (d) At least one wax selected from paraffin wax, olefin wax and these modified waxes
(e)由石油樹脂、萜烯樹脂、萜烯酚系樹脂、松脂系樹脂、烷基酚系樹脂、二甲苯系樹脂及此等的氫化物中選出的至少1種樹脂 (e) At least one resin selected from petroleum resins, terpene resins, terpene phenol resins, rosin resins, alkylphenol resins, xylene resins, and hydrogenated products of these
(f)由脂肪酸、脂肪酸金屬鹽及脂肪酸醯胺中選出的至少1種潤滑劑。 (f) At least one lubricant selected from fatty acids, fatty acid metal salts, and fatty acid amides.
上述的蠟可使用周知者，可使用石蠟、烯烴蠟及此等的改質蠟。例如為烯烴蠟時，可使用聚乙烯蠟、聚丙烯蠟、聚丁烯蠟或此等的改質蠟。又，本發明所使用的蠟係熔點較佳為70~170℃，更佳為90~160℃，再更佳為110~160℃。熔點小於70度時會發生黏稠；而高於160℃時則成形性較差，不易取用處理。組成物中之蠟的含量，若設組成物全體為100質量%時，較佳為10質量%以下。多於10質量%時，黏著性較差。 Well-known waxes can be used for the above waxes, and paraffin waxes, olefin waxes, and modified waxes such as these can be used. For example, in the case of olefin wax, polyethylene wax, polypropylene wax, polybutene wax, or these modified waxes can be used. In addition, the melting point of the wax used in the present invention is preferably 70 to 170°C, more preferably 90 to 160°C, and still more preferably 110 to 160°C. When the melting point is less than 70 degrees, it will become sticky; when the melting point is higher than 160 degrees, the formability is poor and it is not easy to handle. The content of the wax in the composition is preferably 10% by mass or less when the total composition is 100% by mass. When it is more than 10% by mass, the adhesiveness is poor.
又，作為上述(e)之樹脂，可使用一般用作增黏劑者，例如為石油樹脂時可使用脂肪族系共聚物、芳香族系共聚物、脂肪族‧芳香族系共聚物系或脂環族系共聚物等。上述(e)之樹脂的含量，若設組成物全體為100質量%時，較佳為10質量%以下，更佳為5質量%以下，特佳為3質量%以下。上述(e)之樹脂的含量多於10質量%時，將黏著層以熔融擠出法成型之際，上述(e)之樹脂的一部分昇華而汙染噴嘴，甚至附著於製品上。又，將本發明之積層體貼合於被黏物後，由積層體剝離時會發生殘膠而汙染被黏物。 In addition, as the resin of (e) above, those generally used as tackifiers can be used. For example, in the case of petroleum resins, aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, or lipids can be used. Ring family copolymers, etc. The content of the resin in (e) above is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less when the total composition is 100% by mass. When the content of the resin in (e) is more than 10% by mass, when the adhesive layer is molded by the melt extrusion method, part of the resin in (e) sublimates to contaminate the nozzle and even adhere to the product. In addition, after the laminate of the present invention is attached to an adherend, when peeling from the laminate, adhesive residue may occur and the adherend may be contaminated.
又，上述的潤滑劑可使用周知者，可使用分子中具有至少1個碳數4~60之烷基或烯基，尤為碳數4~30之直鏈烷基或直鏈烯基的脂肪酸、脂肪酸醯胺、脂肪酸金屬鹽，可舉出例如月桂酸、棕櫚酸、硬脂酸、二十二酸、油酸、芥酸等的脂肪酸或此等脂肪酸的金屬鹽或醯胺化合物等。潤滑劑的含量，若設組成物全體為100質量%時，較佳為2質量%以下，更佳為1質量%以下。 當潤滑劑的含量多於2質量%時，會朝表面滲出而汙染被黏物、或黏著性較差。 In addition, the above-mentioned lubricants can be used well-known ones, and fatty acids having at least one alkyl group or alkenyl group with 4 to 60 carbon atoms, especially linear alkyl group or linear alkenyl group with 4 to 30 carbon atoms, can be used in the molecule, Fatty acid amides and fatty acid metal salts include, for example, fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, and erucic acid, or metal salts or amide compounds of these fatty acids. The content of the lubricant is preferably 2% by mass or less, more preferably 1% by mass or less when the total composition is 100% by mass. When the content of the lubricant is more than 2% by mass, it will ooze out to the surface and contaminate the adherend, or the adhesion will be poor.
另外，本發明之組成物亦可添加有別於用作前述之於高溫側具有損失正切之極大值的樹脂者的聚烯烴等的樹脂，藉此，可調整黏著力、或良好地控制作為積層體使用時之黏著層表面的外觀。 In addition, the composition of the present invention may be added with a resin other than polyolefin used as the resin having the maximum value of the loss tangent on the high-temperature side, so that the adhesive force can be adjusted or the build-up can be controlled well. The appearance of the surface of the adhesive layer when the body is used.
作為前述聚烯烴，可舉出低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直鏈狀低密度聚乙烯、低結晶性或者非晶性的乙烯‧α-烯烴共聚物、聚丙烯、丙烯‧乙烯共聚物(隨機共聚物及/或嵌段共聚物)、丙烯‧α-烯烴共聚物、丙烯‧乙烯‧α-烯烴共聚物、聚丁烯、乙烯‧(甲基)丙烯酸乙酯共聚物、乙烯‧(甲基)丙烯酸甲酯共聚物、乙烯‧(甲基)丙烯酸正丁酯共聚物、乙烯‧乙酸乙烯酯共聚物等，此等可單獨使用，亦可併用。此外，作為前述α-烯烴，只要可與丙烯或乙烯共聚合則不特別限定，可舉出例如1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-戊烯、1-庚烯等。上述之聚烯烴當中，更佳為低密度聚乙烯、直鏈狀低密度聚乙烯、乙烯‧α-烯烴共聚物、聚丙烯、丙烯‧α-烯烴共聚物、聚丁烯。前述聚烯烴，若設組成物全體為100質量%時，較佳為50質量%以下，更佳為40質量%以下。 Examples of the aforementioned polyolefins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene·α-olefin copolymers, polypropylene, Propylene‧ethylene copolymer (random copolymer and/or block copolymer), propylene‧α-olefin copolymer, propylene‧ethylene‧α-olefin copolymer, polybutene, ethylene‧ethyl (meth)acrylate copolymer Compounds, ethylene‧(meth)acrylate copolymer, ethylene‧(meth)acrylate copolymer, ethylene‧vinyl acetate copolymer, etc. These can be used alone or in combination. In addition, the α-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, 1-heptene, etc. Among the above-mentioned polyolefins, more preferred are low-density polyethylene, linear low-density polyethylene, ethylene‧α-olefin copolymer, polypropylene, propylene‧α-olefin copolymer, and polybutene. In the aforementioned polyolefin, when the total composition is 100% by mass, it is preferably 50% by mass or less, and more preferably 40% by mass or less.
