WO2014002203A1 - 粘着剤組成物及びそれを用いた粘着テープ - Google Patents
粘着剤組成物及びそれを用いた粘着テープ Download PDFInfo
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- WO2014002203A1 WO2014002203A1 PCT/JP2012/066334 JP2012066334W WO2014002203A1 WO 2014002203 A1 WO2014002203 A1 WO 2014002203A1 JP 2012066334 W JP2012066334 W JP 2012066334W WO 2014002203 A1 WO2014002203 A1 WO 2014002203A1
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- pressure
- sensitive adhesive
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- adhesive composition
- adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
Definitions
- the present invention relates to an adhesive composition excellent in various properties such as waterproofness, load resistance, processability, impact resistance, artificial sebum, artificial sweat oil resistance, and an adhesive tape using the same.
- Patent Document 1 describes a double-sided pressure-sensitive adhesive tape in which an acrylic pressure-sensitive adhesive layer mainly composed of an acrylic polymer is provided on both surfaces of a foam base material.
- Patent Document 2 describes a double-sided pressure-sensitive adhesive tape for fixing a cellular phone lens, in which an acrylic pressure-sensitive adhesive layer mainly composed of an acrylic polymer is provided on both surfaces of a black colored foam base material. ing.
- Patent Document 3 discloses an acrylic copolymer having, as monomer components, a (meth) acrylate having 4 to 12 carbon atoms and a carboxyl group on both surfaces of a foam substrate, and a polymerized rosin ester-based tackifying resin.
- the double-sided adhesive tape which has an adhesive layer which consists of an acrylic adhesive composition containing these is described.
- Patent Document 4 discloses a waterproof double-sided pressure-sensitive adhesive tape used for fixing parts of portable electronic devices, and a pressure-sensitive adhesive layer containing an acrylic copolymer and a tackifying resin is provided on both surfaces of a foam base material. A double-sided adhesive tape is described.
- Patent Document 5 describes a double-sided pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer containing an acrylic copolymer and a tackifier resin is provided on both surfaces of a base material made of polyethylene foam.
- JP 2011-122166 A Japanese Patent No. 4842358 JP 2010-260880 A Japanese Patent No. 4623198 JP 2009-084367 A
- the present invention is based on the above-mentioned pressure-sensitive adhesive in view of the need for sufficient waterproof properties and load-bearing characteristics even with a narrow-width pressure-sensitive adhesive tape with the recent downsizing, thinning, and enlargement of products. It is a further improvement over the prior art relating to tape.
- an object of the present invention is to provide an adhesive composition excellent in various properties such as waterproofness, load resistance, processability, impact resistance, artificial sebum, artificial sweat oil resistance, and an adhesive tape using the same. There is to do.
- the present invention relates to (meth) acrylic acid alkyl ester (A1) having an alkyl group having 4 to 12 carbon atoms, 50 to 90% by mass, Carboxyl group-containing monomer (A2) 3 to 20% by mass, 3 to 20% by mass of a hydroxyl group-containing monomer (A3), and (Meth) acrylic acid alkyl ester (A4) having an alkyl group having 1 to 3 carbon atoms 3 to 15% by mass
- this invention is a single-sided or double-sided adhesive tape which has the adhesive layer formed from the adhesive composition of this invention in the single side
- the pressure-sensitive adhesive composition of the present invention is excellent in waterproofness despite containing a relatively large amount of water-absorbing components, and further, such as load resistance, workability, impact resistance, artificial sebum, artificial sweat oil, and the like. Various characteristics are also excellent. And since the single-sided or double-sided adhesive tape of this invention is excellent in said each characteristic, it can be utilized for various uses in the field
- the pressure-sensitive adhesive composition of the present invention is a composition containing an acrylic copolymer (A) and a crosslinking agent (B).
- the acrylic copolymer (A) includes (meth) acrylic acid alkyl ester (A1), carboxyl group-containing monomer (A2), hydroxyl group-containing monomer (A3), and (meth) acrylic acid alkyl ester (A4) described below. Is an acrylic polymer having a hydroxyl group and a carboxyl group.
- (Meth) acrylic acid alkyl ester (A1) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate may be mentioned.
- carboxyl group-containing monomer (A2) examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, 2-carboxy- Examples include 1-hexene and 2-carboxy-1-heptene.
- the carboxyl group-containing monomer (A2) is a component for improving waterproofness and load resistance. When the content of the carboxyl group-containing monomer (A2) is lower than the range of the present invention, sufficient waterproofness and load resistance cannot be obtained.
- hydroxyl group-containing monomer (A3) examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- (Meth) acrylic acid alkyl ester (A4) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Of these, methyl (meth) acrylate is preferred.
- the content of the component (A1) is 50 to 90% by mass (preferably 50 to 80% by mass), and the component (A2)
- the content is 3 to 20% by mass (preferably 3 to 12% by mass), and the content of component (A3) is 3 to 20% by mass (preferably 3 to 18% by mass).
- the content of the component (A4) is 3 to 15% by mass (preferably 3 to 12% by mass).
- the total content of the component (A2) and the component (A3) is preferably 13% by mass or more.
- the acrylic copolymer (A) can be obtained by copolymerizing at least the components (A1) to (A4) described above.
- the polymerization method is not particularly limited, but radical solution polymerization is preferable from the viewpoint of easy polymer design.
- an acrylic syrup composed of the acrylic copolymer (A) and its monomer may be prepared first, and the acrylic syrup may be blended with a crosslinking agent (B) and an additional photopolymerization initiator for polymerization.
- monomers other than the components (A1) to (A4) may be copolymerized within a range not impairing the effects of the present invention.
- the weight average molecular weight of the acrylic copolymer (A) is 700,000 to 2,000,000, preferably 700 to 1,500,000.
- the lower limit of these ranges is significant in terms of load resistance and workability.
- the upper limit is significant in terms of the coating properties of the pressure-sensitive adhesive composition.
- This weight average molecular weight is a value measured by the GPC method.
- the theoretical Tg of the acrylic copolymer (A) is ⁇ 40 ° C. or lower, preferably ⁇ 50 ° C. to ⁇ 75 ° C. This theoretical Tg is a value calculated by the formula of FOX.
- the acrylic copolymer (A) described above is used as a resin component, but other types of resin components can be used in combination as long as the effects of the present invention are not impaired.
- the crosslinking agent (B) used in the present invention is a compound that is blended to react with the acrylic copolymer (A) to form a crosslinked structure.
- a compound capable of reacting with a carboxyl group and / or a hydroxyl group of the acrylic copolymer (A) is preferred.
- the amount of the crosslinking agent (B) is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the acrylic copolymer (A).
- the crosslinking agent (B) preferably contains an isocyanate crosslinking agent (B1) or an epoxy crosslinking agent (B2), or both.
- the isocyanate-based crosslinking agent (B1) include tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and modified prepolymers thereof. Two or more of these may be used in combination.
- the blending amount of the isocyanate-based crosslinking agent (B1) is preferably 0.02 to 1 part by mass, more preferably 0.05 to 0.2 part by mass with respect to 100 parts by mass of the acrylic copolymer (A). .
- the epoxy-based crosslinking agent (B2) examples include N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, etc. And compounds having two or more epoxy groups. Two or more of these may be used in combination.
- the compounding amount of the epoxy-based crosslinking agent (B2) is preferably 0.001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). It is.
- the pressure-sensitive adhesive composition of the present invention may further contain a light-shielding filler or a pigment.
- a light-shielding filler include carbon black, carbon nanotube, and black inorganic filler.
- Specific examples of the pigment include carbon black, aniline black, acetylene black, ketjen black and the like.
- the pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention on one or both sides of a substrate.
- the thickness of the pressure-sensitive adhesive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 100 ⁇ m.