本發明之組成物，除前述成分以外，亦可含有抗氧化劑、耐候劑、抗靜電劑、黏著亢進防止劑等的添加劑。此等添加劑能以單質使用，亦可併用；就其總含量，若設組成物全體為100質量%時，較佳為3質量% 以下，更佳為2質量%以下。當添加劑的總含量多於3質量%時，則會由黏著層中滲出，而使製品產生瑕疵、或汙染被黏物。 In addition to the aforementioned components, the composition of the present invention may also contain additives such as antioxidants, weathering agents, antistatic agents, and anti-adhesion agents. These additives can be used as a simple substance or can be used in combination; as for the total content, if the total composition is 100% by mass, it is preferably 3% by mass. Hereinafter, it is more preferably 2% by mass or less. When the total content of additives is more than 3% by mass, they will ooze from the adhesive layer, causing defects in the product or contaminating the adherend.
本發明之組成物係丙酮溶解率較佳為5%以下。於本發明中，組成物的丙酮溶解率(S)係依下述方法求得。首先，將以後述之實施例所示方法成型為厚度2mm的組成物與丙酮以1：9的質量比加以混合，在25℃的室內攪拌5小時後，取出殘餘固體成分，在80℃的烘箱中乾燥3小時後測定質量(W1)。其後，由丙酮溶解前之組成物的質量(W0)及上述求得之丙酮不溶成分的質量(W1)，依下式(a)算出丙酮溶解率。 The acetone dissolution rate of the composition of the present invention is preferably 5% or less. In the present invention, the acetone dissolution rate (S) of the composition is obtained by the following method. First, the composition formed into a thickness of 2mm by the method shown in the following examples is mixed with acetone at a mass ratio of 1:9, and after stirring in a room at 25°C for 5 hours, the residual solid content is taken out and placed in an oven at 80°C. The mass (W 1 ) was measured after drying for 3 hours. Thereafter, the acetone dissolution rate was calculated according to the following formula (a) from the mass (W 0 ) of the composition before the acetone dissolution and the mass (W 1 ) of the acetone-insoluble component obtained above.
S=((W0-W1)/W0)×100…(a) S=((W 0 -W 1 )/W 0 )×100…(a)
S：丙酮溶解率(%) S: Acetone dissolution rate (%)
W0：丙酮溶解前之組成物的質量(g) W 0 : The mass of the composition before the acetone is dissolved (g)
W1：丙酮不溶成分的質量(g)。 W 1 : Mass (g) of the acetone-insoluble component.
本發明之積層體係在基材的其中一面具有黏著層的積層體，前述黏著層係包含前述之組成物。以下，就本發明之積層體詳細加以說明。 The laminate system of the present invention has a laminate having an adhesive layer on one side of a substrate, and the adhesive layer includes the aforementioned composition. Hereinafter, the laminate of the present invention will be described in detail.
構成本發明之積層體的基材不特別限定，可使用例如聚烯烴或聚酯等的樹脂。其中，基於生產性或加工適性等觀點，較佳以聚烯烴為主成分。於此，所稱「以聚烯烴為主成分」，係指設基材全體為100質量%時，聚烯烴的比例為50質量%以上之意，更佳為70質量%以上。 The base material constituting the laminate of the present invention is not particularly limited, and resins such as polyolefin or polyester can be used, for example. Among them, it is preferable to use polyolefin as the main component from the viewpoint of productivity, processability, and the like. Here, the term "mainly composed of polyolefin" means that when the total base material is 100% by mass, the proportion of polyolefin is 50% by mass or more, more preferably 70% by mass or more.
作為前述聚烯烴，可舉出例如低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直鏈狀低密度聚乙烯、低結晶性或者非晶性的乙烯．α-烯烴共聚物、聚丙烯、丙烯．乙烯共聚物(隨機共聚物及/或嵌段共聚物)、丙烯．α-烯烴共聚物、丙烯．乙烯．α-烯烴共聚物、乙烯．(甲基)丙烯酸乙酯共聚物、乙烯．(甲基)丙烯酸甲酯共聚物、乙烯．(甲基)丙烯酸正丁酯共聚物、乙烯．乙酸乙烯酯共聚物等。此等可單獨使用，亦可併用。此外，作為前述α-烯烴，只要可與丙烯或乙烯共聚合則不特別限定，可舉出例如1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-戊烯、1-庚烯等。上述之聚烯烴當中，更佳為可得高剛性之聚丙烯、丙烯．乙烯共聚物(隨機共聚物及/或嵌段共聚物)、丙烯．乙烯．α-烯烴共聚物、丙烯．α-烯烴共聚物等的丙烯系材料。 As the aforementioned polyolefin, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene can be cited. α-olefin copolymer, polypropylene, propylene. Ethylene copolymer (random copolymer and/or block copolymer), propylene. α-olefin copolymer, propylene. Ethylene. α-olefin copolymer, ethylene. (Meth) ethyl acrylate copolymer, ethylene. (Meth) methyl acrylate copolymer, ethylene. (Meth) n-butyl acrylate copolymer, ethylene. Vinyl acetate copolymer, etc. These can be used alone or in combination. In addition, the α-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, 1-heptene, etc. Among the above-mentioned polyolefins, polypropylene and propylene with high rigidity are more preferable. Ethylene copolymer (random copolymer and/or block copolymer), propylene. Ethylene. α-olefin copolymer, propylene. Propylene-based materials such as α-olefin copolymers.
本發明之基材主要使用的聚烯烴的熔融流動率(MFR；以230℃、2.16kg之條件測定)較佳為2~30g/10分的範圍，尤以5~30g/10分的範圍為佳。MFR小於2g/10分時，因熔融黏度過高而導致生產性降低。又，MFR大於30g/10分時，基材會脆化而於積層體製造時或使用時不易取用處理。 The melt flow rate (MFR; measured at 230°C and 2.16 kg) of the polyolefin mainly used for the substrate of the present invention is preferably in the range of 2-30 g/10 minutes, especially in the range of 5-30 g/10 minutes good. When the MFR is less than 2g/10 minutes, the melt viscosity is too high, resulting in a decrease in productivity. In addition, when the MFR is greater than 30 g/10 minutes, the base material may become brittle, making it difficult to handle it during the production or use of the laminate.
本發明之基材亦可作成2層構成以上。 The substrate of the present invention can also be made into a two-layer structure or more.
又，構成本發明之基材的組成物中，在不損及作為本發明之積層體之特性的範圍，亦可適當添加潤滑劑、抗氧化劑、耐候劑、抗靜電劑、晶核劑、顏料等的各種添加劑。 In addition, in the composition constituting the substrate of the present invention, lubricants, antioxidants, weathering agents, antistatic agents, crystal nucleating agents, and pigments may be appropriately added within the range that does not impair the characteristics of the laminate of the present invention. Various additives such as.
基材的厚度可配合積層體的要求特性來適當調整，較佳為5~200μm，更佳為10~100μm，特佳為10~80μm。薄於5μm時強度不足，於製造步驟不易運送、或於加工時或使用時發生破裂。厚於200μm時，則薄膜的透明性不足、或生產性降低。 The thickness of the substrate can be appropriately adjusted according to the required characteristics of the laminate, and is preferably 5 to 200 μm, more preferably 10 to 100 μm, and particularly preferably 10 to 80 μm. When it is thinner than 5 μm, the strength is insufficient, and it is difficult to transport in the manufacturing step, or cracks occur during processing or use. When it is thicker than 200 μm, the transparency of the film is insufficient, or the productivity is reduced.
構成本發明之積層體的黏著層較佳使用前述之組成物。 The adhesive layer constituting the laminate of the present invention preferably uses the aforementioned composition.
本發明之黏著層的厚度可配合被黏物的材質、厚度、表面形狀或要求程度來適當調整，較佳為1~20μm，更佳為2~10μm，特佳為2~8μm。黏著層的厚度小於1μm時，無法對被黏物展現充分的黏著力；大於20μm時則黏著力過大、或生產性降低。 The thickness of the adhesive layer of the present invention can be adjusted appropriately according to the material, thickness, surface shape or required degree of the adherend, preferably 1-20 μm, more preferably 2-10 μm, particularly preferably 2-8 μm. When the thickness of the adhesive layer is less than 1 μm, it cannot exhibit sufficient adhesion to the adherend; when it is greater than 20 μm, the adhesion is too high or productivity is reduced.
本發明之積層體係至少具有基材與黏著層的積層體，其較佳之一態樣係在基材之與黏著層相反之一側的面設置脫模層而作成3層積層構成。構成脫模層的材料或厚度、表面形狀，只要基於黏著層的黏著力、積層體製造時或使用時的加工適性等觀點來選擇、調整即可，可採用該領域所熟知之技術。較佳的是，基於良好地控制脫模性觀點，較佳為以含有0.5質量%~10質量%之同時具有多氟烴基及聚氧乙烯基的含氟化合物的丙烯系樹脂為主而構成。 The laminated system of the present invention has at least a laminated body of a base material and an adhesive layer, and a preferred aspect is that a release layer is provided on the surface of the base material on the side opposite to the adhesive layer to form a three-layer laminated structure. The material, thickness, and surface shape of the release layer may be selected and adjusted based on the adhesive force of the adhesive layer, the processing suitability at the time of manufacture or use of the laminate, and the like, and techniques well known in the field can be used. Preferably, from the viewpoint of good control of mold release properties, it is preferably composed mainly of a propylene-based resin containing 0.5% by mass to 10% by mass of a fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group.
作為所述丙烯系樹脂，可為與構成上述基材的丙烯系樹脂相同者或相異者，在將後述之該脫模層的 表面粗糙度粗面化成以Rz表示為3.0μm以上方面，較佳含有至少20質量%以上的丙烯與乙烯及/或α-烯烴的共聚物。當丙烯系聚合物為與乙烯及/或α-烯烴之共聚物時，單體含量愈多，愈可降低該共聚物的熔點，容易實施共擠出、可低溫擠出，因此，就單體含量而言更佳為3~7質量%的範圍。此外，欲對脫模層賦予耐熱性時，亦可適當加以選定，俾能減少所述單體含量，而得到所期望的耐熱性。 The acrylic resin may be the same or different from the acrylic resin constituting the above-mentioned base material, and the mold release layer will be described later. When the surface roughness is roughened to be 3.0 μm or more in terms of Rz, it is preferable to contain at least 20% by mass or more of a copolymer of propylene, ethylene and/or α-olefin. When the propylene-based polymer is a copolymer with ethylene and/or α-olefin, the more the monomer content, the more the melting point of the copolymer can be lowered, the co-extrusion is easy, and the low-temperature extrusion is possible. Therefore, the monomer The content is more preferably in the range of 3 to 7 mass%. In addition, when it is desired to impart heat resistance to the release layer, it can be appropriately selected so that the monomer content can be reduced and the desired heat resistance can be obtained.
又，前述丙烯系樹脂在230℃下的MFR較佳為3~40g/10分的範圍。尤其是，MFR為10~40g/10分的範圍者，可低溫擠出，而且，透過與低密度聚乙烯組合，易將脫模層粗面化，因而更佳。 In addition, the MFR of the propylene-based resin at 230°C is preferably in the range of 3 to 40 g/10 minutes. In particular, those with an MFR in the range of 10-40 g/10 minutes can be extruded at low temperature, and by combining with low-density polyethylene, the release layer can be easily roughened, which is more preferable.
此外，為將脫模層粗面化，較佳含有至少4質量%之與前述丙烯系樹脂缺乏相溶性的高壓法低密度聚乙烯。 In addition, in order to roughen the mold release layer, it is preferable to contain at least 4% by mass of high-pressure process low-density polyethylene lacking compatibility with the aforementioned propylene-based resin.
再者，上述脫模層較佳由含有0.5質量%~10質量%之同時具有多氟烴基及聚氧乙烯基的含氟化合物的丙烯系樹脂構成而成。所述具有多氟烴基及聚氧乙烯基的含氟化合物，例如作為單體(a)可舉出具有碳數1~18之全氟烷基的(甲基)丙烯酸酯等，可將後述之單體(b)、單體(c)之具有聚氧乙烯基的(甲基)丙烯酸酯等共聚合而得。 Furthermore, the mold release layer is preferably made of a propylene-based resin containing 0.5% by mass to 10% by mass of a fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group. The fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group, for example, monomer (a) includes (meth)acrylate having a perfluoroalkyl group having 1 to 18 carbon atoms, etc., which may be described later It is obtained by copolymerization of monomer (b) and (meth)acrylate having polyoxyethylene group of monomer (c).
作為上述單體(a)之全氟烷基較佳為碳數1~18，尤以1~6者為更佳。所述全氟烷基可為直鏈狀及分支狀任一種。此等可僅單獨使用1種，亦可組合使用2種以上。 The perfluoroalkyl group as the above-mentioned monomer (a) preferably has 1 to 18 carbon atoms, and more preferably 1 to 6 carbon atoms. The perfluoroalkyl group may be either linear or branched. These may be used individually by 1 type, and may be used in combination of 2 or more types.