- the pressure-sensitive adhesive layer can be formed by crosslinking reaction of the pressure-sensitive adhesive composition of the present invention.
- the pressure-sensitive adhesive composition can be applied on a substrate and subjected to a crosslinking reaction by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the substrate.
- the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to a crosslinking reaction by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer, and this pressure-sensitive adhesive layer is bonded to one or both sides of the substrate. You can also.
- a coating device such as a roll coater, a die coater or a lip coater can be used.
- the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
- the base material of the adhesive tape include foam (for example, polyethylene foam, polypropylene foam, polyurethane foam), plastic film, optical film (for example, film light guide plate, antireflection film, conductive film, wide viewing angle). Film, retardation film, polarizing plate).
- foam for example, polyethylene foam, polypropylene foam, polyurethane foam
- plastic film for example, polyethylene foam, polypropylene foam, polyurethane foam
- optical film for example, film light guide plate, antireflection film, conductive film, wide viewing angle.
- Film, retardation film, polarizing plate for example, retardation film, polarizing plate.
- a foam is preferable and a foam having a skin layer on both sides is more preferable.
- This foam is preferably a tape-like material having a thickness of 0.05 to 2.0 mm.
- the thickness of the skin layer is preferably 0.5% to 15% with respect to the total thickness of the foam.
- part means parts by mass
- % means mass%
- This pressure-sensitive adhesive composition was applied on a silicone-treated release paper so that the thickness after drying was 0.05 mm. Next, the solvent was removed and dried at 120 ° C. and a crosslinking reaction was performed to form an adhesive layer.
- This pressure-sensitive adhesive layer was bonded to both sides of a PE foam (0.2 mm thickness) having a skin layer of about 0.005 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
- ⁇ Production Example 18 (Preparation of acrylic syrup)> In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, UV lamp and nitrogen gas inlet, components (A1) to (A4) in the amounts (%) shown in Table 1 and n-dodecyl mercaptan as a chain transfer agent An acrylic syrup was prepared by adding 0.01 part and 0.01 part of a photopolymerization initiator (trade name DAROCURE 1173, manufactured by BASF Japan Ltd.) and irradiating with UV light in a nitrogen atmosphere. The acrylic polymer concentration in the acrylic syrup was about 13%, and the weight average molecular weight was about 1.5 million.
- a photopolymerization initiator trade name DAROCURE 1173
- Example 14 (Production of adhesive tape)> To 100 parts of the acrylic syrup obtained in Production Example 18, hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent (B), 0.08 part, additional light 0.5 part of a polymerization initiator (BASF Japan, trade name Darocur 1173) was added and stirred uniformly. Air bubbles mixed during stirring and mixing were removed by a defoaming operation to prepare a UV curable pressure-sensitive adhesive composition.
- a polymerization initiator BASF Japan, trade name Darocur 1173
- the UV curable pressure-sensitive adhesive composition was applied on a 0.05 m thick polyethylene terephthalate (PET) film whose surface was treated with a release agent so that the thickness after curing was 0.05 mm.
- the top was covered with a 50 ⁇ m thick PET film and irradiated with ultraviolet rays to form an adhesive layer.
- This pressure-sensitive adhesive layer was bonded to both sides of a PE foam (0.2 mm thickness) having a skin layer of about 0.005 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
- Example 15 (Production of adhesive tape)> The pressure-sensitive adhesive composition described in Example 1 was bonded to both sides of a PP foam (2.0 mm thickness) having a skin layer of about 0.20 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
- Example 1 (Preparation of adhesive tape)> The pressure-sensitive adhesive composition described in Example 1 was bonded to both sides of a PE foam having no skin layer on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
- Example 2 (Preparation of adhesive tape)> The pressure-sensitive adhesive composition described in Example 1 was bonded to both surfaces of a urethane foam foam having no skin layer on both surfaces. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
- the adhesive tape is cut into a frame of 40 mm ⁇ 50 mm with a width of 5 mm, one release paper is peeled off and bonded to a 2.0 mm thick glass plate, and the other release paper is peeled off to a 2.0 mm thickness.