所述具有全氟烷基的(甲基)丙烯酸酯係由共榮社化學(股)等販售，或者亦能以市售之含氟化合物為原料，以既知之方法來合成。 The (meth)acrylate having a perfluoroalkyl group is sold by Kyoeisha Chemical Co., Ltd., etc., or it can be synthesized by a known method using a commercially available fluorine-containing compound as a raw material.
含有聚氧乙烯基的單體(b)，較佳為具有氧乙烯單元(-CH2-CH2-O-)以1~30個接連而成的結構者，尤以該單元有1~20個者為佳。此外，該鏈中亦可含有氧丙烯單元(-CH2-CH(CH3)-O-)。作為較佳實例，可例示氧乙烯單元為8個的聚乙二醇單甲基丙烯酸酯等。單體(b)可僅單獨取1種、或組合2種以上。 The polyoxyethylene group-containing monomer (b) preferably has a structure in which 1 to 30 oxyethylene units (-CH 2 -CH 2 -O-) are successively connected, especially the unit has 1 to 20 Individual is better. In addition, the chain may contain an oxypropylene unit (-CH 2 -CH(CH 3 )-O-). As a preferable example, polyethylene glycol monomethacrylate having 8 oxyethylene units and the like can be exemplified. The monomer (b) may be used alone or in combination of two or more kinds.
又，作為含有聚氧乙烯基的另一個其它的單體(c)，係具有氧乙烯單元以1~30個接連而成的結構，且於兩末端具有雙鍵的二(甲基)丙烯酸酯，作為較佳之具體實例，可舉出鏈數為8的聚乙二醇二甲基丙烯酸酯等。所述單體(c)亦可僅單獨取1種、或組合2種以上。 In addition, as another other monomer (c) containing polyoxyethylene group, it is a di(meth)acrylate having a structure in which 1-30 oxyethylene units are successively connected, and having double bonds at both ends As a preferred specific example, polyethylene glycol dimethacrylate with a chain number of 8 can be cited. The monomer (c) may be used alone or in combination of two or more kinds.
就所述單體(a)、單體(b)、單體(c)各者的比例而言，較佳的是單體(a)為1~80質量%、單體(b)為1~80質量%、單體(c)為1~50質量%。 In terms of the ratio of each of the monomer (a), monomer (b), and monomer (c), it is preferable that the monomer (a) is 1 to 80% by mass, and the monomer (b) is 1 ~80% by mass, and monomer (c) is 1-50% by mass.
此外，對於上述具有多氟烴基及聚氧乙烯基的含氟化合物，除上述3種單體外，亦能以小於50質量%的範圍共聚合可與此等共聚合的單體。作為所述單體，可舉出亞甲基、乙酸乙烯酯、氯乙烯、氟乙烯、鹵乙烯、苯乙烯、甲基苯乙烯、(甲基)丙烯酸及其酯、(甲基)丙烯醯胺單體、(甲基)烯丙基單體等。 In addition, for the above-mentioned fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group, in addition to the above three monomers, monomers copolymerizable with these can also be copolymerized in a range of less than 50% by mass. Examples of the monomer include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methyl styrene, (meth)acrylic acid and its esters, and (meth)acrylamide Monomers, (meth)allyl monomers, etc.
用於使用上述單體來獲得上述具有多氟烴基及聚氧乙烯基的含氟化合物之聚合方式，可為塊狀聚 合、溶液聚合、懸浮聚合、乳化聚合任一種，而且除熱聚合以外，還可採用光聚合、能量線聚合。 The polymerization method used to use the above monomers to obtain the above fluorine-containing compounds with polyfluorocarbon groups and polyoxyethylene groups, which can be bulk poly Any one of polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and besides thermal polymerization, photopolymerization and energy ray polymerization can also be used.
作為聚合起始劑，可使用既有之有機偶氮化合物、過氧化物、過硫酸鹽等。 As the polymerization initiator, existing organic azo compounds, peroxides, persulfates, etc. can be used.
本發明所使用之該含氟化合物的重量平均分子量較佳為1,000~100,000，尤以5,000~20,000為佳。重量平均分子量的調整可藉由硫醇(thiol)、硫醇(mercaptan)、α-甲基苯乙烯等的聚合鏈轉移劑來調整。 The weight average molecular weight of the fluorine-containing compound used in the present invention is preferably 1,000 to 100,000, especially 5,000 to 20,000. The weight average molecular weight can be adjusted with a polymer chain transfer agent such as thiol, mercaptan, and α-methylstyrene.
又，本發明之脫模層中的該含氟化合物的比例較佳為0.5質量%~10質量%。小於0.5質量%時易發生與黏著層的黏連，而不易獲得所期望的收捲力。又，欲使其含有大於10質量%時，由於對樹脂的溶解度較低，不易均勻地攪拌，此外，在熔融擠出時，構成脫模層用之丙烯系樹脂會受到該含氟化合物的影響，沿擠出螺桿部滑動，而不易均勻地排出。 In addition, the ratio of the fluorine-containing compound in the release layer of the present invention is preferably 0.5% by mass to 10% by mass. When it is less than 0.5% by mass, adhesion to the adhesive layer is likely to occur, and it is difficult to obtain the desired winding force. In addition, if it is desired to contain more than 10% by mass, it is difficult to uniformly stir because of its low solubility in the resin. In addition, during melt extrusion, the propylene-based resin that constitutes the release layer will be affected by the fluorine-containing compound. , Sliding along the extrusion screw part, not easy to uniformly discharge.
此外，本發明之脫模層，除所述含氟化合物外，更佳同時含有0.1質量%~10質量%之平均粒徑1~20μm的無機或有機粒子。基於平滑性及黏連性觀點，特佳為所述無機或有機粒子的平均粒徑為3~15μm的較大之粒徑者。 In addition, the release layer of the present invention, in addition to the fluorine-containing compound, preferably contains 0.1% to 10% by mass of inorganic or organic particles with an average particle diameter of 1 to 20 μm. From the viewpoint of smoothness and adhesion, it is particularly preferable that the average particle diameter of the inorganic or organic particles is a larger particle diameter of 3-15 μm.
作為所述無機粒子，除二氧化矽以外，尚可舉出碳酸鈣、碳酸鎂、氧化鈦、黏土、滑石、氫氧化鎂、氫氧化鋁、沸石等，其中更佳為二氧化矽。 As the inorganic particles, in addition to silica, calcium carbonate, magnesium carbonate, titanium oxide, clay, talc, magnesium hydroxide, aluminum hydroxide, zeolite, etc. can be cited, and among them, silica is more preferred.
作為有機粒子，可舉出聚苯乙烯或聚甲基丙烯酸甲酯等。 As the organic particles, polystyrene, polymethyl methacrylate, and the like can be mentioned.
藉由上述含氟化合物、無機或有機粒子與後述之脫模層的表面粗糙度的相乘效果，不易發生黏連，更容易獲得良好的捲出性。 Due to the synergistic effect of the above-mentioned fluorine-containing compound, inorganic or organic particles and the surface roughness of the release layer described later, blocking is less likely to occur, and it is easier to obtain good roll-out properties.
本發明之脫模層的表面粗糙度以十點平均粗糙度(Rz)表示較佳為3μm以上。Rz小於3μm時，在積層體的製造步驟中捲繞成捲筒狀時，容易產生皺褶，而致使品質劣化。所述表面粗糙度能以對作為主體的丙烯系樹脂少量混合添加如前述缺乏相溶性的乙烯系樹脂之方法等來達成。 The surface roughness of the release layer of the present invention is preferably 3 μm or more in terms of ten-point average roughness (Rz). When Rz is less than 3 μm, when the layered body is wound into a roll shape in the manufacturing step of the layered product, wrinkles are likely to occur, and the quality is deteriorated. The surface roughness can be achieved by the method of mixing and adding a small amount of propylene-based resin as the main body, such as the aforementioned poorly compatible ethylene-based resin.
其次就本發明之積層體的製造方法加以說明。 Next, the manufacturing method of the laminate of the present invention will be described.
本發明之積層體的製造方法不特別限定，例如為基材、黏著層、脫模層之3層積層構成時，可舉出將構成各者的樹脂組成物由個別的擠出機中熔融擠出，使其在噴嘴內積層一體化的所謂的共擠出法；或將上述基材、黏著層、脫模層各自個別地熔融擠出後，藉由層合法予以積層的方法等，而基於生產性觀點較佳以共擠出法來製造。構成各層的材料，能以亨舍爾混合機等各自加以混合後使用，亦可預先將各層的全部或一部分的材料混煉後使用。就共擠出法而言，可採用充氣法、T模法等周知之方法，而基於厚度精確度優良或控制表面形狀觀點，特佳為採T模法的熱熔融共擠出法。 The manufacturing method of the laminate of the present invention is not particularly limited. For example, when it is a three-layer laminate structure of a base material, an adhesive layer, and a release layer, the resin composition constituting each of them may be melt-extruded in a separate extruder. The so-called co-extrusion method in which the layers are integrated in the nozzle; or the method in which the above-mentioned base material, adhesive layer, and release layer are individually melt-extruded and then laminated by the laminating method, etc., based on From the viewpoint of productivity, it is preferable to manufacture by a coextrusion method. The materials constituting each layer can be used after being individually mixed with a Henschel mixer or the like, or all or part of the materials of each layer can be kneaded in advance and used. As far as the co-extrusion method is concerned, well-known methods such as the inflation method and the T-die method can be used, and the hot-melt co-extrusion method using the T-die method is particularly preferred from the viewpoint of excellent thickness accuracy or control of the surface shape.
由本發明之組成物構成的積層體可作為防止合成樹脂板、金屬板、玻璃板等的製造、加工、運送時的劃傷、防止髒汙附著用的表面保護薄膜使用，特別適用於具有凹凸的被黏物。例如使用於屬包含合成樹脂之顯示器用構件的擴散板或稜鏡片等，其中由本發明之組成物構成的積層體特佳使用於稜鏡片的表面保護。 The laminate composed of the composition of the present invention can be used as a surface protective film to prevent scratches during the manufacture, processing, and transportation of synthetic resin plates, metal plates, glass plates, etc., and to prevent dirt adhesion. It is especially suitable for uneven surfaces. Stickies. For example, it is used for a diffuser or a sheet of a display member containing a synthetic resin. Among them, a laminate made of the composition of the present invention is particularly suitable for the surface protection of a sheet.
由本發明之組成物構成的積層體所保護的稜鏡片，係於片體的單面，以三角柱狀的稜鏡其稜線為外表面的方式與片體表面平行地配置者。構成稜鏡的材料不特別限定，係使用具透光性之樹脂，可舉出例如丙烯酸系樹脂或聚碳酸酯等。稜鏡之相鄰稜線間的距離較佳為10~1,000μm，更佳為10~300μm。稜鏡的高度(三角柱的底邊起至稜線之垂線的長度)較佳為5~200μm，更佳為10~100μm。又，由本發明所保護的稜鏡片，可僅由相同形狀的稜鏡構成，亦可由2種以上之不同形狀的稜鏡構成。若由不同形狀的稜鏡構成時，有例如高度不同的大小稜鏡逐一交互地配置、或1個大的稜鏡與複數個小的稜鏡交互地配置的情形，可視目的適當設計。 The lamella sheet protected by the layered body composed of the composition of the present invention is attached to a single surface of the sheet body, and is arranged in parallel with the surface of the sheet body in such a way that the ridgeline of the triangular columnar lamella body is the outer surface. The material constituting the scallop is not particularly limited, and a light-transmitting resin is used. For example, acrylic resin or polycarbonate can be mentioned. The distance between adjacent ridges of the ridge is preferably 10 to 1,000 μm, more preferably 10 to 300 μm. The height (the length from the base of the triangular column to the vertical line of the ridge line) of the ridge is preferably 5 to 200 μm, more preferably 10 to 100 μm. In addition, the scallop sheet protected by the present invention may be composed of only scallops of the same shape, or two or more types of scallops with different shapes. If it is composed of different shapes of fins, for example, large and small fins with different heights are alternately arranged one by one, or one large fin and a plurality of small fins are alternately arranged, and it can be designed appropriately depending on the purpose.
又，由本發明之積層體所保護的稜鏡片，其稜鏡部分的壓縮強度較佳為3,000mN/mm以下，更佳為2,000mN/mm以下，特佳為1,000mN/mm以下，最佳為500mN/mm以下。此外，於本發明中，稜鏡的壓縮強度係指以後述之實施例記載的方法所算出的值。本發明之積層體對上述稜鏡顯示出良好的貼合性，可特佳地使用。 In addition, the compressive strength of the scalloped sheet protected by the laminate of the present invention is preferably 3,000 mN/mm or less, more preferably 2,000 mN/mm or less, particularly preferably 1,000 mN/mm or less, and most preferably Below 500mN/mm. In addition, in the present invention, the compressive strength of the ridge refers to the value calculated by the method described in the examples described later. The laminate of the present invention shows good adhesion to the above-mentioned scallops, and can be used particularly well.
以下，基於實施例對本發明更具體地加以說明，惟本發明不受此等實施例所限定。此外，各種物性的測定及評定係根據以下方法實施。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited by these examples. In addition, the measurement and evaluation of various physical properties were carried out according to the following methods.