- a glass plate was bonded.
- This sample was subjected to pressure treatment (0.5 Mpa) for 1 hour at 23 ° C. using an autoclave, and then submerged temporarily based on JIS IPX7 (waterproof standard). evaluated.
- this sample was subjected to pressure treatment (0.1 Mpa, 0.25 Mpa, 0.5 Mpa) for 1 hour at 23 ° C. using an autoclave, and then underwater at a depth of 10 cm based on JIS IPX8 (waterproof standard).
- the water resistance was evaluated according to the following criteria. “ ⁇ ”: Water did not enter the frame. “ ⁇ ”: Water entered the frame.
- the adhesive tape is cut into a frame of 40 mm ⁇ 50 mm with a width of 5 mm, one release paper is peeled off and bonded to a 2.0 mm thick glass plate, and the other release paper is peeled off to a 2.0 mm thickness. A glass plate was bonded. And the pressurization process of 23 degreeC, 0.5 Mpa, and 1 hour was performed using the autoclave. This sample was immersed in artificial sebum (33.3% triolein, 20.0% oleic acid, 13.3% squalene, 33.4% myristyl octadodecylate) or artificial sweat oil for 1 hour.
- the adhesive tape was cut into a size of 25 mm ⁇ 25 mm, and one release paper was peeled off. Then, as shown in FIG. 1, the adhesive tape 1 (base material 1 a, adhesive layer 1 b) was bonded to the hook 2, and then the other release paper was peeled off and bonded to the adherend 3.
- adherend 3 SUS304, a polycarbonate plate, an acrylic plate, an EGI steel plate, a galvalume steel plate, and a glass plate were used.
- a load of 1 kgf (weight 4) was applied to the hook 2, held at 85 ° C. for 60 minutes, and load resistance was evaluated according to the following criteria. “ ⁇ ”: The hook 2 did not fall for 60 minutes.
- "X” The hook 2 fell within 60 minutes.
- the adhesive tape was left for 1 day in an atmosphere of 65 ° C. and 80% Rh with the adhesive tape being chopped into 10 pieces having a size of 5 mm ⁇ 125 mm. And it peeled with the release paper in the 180 degree direction for every one, the adhesion with the adjacent part was confirmed visually, and the workability was evaluated on the following references
- the thickness of the skin layer of the foam as a base material was measured with a 175-fold microscope.
- the adhesive tape was cut into a size of 25 mm ⁇ 25 mm, and one release paper was peeled off. Then, as shown in FIG. 2, the adhesive tape 1 (base material 1 a, adhesive layer 1 b) was bonded to the hook 2, and then the other release paper was peeled off and bonded to the adherend 3. The hook 2 was pulled upward at a speed of 50 mm / min, and the strength [N / cm 2 ] when the foam was cut was measured.
- the pressure-sensitive adhesive tape of each Example in which the pressure-sensitive adhesive composition of the present invention was coated on both sides of a foam having skin layers on both sides is waterproof, load-resistant, It was excellent in various properties such as processability, impact resistance, artificial sebum resistance, and artificial sweat oil resistance.