以既定的混合比摻混實施例1~9及比較例1~3所示之組成物，利用東洋精機製作所製LABO PLASTOMILL 100MR3，以溫度200℃、旋轉數20rpm進行混煉15分鐘。接著，將所得混煉物熔融成型為厚度2mm，利用TA Instruments公司製流變儀AR2000ex，在溫度-80~120℃、升溫速度3℃/分、頻率1Hz、應變0.01%下，以剪切模式評定組成物的黏彈性。由所得結果，確認-50℃以上50℃以下之損失正切的溫度分散之極大值的數目。又，當前述極大值為2個以上時，求取高溫側的極大值。 The compositions shown in Examples 1 to 9 and Comparative Examples 1 to 3 were blended at a predetermined mixing ratio, and kneading was performed for 15 minutes using LABO PLASTOMILL 100MR3 manufactured by Toyo Seiki Seisakusho at a temperature of 200°C and a rotation speed of 20 rpm. Next, the obtained kneaded material was melt-molded to a thickness of 2mm, and the shear mode was used at a temperature of -80 to 120°C, a heating rate of 3°C/min, a frequency of 1 Hz, and a strain of 0.01% using the AR2000ex rheometer manufactured by TA Instruments. Evaluate the viscoelasticity of the composition. From the obtained results, the number of the maximum value of the temperature dispersion of the loss tangent at -50°C or higher and 50°C or lower was confirmed. In addition, when the aforementioned maximum values are two or more, the maximum value on the high temperature side is obtained.
將以與上述(1)同樣方式獲得之厚度2mm的組成物與丙酮以1：9的質量比加以混合，在25℃的室內攪拌5小時後，取出殘餘固體成分，在80℃的烘箱中乾燥3小時後測定質量(W1)。其後，由丙酮溶解前之組成物的質量(W0)及上述求得之丙酮不溶成分的質量(W1)，依下式(a)算出丙酮溶解率。 The composition with a thickness of 2 mm obtained in the same manner as in (1) above was mixed with acetone at a mass ratio of 1:9, stirred in a room at 25°C for 5 hours, and then the residual solid content was taken out and dried in an oven at 80°C. The mass (W 1 ) is measured after 3 hours. Thereafter, the acetone dissolution rate was calculated according to the following formula (a) from the mass (W 0 ) of the composition before the acetone dissolution and the mass (W 1 ) of the acetone-insoluble component obtained above.
S=((W0-W1)/W0)×100…(a) S=((W 0 -W 1 )/W 0 )×100…(a)
S：丙酮溶解率(%) S: Acetone dissolution rate (%)
W0：丙酮溶解前之組成物的質量(g) W 0 : The mass of the composition before the acetone is dissolved (g)
W1：丙酮不溶成分的質量(g)。 W 1 : Mass (g) of the acetone-insoluble component.
利用島津製作所製之微小壓縮試驗機MCTW-500，在負荷速度41mN/s、室溫23℃的室內以鑽石製平面壓件(
將下述之實施例1’~9’、2”及比較例1’~3’中所得的積層體，利用輥壓機(安田精機製作所(股)特殊壓接輥)，以0.35MPa之條件予以貼合於各實施例或比較例所示之既定的稜鏡片上。 The laminates obtained in the following Examples 1'to 9', 2" and Comparative Examples 1'to 3'were used with a roll press (Ysuda Seiki Seisakusho Co., Ltd. special pressure bonding roll) under the condition of 0.35 MPa It was pasted on the predetermined 稜鏡 sheet shown in each example or comparative example.
針對上述(4)所得之試樣，觀察在貼合後隨即於25℃的室內保存1週後的貼合狀態，就貼合性以下述5階段加以評定。 For the sample obtained in (4) above, the bonding state after being stored in a room at 25°C for 1 week immediately after bonding was observed, and the bonding performance was evaluated in the following five stages.
5：貼合後不久、保存1週後均全面地貼合。 5: It is fully bonded shortly after bonding and after 1 week of storage.
4：貼合後不久係全面地貼合，但保存1週後端部有些許剝離。 4: Soon after bonding, it was fully bonded, but the rear end was slightly peeled off after storage for 1 week.
3：貼合後不久、1週後，端部均有些許剝離。 3: Soon after bonding and one week later, the ends were slightly peeled off.
2：貼合後不久，貼合面的1/2以上發生剝落。 2: Soon after bonding, more than 1/2 of the bonding surface peeled off.
1：貼合後不久，貼合面的全面發生剝落。 1: Soon after bonding, peeling occurred on the entire bonding surface.
將上述(4)所得之試樣，在50℃的熱風乾燥機中、10g/cm2的負載下保存3日後，剝離積層體，以目視確認對稜鏡片表面的汙染性，以如下3階段加以評定。 The sample obtained in (4) above was stored in a hot-air dryer at 50°C under a load of 10g/cm 2 for 3 days. The laminate was peeled off, and the contamination to the surface of the sheet was visually confirmed. assessment.
5：全體未看出汙染 5: No pollution is seen in all
3：僅有一小部分看出汙染 3: Only a small part sees pollution
1：可明確看出汙染。 1: Pollution can be clearly seen.
對下述之實施例1’~9’、2”及比較例1’~3’所得之積層體的黏著層，利用小坂研究所(股)製之高精度微細形狀測定器(SURFCORDER ET4000A)，依據JIS B0601-1994，以朝薄膜橫向2mm、長度方向(機械方向)10μm的間隔測定21次以進行三維解析，求出算術平均粗糙度(Ra)，以如下3階段加以評定。此外，使用觸針尖端半徑2.0μm的鑽石針，以測定力100μN、截距0.8mm進行測定。又，目視觀察黏著薄膜的外觀的結果，下述評定的數值愈大，亦即算術平均粗糙度(Ra)愈小，則黏著層表面的粗糙愈少，為外觀良好之結果。 For the adhesion layers of the laminates obtained in the following Examples 1'~9', 2" and Comparative Examples 1'~3', the high-precision fine shape measuring device (SURFCORDER ET4000A) manufactured by Kosaka Laboratory Co., Ltd. was used, According to JIS B0601-1994, measurement was performed 21 times at intervals of 2 mm in the transverse direction of the film and 10 μm in the longitudinal direction (machine direction) for three-dimensional analysis, and the arithmetic average roughness (Ra) was calculated, and evaluated in the following three stages. In addition, touch A diamond needle with a needle tip radius of 2.0 μm was measured with a measuring force of 100 μN and an intercept of 0.8 mm. In addition, as a result of visual observation of the appearance of the adhesive film, the greater the value of the following evaluation, the greater the arithmetic average roughness (Ra) Smaller, the less rough the surface of the adhesive layer, which is the result of good appearance.