Abstract
Description
カルボキシル基含有モノマー(A2)3~20質量%、
水酸基含有モノマー(A3)3~20質量%、及び、
炭素原子数1~3のアルキル基を有する(メタ)アクリル酸アルキルエステル(A4)3~15質量%
を構成成分として含み、重量平均分子量が70万~200万、理論Tgが-40℃以下である、ヒドロキシル基及びカルボキシル基を有するアクリル系共重合体(A)と、
架橋剤(B)と
を含有する粘着剤組成物である。
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応装置に、表1に示す量(%)の成分(A1)~(A4)と、酢酸エチル、連鎖移動剤としてn-ドデカンチオール及びラジカル重合開始剤としてラウリルパーオキサイド0.1部を仕込んだ。反応装置内に窒素ガスを封入し、攪拌しながら窒素ガス気流下で68℃、3時間、その後78℃、3時間で重合反応させた。その後、室温まで冷却し、酢酸エチルを添加した。これにより、固形分濃度30%のアクリル系共重合体(A)を得た。
表2に示す通り、製造例1~17で得たアクリル系共重合体(A)の固形分100部に対して、架橋剤(B)としてイソシアネート系架橋剤(B1)又はエポキシ系架橋剤(B2)を加えて混合し、粘着剤組成物を調製した。
攪拌機、温度計、還流冷却器、UVランプ及び窒素ガス導入口を備えた反応容器に、表1に示す量(%)の成分(A1)~(A4)と、連鎖移動剤としてn-ドデシルメルカプタン0.01部及び光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)0.01部を添加し、窒素雰囲気下でUV光を照射してアクリルシロップを調製した。アクリルシロップ中のアクリルポリマー濃度は約13%、重量平均分子量は約150万であった。
製造例18で得たアクリルシロップ100部に対して、架橋剤(B)としてヘキサンジオールジアクリレート(新中村化学工業社製、商品名NKエステルA-HD-N)0.08部、追加の光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)0.5部を添加して均一に撹拌した。撹拌混合時に混入した空気泡を脱泡操作により除去して、UV硬化型粘着剤組成物を調製した。
実施例1に記載の粘着剤組成物を、両面に約0.20mm厚のスキン層を有するPP発泡体(2.0mm厚)の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。
実施例1に記載の粘着剤組成物を、両面にスキン層を有しないPE発泡体の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。
実施例1に記載の粘着剤組成物を、両面にスキン層を有しないウレタンフォーム発泡体の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。
「2-EHA」:2-エチルヘキシルアクリレート、
「BA」:n-ブチルアクリレート、
「MA」:メチルアクリレート、
「AA」:アクリル酸、
「2-HEA」:2-ヒドロキシエチルアクリレート。
各実施例及び比較例で得た粘着テープを、以下の方法で評価した。結果を表3~5に示す。
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して2.0mm厚のガラス板に貼り合せ、更にもう一方の離型紙を剥離して2.0mm厚のガラス板を貼り合せた。このサンプルに対して、オートクレーブを用いて23℃で1時間の加圧処理(0.5Mpa)を行い、その後JIS IPX7(防水規格)に基づき一時的に水没させて、以下の基準で防水性を評価した。また、このサンプルに対して、オートクレーブを用いて23℃で1時間の加圧処理(0.1Mpa、0.25Mpa、0.5Mpa)を行い、その後JIS IPX8(防水規格)に基づき水深10cmの水中に沈め、以下の基準で防水性を評価した。
「○」:枠内に水が浸入しなかった。
「×」:枠内に水が浸入した。
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して2.0mm厚のガラス板に貼り合せ、更にもう一方の離型紙を剥離して2.0mm厚のガラス板を貼り合せた。そして、オートクレーブを用いて23℃、0.5Mpa、1時間の加圧処理を行った。このサンプルを、人工皮脂(トリオレイン33.3%、オレイン酸20.0%、スクワレン13.3%、ミリスチルオクタドデシレート33.4%)又は人工汗油に1時間浸漬した。その後サンプルを取り出し、85℃、85%Rhの雰囲気下で72時間静置し、その後通常の雰囲気下に240時間放置した。そのサンプルを目視観察し、以下の基準で耐人工皮脂・人工肝油性を評価した。
「○」:テープの剥れ無し。
「×」:テープの剥れ有り。
粘着テープを25mm×25mmのサイズに裁断し、一方の離型紙を剥離した。そして図1示すように、フック2に粘着テープ1(基材1a、粘着層1b)を貼り合せ、次いでもう一方の離型紙を剥離し、被着体3に貼り合せた。この被着体3としては、SUS304、ポリカーボネート板、アクリル板、EGI鋼板、ガルバリウム鋼板、ガラス板を用いた。そしてフック2に1kgfの荷重(錘4)をかけ、85℃で60分間保持し、以下の基準で耐荷重性を評価した。
「○」:60分間フック2は落下しなかった。
「×」:60分以内にフック2が落下した。
粘着テープを5mm×125mmのサイズで10本に細断した状態のまま、65℃、80%Rh雰囲気下に1日放置した。そして1本毎に180°方向に離型紙ごと剥離し、隣接した部分との癒着を目視にて確認し、以下の基準で加工性を評価した。
「○」:隣接した部分との癒着がほとんど無く、隣接部分を剥すことなく剥離できた。
「×」:隣接した部分に著しい癒着があり、隣接部分が同時に剥れてしまった。
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して、4mm厚のポリカーボネート板に貼り合せ、更にもう一方の剥離紙を剥離し、4mm厚のアクリル板に貼り合せ、20分間養生した。このサンプルを23℃、50%Rh下で、デュポン式衝撃試験機にて300gの錘を高さ600mmから落下させ、テープが剥離した時の落下させた回数を測定し、以下の基準で耐衝撃性を評価した。
「○」:テープが剥離した時に錘を落下させた回数が5回以上。
「×」:テープが剥離した時に錘を落下させた回数が5回未満。
175倍のマイクロスコープにて、基材である発泡体のスキン層の厚さを測定した。
粘着テープを25mm×25mmにサイズに裁断し、一方の離型紙を剥離した。そして図2示すように、フック2に粘着テープ1(基材1a、粘着層1b)を貼り合せ、次いでもう一方の離型紙を剥離し、被着体3に貼り合せた。そしてフック2を上方向に50mm/minの速度で引張り、発泡体が切れた時の強度[N/cm2]を測定した。
1a 基材
1b 粘着層
2 フック
3 被着体
4 錘
Claims (8)
- 炭素原子数が4~12のアルキル基を有する(メタ)アクリル酸アルキルエステル(A1)50~90質量%、
カルボキシル基含有モノマー(A2)3~20質量%、
水酸基含有モノマー(A3)3~20質量%、及び、
炭素原子数1~3のアルキル基を有する(メタ)アクリル酸アルキルエステル(A4)3~15質量%
を構成成分として含み、重量平均分子量が70万~200万、理論Tgが-40℃以下である、ヒドロキシル基及びカルボキシル基を有するアクリル系共重合体(A)と、
架橋剤(B)と
を含有する粘着剤組成物。 - カルボキシル基含有モノマー(A2)と水酸基含有モノマー(A3)の合計含有量が13質量%以上である請求項1記載の粘着剤組成物。
- 架橋剤(B)が、少なくともイソシアネート系架橋剤(B1)を含む請求項1記載の粘着剤組成物。
- 架橋剤(B)が、少なくともエポキシ系架橋剤(B2)を含む請求項1記載の粘着剤組成物。
- 遮光性フィラー又は顔料を含む請求項1記載の粘着剤組成物。
- 基材の片面又は両面に、請求項1記載の粘着剤組成物から形成された粘着剤層を有する片面又は両面粘着テープ。
- 粘着剤層の厚さが5~100μmである請求項6記載の片面又は両面粘着テープ。
- 基材が、両面にスキン層を有する発泡体であり、該スキン層の厚さは発泡体の全体厚に対して0.5%~15%であり、かつ該発泡体の厚さ方向の割裂力が15N/cm2以上である請求項6記載の片面又は両面粘着テープ。
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WO2016084123A1 (ja) * | 2014-11-25 | 2016-06-02 | 株式会社寺岡製作所 | 粘着剤組成物及び粘着テープ |
JP2016125026A (ja) * | 2015-01-07 | 2016-07-11 | 日東電工株式会社 | 粘着テープ |
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