5：Ra<0.3μm 5: Ra<0.3μm
3：0.3μm≦Ra<0.7μm 3: 0.3μm≦Ra<0.7μm
1：Ra≧0.7μm。 1: Ra≧0.7μm.
如實施例1~9、比較例1~3所示製備以下之組成物A~I、X~Z之材料，以上述(1)、(2)之方法評定黏彈性及丙酮溶解率。將結果示於表1。 Prepare the materials of the following compositions A~I, X~Z as shown in Examples 1-9 and Comparative Examples 1~3, and evaluate the viscoelasticity and acetone dissolution rate by the methods (1) and (2) above. The results are shown in Table 1.
組成物A：作為於低溫側具有損失正切之極大值的樹脂係使用80質量%的SEBS(Asahi Kasei Chemicals製Tuftec H1052)，作為於高溫側具有損失正切之極大值的樹脂係使用20質量%的4-甲基-1-戊烯‧丙烯共聚物。此外，前述4-甲基-1-戊烯‧丙烯共聚物其共聚合比率係4-甲基-1-戊烯為73莫耳%、丙烯為27莫耳%；又，使用以與上述(1)所記載之黏著層的黏彈性同樣方式測定所得之損失正切的溫度分散於30℃顯示極大，且其值為2.9者。 Composition A: 80% by mass SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) was used as the resin system with the maximum loss tangent on the low temperature side, and 20% by mass as the resin system with the maximum loss tangent on the high temperature side 4-methyl-1-pentene‧propylene copolymer. In addition, the copolymerization ratio of the aforementioned 4-methyl-1-pentene‧propylene copolymer is 73 mol% of 4-methyl-1-pentene and 27 mol% of propylene; 1) The temperature dispersion of the loss tangent obtained by measuring the viscoelasticity of the adhesive layer in the same manner at 30°C shows a maximum value, and its value is 2.9.
組成物B：於低溫側具有損失正切之極大值的樹脂係使用40質量%的SEBS(Asahi Kasei Chemicals 製Tuftec H1052)與40質量%的苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)，作為於高溫側具有損失正切之極大值的樹脂係使用20質量%的與組成物A所使用者同樣的4-甲基-1-戊烯‧丙烯共聚物。 Composition B: A resin system with a maximum loss tangent on the low temperature side uses 40% by mass SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) and 40% by mass styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) As the resin with the maximum value of the loss tangent on the high temperature side, 20% by mass of the same 4-methyl-1-pentene·propylene copolymer as used for composition A was used.
組成物C：除將SEBS(Asahi Kasei Chemicals 製Tuftec H1052)的比率設為20質量%、將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為50質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為30質量%以外，係採用組成物B相同者。 Composition C: Except that the ratio of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) was set to 20% by mass, the ratio of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was set to 50% by mass, and the ratio of 4- The ratio of the methyl-1-pentene‧propylene copolymer is not set to 30% by mass, and the same composition B is used.
組成物D：除將SEBS(Asahi Kasei Chemicals製Tuftec H1052)的比率設為0質量%、將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為50質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為50質量%以外，係採用與組成物B相同者。 Composition D: Except that the ratio of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) was set to 0% by mass, the ratio of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was set to 50% by mass, and the ratio of 4- Except that the ratio of the methyl-1-pentene‧propylene copolymer was set to 50% by mass, the same as that of the composition B was used.
組成物E：於低溫側具有損失正切之極大值的樹脂係使用10質量%的SEBS(Asahi Kasei Chemicals製Tuftec H1052)與55質量%的苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)，作為於高溫側具有損失正切之極大值的樹脂係使用30質量%的與組成物A所使用者同樣的4-甲基-1-戊烯‧丙烯共聚物，作為增黏劑係使用5質量%的氫化萜烯酚(YASUHARA CHEMICAL製YS Polyster TH130)。 Composition E: The resin system with the maximum value of loss tangent on the low temperature side uses 10% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) and 55% by mass of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) , As the resin system with the maximum loss tangent on the high temperature side, 30% by mass of the same 4-methyl-1-pentene‧propylene copolymer as used for composition A was used, and 5 mass% as the tackifier system % Hydrogenated terpene phenol (YS Polyster TH130 manufactured by YASUHARA CHEMICAL).
組成物F：除將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為70質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為30質量%以外，係採用與組成物D相同者。 Composition F: Except that the ratio of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was 70% by mass, and the ratio of 4-methyl-1-pentene‧propylene copolymer was 30% by mass Otherwise, the same as the composition D was used.
組成物G：除將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為67質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為30質量%，並進一步使用3質量%之作為蠟的聚丙烯蠟(三洋化成製VISCOL 550P)以外，係採用與組成物D相同者。 Composition G: Except that the ratio of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was 67% by mass, and the ratio of 4-methyl-1-pentene‧propylene copolymer was 30% by mass , And further used 3% by mass of polypropylene wax (VISCOL 550P manufactured by Sanyo Chemical Co., Ltd.) as the wax, and the same as the composition D was used.
組成物H：除將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為65質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為30質量%，並進一步使用5質量%之作為增黏劑的氫化萜烯酚(YASUHARA CHEMICAL製YS Polyster TH130)以外，係採用與組成物D相同者。 Composition H: Except that the ratio of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was set to 65% by mass, and the ratio of 4-methyl-1-pentene·propylene copolymer was set to 30% by mass , And further used 5% by mass of hydrogenated terpene phenol (YS Polyster TH130 manufactured by Yasuhara Chemical) as a tackifier, and the same as composition D was used.
組成物I：除將苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)的比率設為69.8質量%、將4-甲基-1-戊烯‧丙烯共聚物的比率設為30質量%，並進一步使用0.2質量%之作為潤滑劑的硬脂酸鈣以外，係採用與組成物D相同者。 Composition I: Except that the ratio of styrene·isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was set to 69.8% by mass, and the ratio of 4-methyl-1-pentene·propylene copolymer was set to 30% by mass , And further use 0.2% by mass of calcium stearate as a lubricant, and use the same as composition D.
組成物X：僅使用苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)。 Composition X: Only styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) was used.
組成物Y：使用70質量%的苯乙烯‧異丁烯系嵌段共聚物(Kaneka製SIBSTAR 062M)、30質量%之作為增黏劑的氫化萜烯酚(YASUHARA CHEMICAL製YS Polyster TH130)。 Composition Y: 70% by mass of styrene-isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) and 30% by mass of hydrogenated terpene phenol (YS Polyster TH130 manufactured by YASUHARA CHEMICAL) as a thickener were used.
組成物Z：使用95質量%的4-甲基-1-戊烯‧丙烯共聚物、5質量%之作為增黏劑的氫化萜烯酚(YASUHARA CHEMICAL製YS Polyster TH130)。 Composition Z: 95% by mass of 4-methyl-1-pentene‧propylene copolymer and 5% by mass of hydrogenated terpene phenol (YS Polyster TH130 manufactured by Yasuhara Chemical) as a thickener were used.
如下述之實施例及比較例所示，作成積層體，並實施評定。將評定結果示於表2。 As shown in the following Examples and Comparative Examples, laminates were prepared and evaluated. The evaluation results are shown in Table 2.
如下準備各層之構成樹脂。 The constituent resins of each layer are prepared as follows.
黏著層：使用實施例1所示之組成物A。 Adhesive layer: The composition A shown in Example 1 was used.
基材：使用在230℃測得之MFR為5g/10分的市售均聚丙烯。 Substrate: A commercially available homopolypropylene with an MFR of 5 g/10 min measured at 230°C was used.
脫模層：添加45質量%之與基材所使用者相同的均聚丙烯、24質量%之在230℃測得之MFR為35g/10分的丙烯-乙烯‧隨機共聚物(乙烯含量5質量%)、6質量%之在190℃測得之MFR為2g/10分的密度0.92g/cm3的低密度聚乙烯，預先準備在90質量%的上述均聚丙烯中包含4質量%之平均粒徑11μm的二氧化矽、6質量%之具有多氟烴基及聚氧乙烯基的含氟化合物的混合組成物作為母料，取25質量%以亨舍爾混合機均勻混合之。 Release layer: Add 45% by mass of homopolypropylene which is the same as the user of the base material, 24% by mass of propylene-ethylene‧random copolymer with an MFR of 35g/10 min measured at 230°C (ethylene content 5 mass) %), 6% by mass of low-density polyethylene with a density of 0.92g/cm 3 and MFR measured at 190°C of 2g/10 minutes, pre-prepared to include an average of 4% by mass in 90% by mass of the above-mentioned homopolypropylene A mixed composition of 11μm in particle size of silicon dioxide and 6 mass% of fluorine-containing compounds having polyfluorocarbon groups and polyoxyethylene groups is used as a masterbatch, and 25 mass% is uniformly mixed with a Henschel mixer.
於此，具有多氟烴基及聚氧乙烯基的含氟化合物係使用：以作為單體(a)的C6F13之丙烯酸全氟烷基酯(CH2=CHCOOC2H4C6F13)取25質量%、作為單體(b)的氧乙烯重複單元為8個的聚乙二醇單丙烯酸酯{CH2=CHCOO(CH2CH2O)8H}取50質量%、及作為單體(c)的氧乙烯重複單元為8個的聚乙二醇二甲基丙烯酸酯{CH2=C(CH3)COO(CH2CH2O)8COC(CH3)=CH2}取25質量%的比例，溶劑使用三氟甲苯，作為聚合起始劑使用 2,2’-偶氮雙(2,4-二甲基戊腈)，且作為鏈轉移劑使用月桂硫醇，在氮氣氣流下，一面攪拌一面使其在60℃下進行5小時聚合，其後，在甲醇中進行沉澱‧過濾後，實施減壓乾燥而成者。 Here, the fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group is used: as the monomer (a), a C 6 F 13 perfluoroalkyl acrylate (CH 2 =CHCOOC 2 H 4 C 6 F 13 ) Take 25% by mass and take the polyethylene glycol monoacrylate {CH 2 =CHCOO(CH 2 CH 2 O) 8 H} with 8 oxyethylene repeating units as the monomer (b) to take 50% by mass, and The oxyethylene repeating unit of monomer (c) is polyethylene glycol dimethacrylate {CH 2 =C(CH 3 )COO(CH 2 CH 2 O) 8 COC(CH 3 )=CH 2 } Take 25% by mass, use trifluorotoluene as the solvent, 2,2'-azobis(2,4-dimethylvaleronitrile) as the polymerization initiator, and lauryl mercaptan as the chain transfer agent. Under a nitrogen stream, it was polymerized at 60°C for 5 hours while stirring, and then precipitated in methanol, filtered, and dried under reduced pressure.
其次，將各層之構成樹脂投入至包含
除黏著層使用實施例2所示之組成物B以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition B shown in Example 2 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除使用稜鏡壓縮強度為1,650mN/mm的稜鏡片以外，係以與實施例2’同樣的方式，作成積層體，並實施評定。 Except for the use of a scallop sheet with a compressive strength of 1,650 mN/mm, a laminate was formed in the same manner as in Example 2'and evaluated.
除黏著層使用實施例3所示之組成物C以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition C shown in Example 3 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例4所示之組成物D以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition D shown in Example 4 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例5所示之組成物E以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition E shown in Example 5 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例6所示之組成物F以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition F shown in Example 6 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例7所示之組成物G以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition G shown in Example 7 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例8所示之組成物H以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition H shown in Example 8 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用實施例9所示之組成物I以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition I shown in Example 9 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用比較例1所示之組成物X以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition X shown in Comparative Example 1 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用比較例2所示之組成物Y以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition Y shown in Comparative Example 2 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
除黏著層使用比較例3所示之組成物Z以外，係以與實施例1’同樣的方式，作成積層體，並實施評定。 Except that the composition Z shown in Comparative Example 3 was used for the adhesive layer, a laminate was formed in the same manner as in Example 1'and evaluated.
滿足本發明之要件的實施例1’~9’及2”，其黏著特性、汙染性、外觀優良；另一方面，未滿足本發明之要件的比較例1’~3’，其黏著特性、汙染性、外觀的平衡較差。 Examples 1'to 9'and 2" that meet the requirements of the present invention have excellent adhesion characteristics, staining properties, and appearance; on the other hand, Comparative Examples 1'to 3'that do not meet the requirements of the present invention have excellent adhesion properties, Poor balance between pollution and appearance.
本發明之組成物及積層體，非僅可使用作為供防止表面具有凹凸的被黏物之傷痕或髒汙的表面保護薄膜，亦可較佳地使用作為包含合成樹脂、金屬、玻璃等各種素材之各式各樣製品的表面保護薄膜用途。 The composition and laminate of the present invention can be used not only as a surface protective film for preventing scratches or dirt on adherends with uneven surfaces, but also as various materials including synthetic resin, metal, glass, etc. The use of surface protection film for various products.
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| CN106795374B (en) | 2020-09-15 |
| KR102323855B1 (en) | 2021-11-09 |
| KR20170063508A (en) | 2017-06-08 |
| JP6604202B2 (en) | 2019-11-13 |
| WO2016047321A1 (en) | 2016-03-31 |
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